TW200843852A - Functional surface catalyst composition - Google Patents

Abstract

A catalyst composition, useful for a diversity of chemical production processes, preferably comprises a glass substrate, with one or more functional surface active constituents integrated on and/or in the substrate surface. A substantially nonporous substrate has (i) a total surface area between about 0.01 m<SP>2</SP>/g and 10 m<SP>2</SP>/g; and (ii) a predetermined isoelectric point (IEP) obtained in a pH range greater than 0, preferably greater than or equal to 4.5, or more preferably greater than or equal to 6.0, but less than or equal to 14. At least one catalytically-active region may be contiguous or discontiguous and has a mean thickness less than or equal to about 30 nm, preferably less than or equal to 20 nm and more preferably less than or equal to 10 nm. Preferably, the substrate is a glass composition having a SARCNa less than or equal to about 0.5.

Description

200843852 IX. Description of the invention: [Technical field to which the invention pertains] In the invention, the invention, the catalyst composition and the preparation method thereof, the catalyst group 2: used in various chemical manufacturing methods and various emission control methods. More specifically: 'The present invention relates to a catalyst composition which preferably comprises glass two: one or more lyophilized surface active ingredients are integrated on the surface of the carbene and/or in the surface of the substrate. [Prior Art] As a catalyst, the compound is used to promote the class-like (four) catalytic reaction or catalysis, + reaction, and the catalysis is important for the effective operation of various chemical processes.卩, 邛 工业 industrial reaction and almost all biological reactions, if not catalytic reaction, 疋 involved in the catalytic reaction before or after the reaction. Just for the United States. 2: The value of a product produced at a certain stage including a catalytic process is close to - US$ (USD). Products produced using catalyst compositions include: foods, clothing, pharmaceuticals, household chemicals, specialty or fine chemicals, plastics, detergents, fuels and lubricants. Catalyst compositions can also be used to treat emissions (such as vehicle exhaust emissions, refinery emissions, utility plant emissions, etc.) and other process emissions streams to reduce potential negative impacts on health or the environment. The content of harmful ingredients. In terms of market sales, the sales of the solid-loaded catalyst for heterogeneous catalytic reactions in the full = market is about $3 billion per year. The solid-loaded catalyst is usually divided into three parts: a petroleum refining catalyst, a chemical processing catalyst, and an emission control catalyst. The market for the sale of the sensor is basically three-thirds of the world. For example, in the year of 1999, in the $1,800 million solid catalyst market of the United States, petroleum refining, chemical processing and emission control catalysts accounted for 37%, 34% and 29% of the market. Take the petroleum refining catalyst market (about $100 million in 1990) as an example. %% of the revenue comes from the Fluid Media Act (FCC) catalyst, while 31.5%, 65% and 45% yield From the hydrotreating catalyst, hydrogenation cracking catalyst and reforming catalyst. From a chemical mechanism point of view, the catalyst generally increases the rate at which a chemical reaction strikes a balance between the reactants and the product without substantially eliminating itself. Therefore, for any relevant reaction, the catalyst does not change the equilibrium state between the reactants and the product, but the catalyst can accelerate the rate of the chemical reaction if properly and/or selected. / / For a variety of purposes, the catalyst is used in a wide range of commercial practical systems / etc. The objectives include the reactivity, selectivity and energy efficiency of the Tynan process and ^ he:! . For example, according to the specified process conditions, the desired reaction rate or reaction @ can be produced to shorten the treatment time, in order to obtain higher product production capacity (for example, increase per unit hour): Or illusory. Therefore, the catalytic activity refers to the ability of the catalyst composition (4) to effectively convert the reactants into the desired product. The same product 20 should be remotely selected to improve the possible reaction products. Need = dichotomous rate · Among these possible reaction products, some products are required for J-sub-b and non-i. Therefore, the step of treatment (4) is corresponding to the removal or conversion of the catalyst. The m-catalyst composition converts the -part of the reactants into the specific &product; the ability to convert to a specific product. In addition, the % of the catalyst can be used in the composition or product of a certain gentleman's juice. ^Converting and reducing contaminants or undesired reactants. Another use is to maintain or improve product production 126422.doc 200843852 while increasing the overall energy-generating capacity and/or reaction selectivity of the reaction process. Scope Differences, ^ For example, but not limited to, catalysts can be used to reduce the content of substances such as menstruation, osmium oxide (C〇), nitrogen oxides (N〇x) and sulfur oxidation (S〇X). These contaminants may be present in the series of processes (eg, gasoline or diesel combustion exhausts of vehicles, classified petroleum refining: coal-fired processes, etc.). The same, T, the catalyst can be used for hydrocarbon treatment.

The Spear King's process is used for different sources of Xu Kezhen's current day (such as straight-running petroleum remnants, recycled petroleum distillates, heavy oils, or lunar rocks, natural gas, and materials containing catalytically reactive materials). The hydrocarbon process of the direct-issued ten anti-matter of the stone has been transformed or upgraded. The catalytic reaction is usually divided into two different types of 夂, which are homogeneous catalysis and heterogeneous catalysis. Homogeneous catalysis broadly describes a catalytic reaction in which a reactant and a catalyst are mixed in a solution phase. Although gas phase catalytic reactions have been used in some cases, homogeneous catalysis is typically a liquid phase (IV). Therefore, concentration gradients and migration of reactants to the catalyst can become important factors in controlling homogeneous catalytic reactions. In addition, 'in some cases' the "solution phase" catalytic reaction can occur across the interface between the two liquid phases, not forming a true solution, but forming an emulsified phase. Some general classes of homogeneous catalysis include acid-base catalysis, organic metals Catalysis, phase transfer catalysis, etc. On the other hand, heterogeneous catalysis describes a type of catalytic reaction as follows: In the reaction, the reactants in the gas phase or the liquid phase are exposed to a substantially solid or semi-solid phase catalyst. Therefore, in the heterogeneous catalysis process, the catalyst and reactants produced a mixed solid-liquid phase or solid phase gas phase reaction. Heterogeneous catalysis has many #^ compared with homogeneous catalysis. y V stations, such as solid catalysts, generally (a) are less corrosive and therefore have lower safety and environmental risks than many white, hexa-/night/night catalysts, and (b) provide a wider range Sound, the current economically feasible temperature and pressure conditions of the country 1 and the (c) are more able to control the exothermic chemical reactions and endothermic chemical reactions that are more intense. Right temporary ^^ A single-Berry transfer limit, which in turn significantly reduces the end-of-life effectiveness of the catalyst. In the case of a typical bismuth (2), a solid catalyst (sometimes referred to as a catalyst particle) is included on a porous material having a high internal surface area. One or more catalytic components (such as 'precious metals, such as her (four), turn (four), nail (four), sister (Re), etc.), within the surface area of the catalytic component, usually on the order of hundreds of square meters per gram. The catalyst composition or catalyst particles comprise a special porous support having a large internal surface area 'catalytic reaction occurring on the porous support." and such a catalyst structure often produces mass transfer limitations, In turn, the effective performance of the calcium M2 low catalyst particles on the activity and selectivity of the catalyst is reduced, and other catalyst performance problems are caused. In a more representative catalyst structure, the reactants must diffuse through the network of pores. Arriving at the inner zone i of the catalyst particles, and the product must be retracted to 'exit the inner region of the catalyst particles. Because of itb, the conventional hole of the catalyst group is different from other @素Balance, that is, depends on the trade-off between the conventional catalyst composition &gt; + # M k characteristics, that is, the surface area of the catalyst and the energy that promotes the mass transfer between the AA 4- &amp; ..., Yueli For example, many catalytic components are present in typical cases; in the carrier with a fine and complex pore structure (by &quot;:,,, U pores, 纟α, ie, &lt; 2 nanometer average maximum diameter) to increase the catalyst 126422.doc 200843852;: surface area. This surface area will generally increase the catalytic activity. Due to the increased activity of the catalyst due to the surface area of the catalyst particles, it is often The problem is caused by the problem of mass transfer resistance (i.e., prevention of reactants and products = movement of the catalyst particles), especially when the carrier comprises a higher percentage of pores. By increasing the percentage of larger pores (e.g., &gt; 50 large pores) in the carrier, 彳 reduces the resistance to mass transfer (i.e., accelerates the transfer of the amount of f). However, this solution tends to reduce the physical strength and durability of the catalyst particles. In other words, from the viewpoint of mechanics, the robustness of the catalyst particles is lowered. At the same time, if the reactants are subjected to a significant mass transfer resistance in the pore structure of the catalyst particles, a concentration gradient will exist under the reaction conditions. Because in the pores, the concentration of the &amp; reactant is the largest around the catalyst particles and the smallest at the center of the catalyst particles. On the other hand, the concentration of the reaction product is higher in the center of the catalyst particles than in the vicinity of the catalyst particles. These concentration gradients provide a driving force for mass transfer. The larger the cut/then gradient, the lower the rate of catalytic reaction. Such a cool wood, the effective properties of the catalyst particles (such as reactivity, selectivity, regeneration)

The life cycle and anti-coking properties between Atr and Dansheng Lai are also reduced accordingly. In general, the purpose of developing a catalyst composition is to improve the processing target of one of the above-mentioned types of guest wire from the commercial point of view. In some cases, factors affecting the performance of the catalyst. One is its ability to promote rapid and efficient reaction between reactants. Therefore, catalyst compositions with lower diffusion limits are often required. However, in other cases, a better product is obtained for the production of a specific product. The selectivity may be π 茺. Thus, it is possible to use 126422.doc •10-200843852 for the additional process and related processing equipment for removing or converting undesired reaction products. For example, 'In 1976, γ·Τ· Shah et al. propose the use of acid leached aluminoborosilicate fibers, in particular E-glass (more specifically, E-621) to produce a catalyst carrier which is compared to conventional catalysts. Has a high surface area to volume ratio, which in turn reduces the catalytic conversion for automotive exhaust systems to &amp; inch (eg, 参xidati〇no/ an Aut〇m〇bile Exhaust f GaS Mlxture by Fiber Catalysts, Ind . Eng. Chem.? Prod.

Res. Dev., pp. 29-35, Vol. 15, No. 1, 1976). At the same time, Shah et al. believe that 'reactive gases (such as carbon monoxide, carbon dioxide, nitrogen oxides, methane, ethane, propane, ethylene, propylene, acetylene, benzene, toluene, etc.) are generally easily accessible in automotive exhaust mixtures. The large surface area produced in acid leached E-glass.

Shah et al. showed a relatively small amount of fiber with a relatively small surface area (75 μm 2 /g) compared to two conventional catalysts (platinum supported on alumina beads or platinum supported on silica beads). The performance of the bismuth-type glass catalyst carrier is better than that of the alumina-supported or cerium oxide-supported catalyst (1 m/g and 317 m2/g, respectively), and the average pore diameter of the e-type glass catalyst It is larger than the catalyst supported by alumina or the catalyst supported by cerium oxide. Despite this, Shah et al. did not propose or suggest that effective vehicle exhaust oxidation can occur at surface areas of less than 75 m2/g. Nearly 25 years later, Kiwi-Minsker et al. studied the reduction of surface area in another acid-impregnated aluminum borosilicate type E glass fiber (EGF) in 1999, relative to the selective liquid phase used in benzene. Hydrogenated die-cut glass fiber 126422.doc -11 - 200843852 (SGF) for the formation of benzyl alcohol (using a platinum-based catalyst) or toluene (using a catalyst based on I bar) (see for example Flush

Catalysts for Novel Multi-phase Reactor Design^ Chem.

Eng. Sci. pp. 4785-4790, Vol. 54, 1999). In this study, Kiwi-Minsker et al. found that SGF could not obtain an increased surface area from acid leaching', so relative to the EGF sample used to carry palladium as a catalytic component of a palladium-based catalyst composition ( The surface area is 15 mVg &amp; 75 m / g) The surface area of the SGF is kept at a low level of 2 m2/g. However, κϋ Minsker et al. noted that the SGF/catalyst has substantially the same effective surface area concentration as its EGF/palladium catalyst counterpart (ie, about 〇1 mm〇i/m2) (mole metal per per The SGF/palladium catalyst composition shows a decrease in activity or reaction rate per gram of palladium compared to its EGF/palladium catalyst counterpart.

Kiwi-Minsker et al. suggest that the SGF/palladium catalyst has a reduced surface area due to reduced surface area and may be explained by the enhanced interaction of the active ingredient (ie, the catalytic component, in this case palladium) with the SGF carrier. Not because of its small surface area (ie 2 m2/g). However, they failed to verify this argument by proving the following arguments: EGF/palladium catalysts with a small surface area (ie, comparable to 2 sgf/palladium), at least with a larger surface area (ie, respectively The EGF/palladium catalyst samples for i5 and 75 m2/g) have the same catalytic activity. Therefore, KiWi-Minsker et al. proposed a limitation on the activity of SGF/palladium (ie, because SGF has higher acidity than EGF). , the interaction between palladium and sgf is enhanced) why it is the main factor, not because the surface area of SGF/pd is small, the reason is not clear. In any case, it is not 126422.doc -12- 200843852 report, relative At the 75 mVg EG bar sample, the b sample was enhanced in catalytic activity due to the diffusion rate of the ancient g EGF/I. Otherwise it shows the beneficial effect due to the smaller catalyst surface area. ..., more recently, at US 75〇60,651AEP i 247 575 A1 (Ep !5

Barelk. Et al. disclose the use of a carrier rich in dioxide dioxide (including sulphur dioxide and non-earthoxide oxides (eg, ai2〇3, b2〇3, Na 〇,

The beneficial effect of MgO, Ca〇, etc. as a catalyst carrier, wherein the 2 cerium-enriched carrier has a pseudo-layered microporous junction in the lower surface of the carrier: (see, for example, EP, 575, u, 13) , 15, 17, 18, 23, like the contents of the η segment). As a more complete description of the European Patent Office (, 〇ρ〇&quot;), in distinguishing the catalytic carrier (&quot;Kiwi-Minsker carrier) disclosed by EP '5 75 and Kiwi-Minsker et al. in the above document, Barelk Zhai et al. assert that the carrier containing cerium oxide has a pseudo-layered microporous structure with a narrow interlayer space, while the Kiwi-Minsker carrier does not. This is more specific, a, Barelko et al. In Kiwi-Minkser et al., there is no basis for assuming that (a) a pseudo-layered microporous structure with a narrow interlayer space is formed in the Kiwi-Minsker carrier; (b) the pseudo-seated space is pseudo-separated. The layered microporous structure helps to enhance the activity of the metal applied to the carrier (see, for example, paragraphs 13, 17-18, 23 and 32 of EP '575).

Barelko et al. further clarify the carrier containing the oxidized stone by distinguishing it from the carrier proposed by Kiwi-Minsker et al. by explaining the following contents to the European Patent Office: since the f' catalytic component is highly dispersed in the active state in the carrier The dominant distribution of the catalytic components in the sub-surface layers of the support 126422.doc -13 - 200843852 in a highly dispersed active statey' (屯脉 XM edge% contains two / oxidation The carrier of ruthenium has a more active catalytic state, so the catalytic state of higher activity allows the catalytic component to withstand sintering, aggregation and self-carrier flaking and contact agents (see, for example, paragraph 11 of EP » 575). EP, 575 confirms that diffusion limitations may hinder the incorporation of cations into the interlayer space of the support and thus hinder the entry of cations into the support by chemisorption (see, for example, paragraph 17 of EP, 575). To address this diffusion limitation problem, 8 Red 6 ^〇 et al. propose (and advocate) a kind of carrier structure in which the 薄-oxygen fragments of the "thin" layer are separated to form a narrow The layer space (ie, the pseudo-layered microporous structure), the narrow interlayer space contains, a large number of "〇H groups, the protons of the 0H groups can be exchanged by cations. , thin &quot;Shi Xi _, the fragment ^ is unique to the high Q3 to the ratio, and they enter the _ step statement, with a large number of pseudo-layered micropores of the 〇H group sandwiched between the narrow interlayer spaces The structure has been confirmed by "Si NMR (nuclear magnetic resonance) and spectroscopy (infrared) spectroscopy, osmium & argon BET and titration surface area measurement. Like a κ Τ in such glass catalyst compositions / Two, many conventional catalyst tests: 35 the above identified processing problems, but in other aspects of the performance of the catalyst is not good. Therefore, the abuse # ^ # 7 Λ 4 Temple Bai Zhi catalyst is often limited In the narrower range of I know the reaction, it is required to re-limit and/or need to be large... The cycle is...the bigger it is! The expensive catalytic component (such as the pin owner) is filled in, thus significantly increasing the catalyst production and carrying out The cost of the catalytic process. Therefore, there is a need for an improved catalyst composition that reacts the same • Into process such as process responsiveness, selectivity, processing, etc. The catalyst composition is preferably efficacious and durable in terms of efficiency and requirements for the phase of the 126422.doc -14- 200843852 =,:! Sexuality, and maintain a relatively long life. ^ Shen has discovered a functional surface catalyst composition that meets the need for this wide range of catalytic reactions. SUMMARY OF THE INVENTION According to one aspect of the invention, a catalyst composition is provided comprising: - a substantially void-free substrate having an outer surface, a surface region and a subsurface region, ... - at least one a catalytic component, and - at least one catalytically active region comprising the at least one catalytic component, wherein the substantially non-porous matrix has a group of -) X i^ free Sa-a^-仏r, and combinations thereof Measured to be a total surface/product between about 0.01 μ仏 and (7) mVg; and a predetermined isoelectric point (IEP) obtained by ι〇 in a range of 1)11 greater than 〇 but less than or equal to 14; b) 忒J/ a catalytically active region may be continuous or discontinuous, and having an average thickness of 0 less than or equal to about 30 nanometers; and a catalytically effective amount of the at least one catalytic component; and C) at least one catalytically active region of the Χ7 Substantially i) on the outer surface, ii) in the surface region, iii) partially on the outer surface, and partly in the surface region, or iv) a combination of (c) (1), (ii) and (iii). 126422.doc -15 - 200843852 Based on the following embodiments and the accompanying drawings, the disclosure of which is incorporated herein by reference. [Embodiment] Definitions The terminology used herein has a hole with a "pore" indicating a depth greater than a width = a "interconnected pore," and a void representing a π closed pore" and a closed channel. Or other pores that communicate with each other. The outer surface of the material in which the pores are located does not have any "opening pores", indicating that there is a direct passage from the outer surface of the material in which the pores are located from the ul, ,, or the gap, or via another pore or interconnecting pores. The pores (ie, pores that are not part of the closed pores) ff pore width" means the distance between the specified square walls. The inner diameter of the pores determined by the method or the relative π pore volume "represents the body π porosity according to the specified side effect, but does not include the closed pores" means the porosity ratio in the material. The total effect of all pores determined by the method. The ratio of the product to the total volume of the material "micropores," means pores having an internal width of less than 2 nanometers (nm). "Mesoporosity" means pores having an internal width of between 2 nm and 5 nm. "Macropod" means a pore with an internal width greater than 5 nanometers. "Outer surface" means - the boundary or skin of the material (thickness near zero), including the outer boundary or the rule of the skin associated with the defect (if any) or not Rule wheel 126422.doc -16- 200843852 Hole wall surface buckle inner boundary or skin (thickness near zero), including any regular or irregular contours on the inner boundary or skin associated with defects, if any, The shape defining any open pores in the material having at least one or more types of pores. The coating, the body surface, and the surface area "surface area" means materials that can be changed depending on the material. The area does not include any = domain defined by the open pores of the material (if any open pores are present) but the surface area (4) is less than or equal to the outer surface of the material (four) —&lt;2G(four)'more W nanometer),·there is any opening in the material 3. The second 'filamental area (8) is less than or equal to the meter's below the surface of the hole wall of the material - better than the nanometer ^ for the External boundary: two = regardless of whether the change is regular or not, along the mean height is used to determine: 1 the average depth of the outer or inner boundary or the flat surface area of the skin. The area of the second and second zones indicates that it can be changed according to the material. The material area, but does not include any open pores from the material, but the h) is defined by any open pores. The lower area (a) is not on the outer surface of the material (preferably > 2〇) Nai Na, #杜达, Bu is greater than 30 nanometer pores, under the surface, "&gt; 0 nanometers"; in the material has any openings (four) Jiaojia is > 20 nm, more preferably > 1 nanometer) . S surface from the bottom (four) Nai: internal surface area "or" open pore wall surface area surface effect of all open pore walls in the cut. The surface area determined by the knowledge method is used to indicate the surface area effect of the surface area effect of all the holes in the specified area &amp; ^ not the coffin I26422.doc 200843852. 'Total surface area' means the sum of the surface area of the material and its external surface area determined by the specified method. The nano-chemical adsorption surface area, or S A.^ indicates the surface area of the material determined by chemical adsorption of sodium cations by chemical adsorption, The (etc.) chemisorption method is similar to GW Sears/., 1956, v〇1. 28, ρ·i98i and R·Iler, C/2(4)(6)〇/57//ca, john wiley &amp; s〇ns 1979, p, 203 and 3 53. ''Na-Chemical adsorption surface area change rate,, or, SARCW, where SARCa^V5 to "/v initial, where (1) V is initially used to initially titrate the aqueous slurry mixture of dilute NaOH The initial volume of the titration solution, at about 25t: temperature

A material that is substantially insoluble in water is included in the 3.4 M NaC1 solution, the pH of the solution reaches pH 9.0 from the initial ΡΗ 4·0 at zero time t0, and (ii) μ to &quot; is used to make the slurry mixture at 15 The total volume of the same concentration of NaOH titration solution maintained at pH 9 for 5 minutes, every 5 minutes (a total of 3 5 minutes, 1 interval, respectively, "," and ^5), the total volume is adjusted as needed as soon as possible . Thus, v* refers to the total volume of NaOH titration used in the titration procedure described in more detail below, where v is initially + V5q. Therefore, % to (a) can be expressed as the difference between v total and v initial, where v#i5=v total - ¥ initial 0. For the purposes of this definition, 30 grams of NaCl (reagent grade) is added to 15 liters of water. In a 3. 4 M NaCl solution, 1.5 grams of sample material was added to the NaCl solution to produce an aqueous slurry mixture. The aqueous slurry mixture must first be adjusted to pH 4.0. In order to make this adjustment prior to titration, a small amount of dilute acid (such as HCl) or a dilute base (such as NaOH) may be used in accordance with 126422.doc -18- 200843852. The titration, in order to obtain the v initial, first use a dilute Na0H titration solution (for example, 〇in or 〇·〇1Ν), and then use Vy&quot; for SARC heart measurement. In addition, for the purposes of this definition, Vs to "is the cumulative volume of the NaOH titrant used in, 110 and 4, wherein the NaOH titrant is titrated as quickly as possible every 5 minutes (3 3 minute intervals) to meet as needed The pH of the slurry mixture is adjusted to 9.0 from t to the final time, within 15 minutes. For the purposes of this definition, any alternative ion exchange (ΐΕχ), counter ion exchange (BIX) and/or electrostatic adsorption is used. (ΕΑ) Processing Method To determine the S arc of the sample material prior to integrating one or more 2-component precursors (described below) onto the surface of the substrate and/or within the surface of the substrate. "Incipient wetness" means Or an aqueous slurry or paste mixture of semi-solid materials at a point in time at which the isoelectric point (, ΙΕρπ) of the material is being measured. At this point, the surface of the solid or semi-solid material is covered. And to the extent that it is filled with any water-permeable pore volume that the material may have, it allows water to enter the aqueous slurry or paste mixture to provide contact between the glass electrode contact and its reference electrode and There is sufficient liquid contact between the IEP to determine the material. ', isoelectric point, or IEP means the pH value of the solid surface charge of the solid or semi-solid material at initial humidity is zero. Known as zero point charge 'ZPC' or zero charge point (PZC) 〇 ''catalytically effective amount' means sufficient to convert at least one reactant into under suitable processing conditions At least a predetermined product of the production of the foot dog to support the amount of catalytic component of the test 126422.doc -19- 200843852 factory or commercial grade process. ''Chalconide'' means a Group 16 (formerly Group VIA) element comprising at least one group consisting of sulfur (S), selenium (Se) and tellurium (Te) and at least one positively charged property. a compound that is stronger than the element or group of its corresponding Group 6 element. The shell metal" is not derived from rhodium (Rh), palladium (pd), silver (Ag), rhodium (L), platinum (Pt), and gold. The transition metal of the group (Au), unless otherwise stated, is in a charged state in the form of a metal complex, a metal ruthenium, a metal cation or a metal anion, and the various transition metals are in a zero oxidation state (while in an unreacted state). w / νπ w Γ 碘 组成 组成 组成 组成 组成 组成 组成 组成 组成 组成 组成 组成 组成 组成 贝 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又 又, new pore formation, pore size expansion, etc. However, the composition of the corrosion-resistant matrix may be u 4 ^ &gt; 匕 匕 匕 上 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲 鬲/, his strong corrosive agent (whether it is a combination of separate 戋 system μ temperature 'high pressure and / or high vibration frequency conditions), such matrix is still considered, anti-corrosion, matrix.疋Surface activity '▼ indicates one; bf* 止 "The surface of the V IT IT material is fully filled with a component state, the filling has - or a plurality of charged materials (1) promotes the catalytic reaction under steady state reaction conditions. No further steps are used to (H) additionally, by means of static and/or ion exchange interactions with one or more shells or 7 private components, for further modification = action under steady state reaction conditions As a catalytic component. And then 126422.doc -20- 200843852 "matrix" sound and glass-like ^ general or semi-solid materials, including but not limited to glass can be according to the base ~ but less than or equal to 14, the surface state of the predetermined composition The intended use in the catalytic component having a catalytic amount is changed. Sub, two::11 are interacted by electrons and/or physicochemicals (eg, clutch, two =:: valence interactions, including but not limited to chlorine bonding, ionic bonding, human 'two', Van der (Van der W-ls)/dipole bonding, affinity bonding, hydrazine bonding, and combinations thereof. The chemical composition and the matrix are combined. The following is an overview of the annotations used only to illustrate the selected aspects of the accompanying patent application. And factors, and therefore only used to facilitate the reader's potential benefits (4) in a brief wording. =, the annotations of this embodiment should not be considered as limiting the scope of the accompanying invention: one aspect of the invention relates to a catalyst composition having an average thickness of the surface active Cuihua active region of less than or equal to about 3 〇. The rice, preferably &lt; 2 m: and more preferably the lake time (10) media combination, the malignant of the present invention, the other form of the method for producing a novel catalyst composition produces a composite form of the catalyst The composition, regardless of the dimorphic medium. A further aspect of the invention relates to the use of a medium in a variety of processes, and a process such as a sigma ' δ hai, such as hydrocarbon, hydrocarbon and/or non-hydrocarbon treatment, conversion, refining and/or emission control and treatment. Process and other types of processes. For example, 'new catalyst compositions can increase smoke, hydrocarbons and/or non-hydrocarbons: 126422.doc 200843852 Conversion, refining and/or emission control and treatment processes and other types of process selectivity, reaction rate, good product Rate and energy efficiency. Several factors should be considered in the production of the catalyst composition, including but not limited to: μ匕(1) Obtaining a matrix having a predetermined isoelectric point ("ΙΕρ.", regardless of the intended use, whether obtained as it is or Obtained after subsequent processing; (ii) the degree of corrosion resistance of the substrate in view of the intended use; (ill) the degree of porosity (if any) of the substrate, and the associated elemental composition (in particular) in view of the intended use, in order to obtain the desired surface properties (on the surface), (d) depending on the intended use of the composition, where appropriate, the chemical sensitivity of the substrate to the generation of the appropriate isoelectric point, and by one or more of the first type of ion and/or electrostatic interaction with the substrate The first component is such that the substrate is surface active, and the substrate can, but does not necessarily, produce a catalytically active region having an average thickness on and/or within the surface of the substrate of &lt; about 30 nm, preferably S. 20 nm, more preferably &lt; about 1 〇 nanometer; &gt;) matrix for optional ion exchange (ΙΕχ), counter ion exchange (BIX) and/or electrostatic adsorption (ΕΑ) treatment The chemical sensitivities of the methods for integrating one or more second components onto the surface of the substrate and/or within the surface of the substrate having a second type of interaction with the matrix ions and/or germanium, and thus The catalytically active region, the average thickness of the catalytic &lt;RTI ID=0.0&gt;&gt;&gt; And 126422.doc -22- 200843852 (10) depending on the intended use of the composition, the chemical sensitivity of the treated substrate to the following reactions: optional calcination and / or reduction, oxidation or further processing The substrate chemically reacts with the first or second catalytic component prior to use of the catalyst composition. Matrix Description For many potential applications, and (4) Fan (four) detail p selection

Preferably, the substrate used to produce the catalyst composition of the present invention is a glass composition having an IEP greater than about 〇 but less than or equal to 14 regardless of whether the surface activity is received as received or treated to produce a surface active state. The availability of a matrix with a suitable IEP (suitable for the production of a catalyst composition for the intended use) depends on various factors, some of which have been outlined above (in the "executives"), given below A detailed discussion, those who are familiar with this technology will be more; Qing Chu master and selection (four) when IEp (four) other factors. For example, for a commercial process with a commercial advantage of 5 noon, the glass (or glass-like) composition and its surface active product preferably have a mass of greater than or equal to about 4. 5 but are small; one is expected to be greater than or equal to about ό. However, a glass composition of less than 14 is better, and it is expected that a glass having a ΙΕΡ greater than or equal to about 7.8 but less than 14 is the most sturdy. However, depending on the intended use of the catalyst composition and the extent and type of porosity in the matrix of the composition, the preferred range may be i~a. Additionally, certain catalytic processes have a surface for the lower pH range. The lively catalyst composition is more sensitive. Therefore, in such cases, a substrate having a P J of 7.8 (#French is α, more preferably ^4·5) is likely to be more suitable for this dressing. Therefore, it is again stated that the selection of the basement within the appropriate range of ΐΕρ not only takes into account the intended use of the catalyst composition, but also 126422.doc -23- 200843852 to combine the porosity of the matrix, the chemical composition and Processing procedures (if any), etc. In addition, depending on the intended catalytic use, many glass types can be potential matrix candidates to achieve the appropriate degree and type of IEP and porosity, whether received or used as one or more of the following treatments. Typically, 'some examples of such glass types include, but are not limited to, E glass, non-corrosive E-glass%, S-glass (V), R glass, AR glass, rare earth silicate powder, 钡_titanium-tellurate glass, nitrogen The glass is 矽_aluminum_oxygen-nitrogen glass, A glass, 〆C glass and CC glass. However, the following is a description of the types of glass that are generally expected for a range of catalytic applications and some possible treatments. Description of AR type glass For example, but not limited to, "AR type" glass is a set of non-porous glass compositions having a wide range of IEp greater than 7.8. Typically, the AR-type glass contains a significant amount of an intrinsic oxide type glass mesh modifier, typically 10 wt.% or more by weight of the total glass composition. Such basic oxide network modifiers include, but are not limited to, cerium (Zr), cerium (Hf), aluminum (A1), lanthanides and lanthanide oxides, alkaline earth metal oxides (Group 2) ), an alkali metal oxide (Group 1), and the like. A glass comprising zirconium (Zr), hafnium (Hf), aluminum (A1), a lanthanide, an alkaline earth oxide, and an alkali metal oxide is preferred, and a glass composition comprising cerium (Zr) (such as but not limited to AR) Type glass) is especially preferred. Type A glass indicates that, for example, without limitation, "Type A" glass is another broad and substantially non-porous glass composition, whether the surface active system is received as received or treated to produce a surface active state, IEP Greater than about 7. 8 but less than 14. Typically, the bismuth glass will include an acidic or basic oxide type glass mesh 126422.doc-24-200843852 modifier, including, but not limited to, (Zn), An oxide of an element such as magnesium (Mg), calcium (Ca), aluminum (A1), (B), titanium (Ti), iron (heart), sodium (Na), and potassium (K). If an alkaline mesh modifier is used, the amount included in the lower IEP glass tends to &lt;12 wt· /〇. Glass containing magnesium, #5, aluminum, rhodium, sodium and potassium is preferred. The unsalted E-glass indicates that the un-leached &quot;E-type&quot; glass is another broad and substantially non-porous glass composition, including infinite examples, whether the surface active is received or treated as it is. Producing a surface active state, IEp is greater than about 7.8 but less than 14 〇 Typically, the non-acid immersed bismuth glass will include an acidic or basic oxide type glass mesh modifier, including, for example, but not limited to Oxides of (Ζη), magnesium (Mg), calcium (Ca), sau (A1), boron (B), titanium (Ti), iron (Fe), sodium (Na) and potassium (κ). When an alkaline network modifier is used, the amount included in the unleached bismuth-type glass tends to be &lt;2. The glass containing magnesium, calcium, aluminum, zinc, sodium and potassium is preferably. Porosity indicates that the porosity of the matrix produces another relevant aspect of the catalyst composition of the present invention. Typically, the matrix should be substantially non-porous, but may actually be quantitatively insignificant, for the preparation of the catalyst composition. Micropores, mesopores and/or large pore volumes without adverse effects due to micro-materials The gap volume is often difficult to detect. This description uses two surface area measurements to determine the absence of pores on the shellfish to identify the catalyst composition of the present invention. The first surface area measurement is applied by accepting The expected surface area measured 126422.doc •25- 200843852 can be used to detect micropore, range of thermal adsorption/desorption methods for determination, medium pores and/or macroporosity. For example,

(Examples. For example, the method described in the larger surface area measurement D3663-03, may be followed by .....

Area (''SAO, can be used for some type of analytical method (R·ner in q(4)(6) π o/A/zca, John Wiley &amp; Sons (1979), pages 2, 3 and 353). Time ratio, and more specifically defined according to SA•change rate (nSARC.). Therefore, as defined herein, the matrix is substantially non-porous, provided that the matrix is SAA^m or is at about m1 m2/g to Between 1 ,,

And its SARC#a is less than or equal to 〇·5. As discussed in more detail above, the SARCw is the ratio of the two volumes of the NaOH titrant, the denominator being the volume of the initially used NaOH titration solution, i.e., initially used at zero time t. The matrix slurry mixture was titrated and the matrix slurry mixture contained 1.5 grams of substrate in a 3.4 M NaCl solution (pH 4 to pH 9) at about 25 °C. However, as noted above, prior to the initial NaOH titration to begin for the SARCw assay, the aqueous slurry mixture must first be adjusted to pH 4 with a small amount of acid (HC1) or base (NaOH), respectively. In addition, as described above, the cumulative volume of the NaOH titrant (for three 5 minute intervals, maintaining the matrix slurry mixture at pH 126422.doc -26- 200843852 9 in 15 minutes) is V total-V Initial (ie Vy ls), this is the numerator of the ratio SARC^. Therefore, if the initial value of V-V is less than or equal to 〇·5 乂, the corresponding ^汉' is less than or equal to 0.5. Thus, as defined herein, the matrix of SARC^^5 is substantially non-porous, provided that the substrate S.A^w lamp or 8·α·^_μγ is also between about 0.01 m2/g to about 10 m2/g. If the surface area parameters are satisfied, there may be insufficient concentration, distribution, and/or type of the matrix in terms of any micropores, mesopores, and/or large pore volumes, thereby achieving the intended use of the catalyst composition. Expected performance has an adverse effect. The nano surface area (S.A.-) is an empirical titration procedure developed for substantially pure cerium oxide (Si〇2) in the form of granules, powders and suspended sol forms. S.A. is a measure of the reactivity and accessibility of the surface proton position (Glass-CTH+), which corresponds to the Si-CrH+ position for pure cerium oxide. Tellurite glass and crystalline niobate and pure niobium dioxide (SiOd are significantly different in composition. For the stoichiometry of this titration procedure, the behavior of niobate glass and crystal niobate cannot be based on SA· - The absolute value of the Na0H titration solution determined in the experiment is known or predicted. Therefore, Sears and Iler used to correlate the volume of the SA·heart experiment with the js^-BET surface area of one of the oxidized stone materials of the nine The equation is not suitable for reliably predicting the absolute surface area of more complex tantalate compositions. This is expected because the Glass_yH+ groups that can be present in different compositions of glass can include, for example, A1-0-ET, Β-ΟΉ+, Τί-ΟΉ+, Mg-CrH+ and a more heterogeneous group of protons (Q2 group) combined with multiple Si-〇-H+ moieties at a single 矽 position. On the other hand, “矽like” glass compositions (eg leaching) The total surface area of quartz may be reliably determined using SA·^ experiments, provided that 126422.doc -27- 200843852 takes a small pore size within the range achievable by standard gas phase BET measurement because it is mainly connected Si〇2 and Si-〇-H+ Composition. However, Gkss Ο Η邛 is the diffusion accessibility for hydroxide ions and sodium ions, and the relative ratio of pores, macropores and/or substantially non-porous regions in multi-pores comparison should be based on NaOH The amount (in the sa heart experiment to maintain the final positive value of 9 ' must be added compared to the time) (titrant). So \ general words 'glass-〇-H+ part for 〇H- and Na+ contrast time And, as determined by the above SARC* experiments, can be used as a reasonable and reliable measure of the presence of micropores, including certain types of porosity that are not possible with standard gas phase BET measurements. Preferably, the surface area of the substrate is after its ion leaching treatment. It will remain essentially unchanged, which is common for most test (i, ar) glasses. However, in some cases, some of the ions consumed from the matrix network do not significantly affect the matrix. The microporous structure, if any, thus avoids adversely affecting the desired properties of the catalyst composition for the intended use. However, if there is significant ion consumption and associated leaching on the matrix network, it is likely to be in a certain quality. Producing micropores Region. Therefore, as described above, when sar^ is greater than about 〇.5, it indicates the presence of such a microporous structure. The bismuth, which exhibits these characteristics, has produced a sufficient microporous structure, particularly in the matrix. In the region, such a microporous structure will produce a 彳p曰 on the ability of the substrate to maintain a surface active state, thus adversely affecting the desired properties of the catalyst composition for the intended use. Matrix shape, form and size description: to produce the touch of the present invention The matrix of the media composition has a variety of shapes and shapes. Examples of suitable shapes include, but are not limited to, fibers, fibrillated fibers, 126422.doc -28-200843852 cylindrical particles (eg, pellets), spherical particles ( For example, spheres, elliptical particles (such as rounded bodies), flat particles (such as flakes), irregularly fractured particles, spiral or spiral particles, and combinations thereof. Examples of suitable shaped bodies or composites that can form such matrix shapes include, but are not limited to, woven composites, non-woven composites, mesh fabrics, extrudates, rings, saddles, cylinders, films, Cyclonic bonding membranes, filters, filaments, chopped fibers, and combinations thereof. r In some cases, depending on the intended use of the catalyst composition, any suitable material may be used as the forming medium to form a shaped body or composite (collectively "composite") with the catalytic substrate, including but not limited to soft water. Aluminite (boehmite), hydrated titanium dioxide and Ti〇2, hydrated cerium oxide and Zr〇2, cerium alumina, alpha alumina, cerium oxide, clay, natural and synthetic polymeric fibers, polymeric resins and solvents, and water soluble polymers Whether or not the matrix includes a type 1 or type 2 catalytic component (described in more detail below). Preferably, the catalytic substrate should be located or substantially in proximity to the outer surface of the composite (i.e., at the outer periphery of the composite). Without being bound by theory, it is believed that if a substantial portion of the catalytic substrate is placed on the outer surrounding region of the catalytic composite (, the periphery of the composite π) and/or within the 'will decrease, the unwanted The extent of the internal composite diffusion effect. Therefore, it should be understood that the proper distance for positioning a substantial portion of the catalytic substrate within and/or over the periphery of the composite will depend on the intended use of the catalytic composite, the overall size and shape of the catalytic composite, and the catalytic substrate. The overall size and shape. Therefore, in the shape and size of various composite materials, the average thickness of the periphery of the composite (on the periphery of the composite and / 126422.doc -29-200843852 or the catalytic substrate can be placed inside) is usually about! From micron to about 4 microns. However, the average thickness of the periphery of the composite is preferably between about meters and about 25 microns, more preferably between about 1 and about 15 microns. However, depending on the intended use of the catalyst composition, in some cases it may be desirable to have the matrix substantially distributed throughout the forming medium. For example, but not limited to, in a process requiring extended exposure of reactants and/or reaction intermediates, preferably a composite matrix (whether a ruthenium type or a type 2 catalytically active substrate) having a controlled pore size distribution over the entire forming medium Although preferred but not necessary. The minimum size of the matrix used to produce the shaped body or composite (i.e., the average largest dimension of the matrix particles) is typically between greater than about 5 microns and less than or equal to about 150 microns, preferably from about 2 microns to less than about 2 microns. Or equal to between about 15 microns, more preferably between about 0.2 microns and about 50 microns. However, depending on the intended use of the mouthpiece and other process variables that may be affected by the shape and form of the combination of catalysts, substrates outside this range may still be effective, for example, in the continuous fiber form described above, not touching The desired properties of the media composition adversely affect. The skilled person should understand that the composite operation may introduce potential large pores, mesopores and/or microporosity into the finished composite. However, during the compounding operation, as described herein, this porosity is not incorporated into the functionalized surface component of the catalyst composition. u. Matrix Surface Activation The substrate used to produce the catalyst composition of the present invention can be surface activated by one or more first components having a first species ion with the substrate and / 126422.doc -30- 200843852 Or electrostatic interaction ("1 type component before π%,,,, wind 77 months]. As described in more detail below, type 1 component precursors may have catalytic potencies themselves or may be further processed to produce catalysis. Active area, average thickness on and/or within the surface of the substrate

The degree is &lt; about 3 nanometers, preferably "the average thickness of about 2 nanometers, more preferably the average thickness of about 10 nanometers of S. For example, in the case of staying for two hours, depending on the catalyst combination The intended use of the material, if the substrate obtained has a suitable type and extent of pore structure (if any) and an isoelectric point (IEP) matrix which may have sufficient surface activity upon receipt, effective Catalytic. Although not necessary but preferred, the substrate can be treated to further modify and/or improve its surface activity. Additionally, the substrate can be treated to remove any organic coating or other material that is expected to interfere with the performance of the catalyst composition. Further, as discussed in more detail below, in the &quot;type 2 precursor precursor integration process, it may be better to use ion exchange (IEX) depending on the intended use of the catalyst composition. , a counter ion exchange (BIX) and/or electrostatic adsorption (EA) phase process for further processing the surface of the substrate, the process comprising integrating one or more second components onto and/or within the surface of the substrate, the substrate surface having Second class and matrix The ions and/or electrostatic interactions, and thus the catalytically active regions, have an average thickness on and/or within the surface of the substrate of (10) nanometers, preferably 220 nanometers, more preferably s1 nanometers. In addition to treating the composition of the substance typically found on the surface of the substrate under typical conditions and whether the substance is expected to interfere with the preparation of the catalyst composition and/or interfere with the desired performance of the intended use of the catalyst composition, For the removal of contaminants, the AR type glass is typically made of an organic coating (also 126422.doc -31 - 200843852 sizing), which is used to facilitate processing, for example in The organic coating or coating can interfere with the preparation of the catalyst composition, even if it does not interfere with the catalytic performance of the majority of the eight (right but not all) intended use of the catalyst composition. Therefore, the organic coating refractory system should be removed for a preferred method of removing such an organic coating. The main goal of this treatment is to remove the spleen, 兮汍% 马 锣 、 、, / / 木 土 贝 贝 贝 贝 贝 贝 贝 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In some cases, depending on the nature of the contaminant to be removed from the substrate, the agent, surfactant, hydrazine, cross, right main, and soil remove contaminants to achieve satisfactory results. However, depending on the degree of calcination used, it is preferred to calcine the substrate in oxidizing properties (e.g., in air or oxygen). It is also important that i choose a high calcination temperature to remove the target contaminant, but the calcination temperature is low enough to avoid the softening point of the material. Generally, the calcination temperature should be at least about 5 (rc lower than the softening point of the selected matrix material. Preferably, the calcination temperature should be at least about 1 Torr (rc) lower than the softening point of the selected matrix material. For example, in use In the case of a glass, the calcination μ of the most linear glass is acceptable to remove contaminants between about 3 GGC and about 7 GG C. Typically, the selected matrix material should be calcined for about 2 to 14 hours, preferably calcined. Mountain hour. Nevertheless, the calcination time can be varied outside of these time ranges by taking the nature of the obtained base and the nature of the target contaminant to be removed from the matrix. Surface activation is achieved by ion leaching treatment in any After the potential contaminants are substantially removed from the substrate, the substrate can be treated to produce the surface active state and the desired isoelectric point (f, iEp"), provided that the initial IEP obtained from the matrix is 126422.doc -32- 200843852 Not within the desired range. However, in some cases the received substrate may have sufficient surface activity and require further modification using one or more other treatments (described in more detail below) without using the first type of ions. Dip (ΙΕΧ-1) treatment (this will be discussed first in other treatments described in more detail below). In other words, the elemental composition of the matrix, especially on the outer surface or substantially close to the outer surface, may be sufficient to achieve the desired However, in many cases, the composition of the matrix will require some modification to change the initial ΙΕρ and obtain a suitable enthalpy, and then obtain a surface that meets the type and degree of conformation according to the intended use of the catalyst composition. Active state. The surface active state, in the case where - or a plurality of first components have (1) a first oxidation state and (π) a first type of ion and/or electrostatic interaction with a matrix, may be sufficient to generate a catalytically active region, The average thickness on and/or within the surface of the substrate is _ &lt; about 3 〇 nanometers, preferably such as tens of meters, more preferably 10 mils, and g) this provides the desired properties of the composition for the intended use of the composition. ° For example, but not limited to, 'formed' or Lewis's acid sites on the surface of and/or within the substrate can be effectively promoted by some hydrocarbons and miscellaneous sites. (eg, oxygenated hydrocarbons) and non-hydrocarbon treatment, conversion and/or refining processes. 2 and 'in other cases' based on the intended use of the catalyst composition, this may be used in a better manner - or as described below The ion exchange method is further used to further treat the surface of the substrate to achieve (1) the same or different conditions as the first or the same, and the use of the ion and/or electrostatic phase of the g J... shell with the substrate is sufficient to generate catalytic activity. Area, on the surface of the Kibe and/or 126422.doc -33 - 200843852 The car is 20 about 20 nm, and the average thickness of the 幺 is about 30 nm 1 〇奈奈. Now turn to Surface activation treatment 'surface activation treatment includes at least - leaching treatment' to obtain a first or a class of ion exchanges.] However, it should be understood that if the substrate received has an IEP suitable for the intended use of the catalyst composition, then IEX] is also used to describe the first type of matrix. Typically, the ion leaching process is performed by any suitable means, i.e., effective removal of the desired ionic species from the entire substrate surface in a manner that is substantially incompatible with the matrix network (e.g., Avoid creating any microporous structures in the surface area and/or under the surface area). For example, but not limited to, large-mouth ί5 酉夂 酉夂 , ,, 沦 无机 inorganic acid or organic acid, and various chelating 岬 are suitable for ion leaching treatment. Preferably, a mineral acid is used, for example, not limited to nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid, acetic acid, perchloric acid, odorous acid, chlorosulfonic acid, trifluoroacetic acid, and combinations thereof. Generally, the concentration of the acid solution used for the ion leaching treatment depends on the characteristics of the substrate (for example, the affinity of the ions to be removed from the glass network, the strength of the glass after removal of the network ions), and the need for the matrix. The degree of change and the pre-U35 of the catalyst composition. Preferably, the concentration of the acid solution used for the ion leaching treatment may be between about 55 wt% to about 5 wt%, more preferably between about 2.5 wt.% and about 25 Wt.%, most preferably Between about 5 corrections and about i〇%. Chelating agents can also be used in ion leaching processes such as, but not limited to, ethylenediaminetetraacetic acid (&quot;EDTA"), crown ethers, oxalates, polyamines, polycarboxylic acids, and combinations thereof. 126422.doc 34- 200843852 Typically, the concentration of the chelating agent solution used in the ion leaching process depends on the characteristics of the substrate (eg, the affinity of the ions to be removed from the glass network, the strength of the glass after removal of the network ions) and the combination of catalysts. The concentration of the chelating agent solution used for the ion leaching treatment may be between about 0.001 wt.% and saturation, more preferably between about 1 wt% and saturation. 'The heat treatment conditions for ion leaching treatment, such as heating temperature, heating time and mixing conditions, are selected depending on the type and concentration of the acid or chelating agent used and the characteristics of the substrate. Depending on the type of fee / gluten or chelating agent The heating temperature varies widely depending on the concentration. However, preferably, the heating temperature suitable for the acid ion leaching treatment is between about 2 (TC to about 20 (rc, more preferably about 4 (rc to about). Between the best at about 6 (TC to about 9 CTC The heating temperature for the chelating agent ion leaching treatment is about 2 Torr. 〇 to about 2 〇 (the range of rc, more preferably in the range of about 4 〇 ° C to about 90 ° C. Ion leaching 'more preferably at about 30 depending on the concentration of the acid solution or chelating agent solution and the heating time. The heating time of the ion leaching treatment may vary. Preferably, the heating time of the treatment is between about 15 minutes and about 48 hours to about Between 12 hours. Usually, depending on the type and concentration of the acid or chelating agent used and the nature of the substrate (for example, the affinity of the ions to be removed from the glass mesh, after removal of the mesh ions) Strength, etc.) and duration of heat treatment, such as, but not limited to, the mixing conditions can be: or broken, male, mechanical mixing, fluidization, tumbling, rolling or manual mixing. 126422. Doc -35- 200843852 In summary, the combination of acid chelating degree, heat treatment conditions and mixing conditions will be based on the degree of sufficient ion exchange (&quot;consistency) between the acid or chelating agent and the target matrix ion. OK, use The appropriate isoelectric point and the type and extent of surface charge are generated to achieve the surface active state required for the post-treatment of the substrate or the intended use of the catalyst composition. After completion of the ion leaching process, preferably in any suitable manner Isolation of the substrate by ion leaching, including but not limited to filtration, mode, centrifugation, decantation, and combinations thereof. Then 'with- or a variety of suitable cleaning solutions (eg, deionized water and/or a suitable water-soluble organic solvent, The ion-leached substrate is washed, for example, with methanol, ethanol or acetone, and dried at about room temperature to 110 c for about 20 to 24 hours. The reverse ion exchange treatment is in some cases 'depending on the composition of the catalyst. Use, perhaps the preferred way is to perform reverse ion exchange (&quot;Βΐχ&quot;) or two-step ion exchange treatment (collectively referred to herein as hydrazine treatment) on selected matrices. The hydrazine treatment is usually called (but not limited to) &quot;counter ion exchange&quot; because the ion leached substrate is mixed with a salt solution including an ion initially removed, and is transferred from the substrate by ion leaching treatment. In addition to this ion (eg Na+) then = or return to the matrix. It is not clear whether the ions removed from the base f will return to the same position originally occupied in the matrix. However, regardless of the initial replacement Whether the ions will completely or partially change position or not change k position due to BIX processing, it should be understood that the processing described in this paper is due to the possible displacement of the 4 points. All catalyst compositions. 126422.doc -36- 200843852 Generally, the type of salt solution used to treat the substrate subjected to ion leaching treatment depends on the type of ions that will undergo reverse ion exchange. Preferably, only the ions are Counter ion exchange, but in some cases, counter ion exchange of two or more ions may be required. Any ions that are easily removed by the above ion leaching process can enter. Reverse ion exchange. Some examples of the plasma include, but are not limited to, the first group (the group of the river's u) alkali metal ions, such as clocks, nano and unloading ions, and come from the second group (formerly „ Earthquake metal ions of Group A), such as wrinkles, towns, mother ions, NH4 and quaternary ammonium cations, and small organic polycations. Preferably, alkali metal ions and NH/ are preferred target ions for BIX treatment. 'Na+ and NH/ are preferred cesium ions, and Na+ is better meth. I. The concentration of the salt solution used for BIX treatment depends on the type of matrix to be mx treated by ion leaching and used for The relative affinity of the BIX ions that are returned to the ion leaching matrix is likewise independent of the site in which the Βιχ ions are returned to the matrix network (eg, the relative affinity of Na+ for matrix versus Η+). For most types of glass matrices, For example, but not limited to, AR glass, bismuth glass or quartz glass, about 1 to 5, a few concentrations of BIX _ salt solution is preferred, and about 〇〇 5 melons ... several to ~ salt solution is more Good. Typically, it will be based on The heat treatment conditions for the BIX treatment, such as the heating temperature, the heating time, and the mixing conditions, are selected for the type and concentration of the salt solution and the characteristics of the substrate. Preferably, the heating is carried out for the hydrazine treatment using the BIX-salt solution. Temperature I26422.doc 200843852 degrees, may be between about 20 ° C to about 200 ° C, more preferably between about 30 ° C to about 95 ° C. Depending on the concentration of BIX - salt solution and the selected heating temperature The heating time for the BIX treatment may vary. Preferably, the heating time of the hydrazine treatment is between about 5 minutes and about 24 hours, more preferably between about 30 minutes and about 8 hours. The mixing conditions are selected using the type and concentration of the BIX solution and the characteristics of the substrate (e.g., the affinity of the ions to be removed from the glass network, the strength of the glass after removal of the network ions, etc.) and the duration of the heat treatment. For example, without limitation, the mixing conditions can be continuous or intermittent, or mechanical mixing, fluidization, tumbling, rolling, or manual mixing. The combination of human total BDC salt solution concentration, heat treatment conditions, and mixing conditions is substantially determined based on returning a sufficient amount and dispensing a sufficient amount of hidden ions back to the matrix, and the ions are at a site in the matrix network. A sufficient amount of BIX_ionic is distributed to produce the desired table = type and extent ' to produce a surface active state desired for the intended use of the substrate or for the intended use of the catalyst composition. By adjusting the pH to adjust the surface charge of the substrate, it is also necessary to use the negative surface charge on the substrate to support the static + phase % ionic transition metal component of the positive charge or the like. Missing media, έr- ..., 'For some potential catalyst composition applications, you can hit the surface of the eight uu surface charge to support the components with negative charge (such as an anionic transition)贵 凰 Α Α Α Α Α 、 、 、 、 、 、 、 、 、 、 、 、 、 、 静电 静电 静电 静电 静电 静电 静电 静电 静电 126 126 126 126 126 126 126 126 126 126 126 126 126 126 Generally, the surface charge of the substrate can be changed to a net positive state or a net negative by adjusting the pH of the ion leaching substrate/ruthenium mixture to be lower or higher than the isoelectric point of the matrix (, IEp"). Sexual state. Think back, IEP is also known as zero charge (&quot;ZPC&quot;). Therefore, in other words, IEP (or zpc) can be regarded as the pH value of the material with a net zero surface charge on the surface at the initial humidity. Adjusting the pH of the 夤/IEX water mixture to a value greater than the matrix IEp (or 21^) produces a net negative surface charge on the kebab. In addition, the pH of the matrix/hydrophobic mixture is adjusted to be less than the matrix ΙΕρ (or The value of ??9 of zpc) can produce a net positive surface charge on the substrate. For example, but not limited to, if the IEP of the AR glass is equal to 96, if the pH of the AR glass subjected to ion leaching treatment is adjusted to &gt; 9.6 The pH will produce a net negative surface charge on the glass surface. Depending on the IEP distribution of the AR glass, the preferred way may be to adjust the pH to one or two or more pH values above the IEp of the matrix. Unit to ensure that its surface charge is fully supported. The type of solution to which the pH is adjusted will depend on compatibility with other reactants, glass stability, and required charge density, among other factors. Generally, any dilute base can be used to adjust the surface charge of the substrate to its , side (ie, negative surface charge generated/contented), and any dilute acid can be used to adjust the surface charge to the left side of its IEP (ie, to produce a net positive surface). Inorganic acids and bases or organic acids And the base can be used in a dilute concentration, and the suspension is preferably a mineral acid. Generally, the concentration of the dilute acid solution or the dilute alkali solution will depend on the type of acid or base used, its dissociation constant, and the type of surface charge to be obtained. And the pH of the density. 126422.doc -39- 200843852 In some cases, it may be necessary to integrate the catalytic component or precursor at a pH that causes the surface charge to produce the same sign as a catalytic component or precursor. Under these conditions, electrostatic adsorption (EA) type integration mechanisms are unlikely to occur. However, without being bound by theory, direct ion exchange may occur at exchangeable surface locations. ΙΕχ) or reverse exchange (BIX), resulting in the surface integration of catalytic components or precursors, which may be physically and/or chemically different from the same components integrated in the electrostatic adsorption f (EA) mechanism For example, certain substrate surface portions include cations (or anions) that may be replaced by ionic catalytic components or precursors of the same symbol, which may provide an appropriate but effective exchange of IEX or hydrazine with the surface portion of the substrate. Position, such as, but not limited to, such moieties, such as decyloxy (_Si_0. Na+) moieties, including at least partially displaced by a positively charged catalytic metal or metal complex precursor (such as, but not limited to, PcUNH3) 4^) The Na+ ions, in turn, produce a matrix having a catalytically effective amount of catalytic component. ‘k By adjusting? The value of 11 controls the surface charge of the matrix treated by the ruthenium as in the case of ruthenium treatment or second [[ΕΧ treatment ("ΙΕχ-2 treatment, as discussed below), for some ΒΙΧ treatments, it may be necessary to adjust the 1311 value However, it is necessary for Asia and Africa. Similarly, depending on the type of BIX-ion that will be integrated into the surface of the ΙΕΧ-2 treatment and the exchange of BIX-ions, the degree of adjustment required depends on the enthalpy of the matrix and its surface charge. The distribution curve and the type of charge required. The type of solution used to carry out the pH adjustment will depend on compatibility with other anti-objects, stability of the matrix over the relevant pH range, and the desired 126422.d〇 C -40- 200843852 Charge density and other factors. Generally, any rare test can be used to adjust the surface charge of the substrate to the right side of its IEP (ie, to produce a net negative surface charge), and any dilute acid can be used to charge the surface of the substrate. Adjust to the left side of the IEp (ie, produce a net positive surface charge). The inorganic acid or base or organic acid or base can be diluted. Usually, the concentration of the dilute acid solution or the rare test solution, Depending on the type of acid or base used, its dissociation constant, and the pH suitable for obtaining the type and density of the surface charge to be obtained. 〆III· Type 2 component precursor integration treatment Whether the substrate surface active system is received as it is, or is ionized Leaching treatment (ie, substrate treated with IEX-1), or treatment with hydrazine, preferably, (1) second ion exchange enthalpy-2&quot;), (ii) electrostatic adsorption (EA) treatment or (out) The combination of IEX-2 and EA treatment uses at least one second component precursor ("type 2 component precursor") to further process the substrate to integrate one or more second component precursors with a second and matrix On and/or within the surface of the ionic and/or electrostatic interaction substrate. Next, certain Type 2 component precursors may be subjected to a catalytically active zone $ without further treatment, or further processed, depending on the intended use. Producing a catalytically active region comprising one or more Type 2 components. However, the catalytically active region consists of a precursor of the (4) type 2 component and (b) consists of a type 2 component of the precursor of the type 2 component' or Consisting of a combination of (4) and (8), the average thickness of the catalytic region on and/or within the surface of the substrate is about 3 nanometers, preferably about 2 nanometers, more preferably &lt; about 1 nanometer. As mentioned previously, in some cases, depending on the intended use of the catalyst composition, the substrate received as received or ion leached may have a catalytic effect of 126422.doc -41 - 200843852. However, for many potential applications The method of τ v is 4 is to treat the selected base 仃ΙΕχ and/or 6 into the process. For example, but not limited to, a plurality of process ports using the catalyst composition of the present invention Can be 4 six-level emperor ^ ^ long-term catch rate, selectivity and / or efficiency in the month b, can be replaced by at least one will be flute - 锸 + v, 丨 knife brother a component ("1 type ingredients and brother one ingredient ("Type 2 Ingredients") The 舆 base coat was positively combined and significantly improved. In the case of unconstrained theory, the specific ion exchange position r ^ m on the surface of the mussel and/or the opposite V is discussed, by the opposite or indirect ionic interaction, The charge of the matrix, the surface of the shell, the electrostatic adsorption, and the combination of some ionic interactions and electrostatic adsorption interactions or other types of precursor charge-surface interactions to be understood, the type 2 precursor ions can be Integration. However, regardless of the nature of the interaction, 'type 2 component precursors' in the case of a substrate that is received as received, a substrate with IEX_W or a BIX-treated substrate that produces a second precursor charge-surface interaction It is thus possible to produce a catalytically active region having an average thickness on and/or within the surface of the substrate of - 30 nanometers, preferably &lt; about 2 nanometers, more preferably &lt; about nanometers. For the convenience of the following discussion, and without intending to limit the scope of the invention described herein, IEX_2 is used herein to collectively refer to a broad range of mutual interactions between charge-surface interactions or type 2 precursor precursors commonly referred to as type 2_component precursors. effect. In general, the salt&apos;s liquid type used to treat the matrix treated by the 圯-丨 or Βΐχ-process will depend on the type of ion to be ion exchanged in the ΐΕχ_2 treatment. Either an ion will be ion exchanged or, in some cases, two or more ions will be exchanged, or ion exchanges may be performed simultaneously, or ion exchange may be performed sequentially. In the case where the precursor precursor ions of two different dog-type types are integrated with the matrix, the swelling treatment in this paper is called two ion exchanges or two mouths, which are in two different types of component precursors. In the case where ions are integrated with the matrix, the IEX-2 treatment is referred to as tertiary ion exchange or tertiary expansion. The type 2 component and the precursor indicate any salt solution of the deionized ion, if it is chemically easy to replace (four) sample receiving, (4) X-directed or ion treated on the surface of the substrate, or has charge affinity to achieve and win 1 Electrostatic interaction of the treated or BIX-treated substrate surface can be used. Therefore, the IEX-2 ion can be used as a precursor to the type 2 component. As described above, the plasma secret 2 precursor (ie, the (four) component precursor) may have catalytic effect, and if so, the plasma IEX 2 4 precursor can act like a certain type of catalyst composition. The Type 2 component works as its precursor state, but the ion can also function as a ΙΕΧ-2 precursor in the preparation of another catalyst composition. However, in the case of pass 2, the ionic and the -2 drive (which can be used to obtain the type 2 component integrated with the surface of the substrate) includes, but is not limited to, Blenzel or Lewis acid, Brunsett or Lewis, precious metal cations. And noble metal complex cations and anions, transition metal cations and transition metal complex cations and anions, transition to oxyanions, transition metal chalcogenide anions, main oxyanion ions, rare earth ions, rare earth complex cations and anions and Combinations 0 126422.doc 43- 200843852 Again, depending on the intended use of the catalyst composition, certain ΙΕχ_2 ions themselves have catalytic potencies in the precursor state and can produce 21 components when combined with a suitable matrix. Selective ionic ΙΕχ 2 precursors with catalytic potency without further processing, some examples including, but not limited to, ruthenium, stellite or Lewis acid, brunite or Lewis, noble metal cations, transition metal cations, Transition metal oxyanions, main oxyanions, halides, rare earth hydroxide ions, rare earth oxide ions, and combinations thereof. Examples of certain noble metals and transition metals that can be used as precursors for type 2 components, including but not limited to Groups 7 through 11 (formerly Groups _, IIb, Vbk, Vlb, Vb, and νπι Family), such as Ming, Hand, Record, Copper, Silver, Gold, 铑, 铱, 钌, 铢, Hungry, Cobalt, Iron, Manganese, ionic salts and complex ion salts and combinations thereof. For the muscle 2 treatment, the ionic salts of the face, the enamel, the nail, the chain, the copper, the silver, the gold and the nickel are particularly preferably 0. For convenience, the elements of the group can be used by using international theory and application. The element family number assigned to the Federation/PAC) naming system is queried in the periodic table of chemical elements (and the family numbers previously used) displayed in jtp.'//pearu.lanI.gov/periodic/default htm. Examples of certain transition metal oxyanions that can be used as precursors for type 2 components, including but not limited to ionic salts of Groups 5 and 6 (formerly known as the Vb and VIb of Linyigang), such as V 〇43-, w〇2·, Λ, , U4 H2W12〇4〇6·, MOO, μ〇7〇24, Nb6〇196-, Re〇- and Α human/,, and σ. For the ΙΕΧ-2 treatment, ionic salts of chains, molybdenum, tungsten and vanadium are especially preferred. It can be used as a precursor of a type 2 component, such as a metal sulphide anion vapor, including but not limited to the ionic salt of Group 6 (formerly 坌ντκ, (other brother Vlb)) , 126422.doc -44- 200843852 such as M〇S4 ·, WS42- and combinations thereof. Examples of some main group oxygen anions that can be used as precursors of type 2 components, including but not limited to the first group (formerly Group VIa) Ionic salts, such as (10), P〇43, W, and combinations thereof. For the IEX-2, S (V- is 4 is preferred). y is a precursor of the type 2 component. Examples of tooth ions, including but not limited to the ionic salts of Group 17 (formerly Group VIIa), such as F-, ο·, with &quot;_, ι-, and combinations thereof. For ΙΕχ_2 treatment, F^ci• ions Salts are particularly useful as examples of certain rare earth ions and rare earth complex cations or ions of precursors of type 2, including but not limited to lanthanides and ionic salts of (iv) elements such as La, Pr, Nd, Pm, Sm, Eu. , (5), several, d" H〇, Er, Tm, Yb, Lu, Th, u, and combinations thereof, can be used to produce a transition as a type 2 component Examples of certain transition metals of genus-carbide, transition metal-nitride, transition metal-boride, and transition metal-phosphide, including but not limited to ions of chromium, molybdenum, tungsten, rhenium, knob, iron, cobalt, nickel Salts and combinations thereof. IEX-2 treatment instructions. The concentration of the salt solution used for IEX-2 treatment depends on the type of substrate that has been treated or BIX-treated and treated with ΙΕχ_2 and used in conjunction with IEX- 1 The relative affinity of the treated matrix interactions and/or integrated ΐΕχ_2 ions. For most types of glass substrates (such as but not limited to ar type, A type or sodium silicate (S0 (ia-iime) glass), about 〇〇 〇1 wt% to saturated IEX-2 salt solution is preferred, and about 〇〇〇1% to 5% and _2 salt 126422.doc -45- 200843852 solution is more m' visually regarded as reaching catalyst The functional surface concentration of the catalytic component necessary for the intended use of the composition is, ΐΕχ_2: possibly less than 0.001 wt.%. Wind/night, right-night ion types are exchanged with the matrix, either simultaneously or sequentially. The concentration of the salt solution will follow the precursors of the various components on the substrate. The relative loading and matrix are adapted to adjust the relative affinity of a component precursor to another component precursor, such as, but not limited to, two IEX-2 treatments (ie, two different catalytic component precursors and warp _ι or The concentration of the salt solution used for the various ions in the shoal will depend on the application of the machicho-treated matrix integration) or the tertiary ΙΕχ_2 treatment (ie, the integration of three different catalytic component precursors with the ruthenium or the ruthenium-treated matrix). Target relative concentrations of various constituent precursors integrated with the surface of the substrate and surface affinities for various separations. Typically, the heat treatment conditions applicable to ΙΕΧ_2 treatment are selected based on the type and concentration of the ΙΕχ2 salt solution used and the characteristics of the substrate:

Such as heating temperature, heating time and mixing conditions. Preferably, the twisting temperature suitable for the treatment of the parent 2 treatment using an acid may be between about 2 (TC to about 20 (TC), more preferably between about 30 t and about 9 (rc2. Depending on the IEX) The concentration of the -2 salt solution and the selected heating temperature may vary depending on the heating time of the IEX-2 treatment. Preferably, the heating time for the pressure treatment is between about 5 minutes and about 48 hours, more preferably about Between 1 minute and about 5 hours. Usually, depending on the type and concentration of the ΙΕΧ-2 salt solution used and the characteristics of the substrate 126422.doc -46- 200843852 (for example, the affinity of ions to be removed from the glass mesh) The mixing conditions are selected, such as, but not limited to, the mixing conditions may be continuous or broken, or may be mechanical mixing, fluidization, tumbling, rolling. Or manual mixing. The combination of IEI-2 salt solution concentration, heat treatment state and mixing conditions is determined based on the distribution of a sufficient number of IEX-2 ions and IEX_2 ions on the substrate and/or in the matrix. And physical and chemical bonding with the surface of the substrate Regardless of the quality, to produce the desired type and extent of surface charge 'to produce the desired surface activity state for the intended use of the catalyst composition. Adjusting the pH of the substrate to adjust the surface charge of the substrate, as described above, The degree of 1)11 adjustment required for the type II component precursor to be integrated with the surface in the IEX ("IEX-2,") treatment will generally depend on the IEP of the matrix, the IEP contrast surface charge distribution curve of the matrix, and the desired The type of charge, such as, but not limited to, for a substrate having an IEp equal to 8, preferably, the pH of the kebab/IEX-2 mixture is adjusted to be between about 8 and about 12, more preferably between about 9 and about 11. The type of solution used to effect the pH adjustment will depend on the phase of the other reactants, the stability of the matrix over the relevant pH range, and the desired fast charge and other factors. Typically, any dilute base It can be used to load the surface of the substrate to the right side of its IEP (ie, to produce a net negative surface charge), and any dilute acid can be used to adjust the surface charge of the substrate to the left side of its IEp (ie, to produce a net positive surface charge). ) inorganic acid or alkali or The acid or base can be used in a dilute concentration, and is usually preferably an organic base. Usually, the concentration of the dilute acid solution or the dilute alkali solution 126422.doc -47-200843852 will depend on the type of acid or base used, Dissociation constants and pH values suitable for obtaining the desired surface charge type and density. After completion of the IEX-2 treatment, preferably, the substrate treated with 乂-2 can be separated using any suitable method, including but not limited to filtration. , centrifugation, decantation, and combinations thereof. The IEX-2 treated substrate is then treated with one or more suitable cleaning solutions (eg, distilled or deionized water, dilute or dilute acid and/or a suitable water-soluble organic solvent, For example, decyl alcohol, ethanol or acetone) is washed and dried at a temperature of about 11 〇c for about 20 to 24 hours. IV. Post-precipitation treatment description If necessary, the substrate treated by IEX-2 can be separated, calcined, calcined under oxidizing conditions, then reduced or further oxidized, reduced or not calcined without calcination. In the case of oxidation. It can be as follows: to use a suitable reduction, vulcanization, carbonization, nitridation, phosphating or to perform a surface precipitation of a transition metal = oxyanion and / or sulfur anion in the gas or liquid phase to produce Corresponding: Chemical: Metal Sulfide / Sulfur Oxide, :. , metal nitride / oxynitride, metal sinter or metal squaring = the purpose of the purpose is to decompose gold metal oxides, metal chalcogenization sub-removal of any non-previous dry, usually but not limited to, post-precipitation calcination It is a counter ion or ligand, and the metal, matter, etc. are more closely integrated with the surface of the substrate, and the residual water removed in the drying process. The calcination treatment conditions which are successful in the surface activation of the IEX-2-treated surface are not particularly heavy, for the matrix, and the conditions should only be sufficiently strict 126422.doc -48-200843852::, can be catalytically effective The amount produces at least one with a sinking U. For example, the substrate is first calcined in an oxidative hearing (for example in air or oxygen). In addition, it is important to choose a high calcination temperature to ensure that the precursor of the type 2 component of interest is oxygenated: and any residual water is removed (if any residual water is still present) It should also be low enough to reasonably avoid the softening point of the matrix and the decomposition of the undesired precursors. For example, without limitation, the sulphate salt f is subjected to calcination conditions to decompose the bound cations and immobilize the sulfate on the surface, but such conditions must not reveal the decomposition of the sulfate into volatile sulfur oxides. Similarly, metal anion ions require calcination conditions to decompose the bound cations and immobilize the anions as oxides on the surface, provided that the conditions are not critical to volatilize the metal oxides from the surface or cause the metal oxides to dissolve into the matrix. Finally, precious metals and faults = should be burned under the following conditions: decomposition of the ligands and anions present, but not strictly such that the shellfish accumulate on the surface. For this reason, as explained in more detail below, the noble metal is preferably directly reduced without calcination. . Generally, the calcination temperature should be at least about 1 ° C below the softening point of the selected substrate. The calcination temperature should be between about 10 (rc and 70 (rc), more preferably between about 2 Torr (3c to 600 ° C, optimally between about 300 ° C and 500 ° C. Typically, The IEX-2 treated substrate is calcined from about i to about 24 shovel preferably calcined for about 2 to about 12 hours. Nevertheless, depending on the type 2 component of the matrix integration, the calcination time can be in the ranges Usually, but not limited to, the purpose of the post-precipitation reduction treatment is to at least substantially (if 126422.doc -49 - 200843852 Extraordinary King) catalyze the destruction of the constituent precursors (such as metals, metal oxides or metalloids) A lower oxidation state integrated with the surface of the substrate. Examples of suitable reducing agents include, but are not limited to, (3) and out. h2 is a preferred reducing agent, preferably having a flow rate of from about 1 L/hr to about gram per gram of substrate. Between l 〇〇 L / h, the flow rate is preferably between 01 1 ^ 1 and 1 L / hr per gram of matrix. Typically, the reduction temperature should be between 〇 〇 and 〇〇 to 6 〇〇. , provided that the temperature selected is at least l〇〇〇c lower than the softening point of the matrix. Typically, the substrate treated with IEX-2 is subjected to about U hours. Reduction treatment to about 48 hours, preferably from about 丨 to about 8 hours. Alternatively, the IEX-2 treated substrate can be reduced by solution phase treatment. The solution phase treatment uses a soluble reducing agent (eg But not limited to hydrazine, sodium hydride, lithium aluminum hydride, and combinations thereof, are carried out in a suitable solvent such as water or diethyl ether. Typically, but not limited to, after precipitation, the purpose of the IDING reaction treatment is to additionally reduce the metal with The reagent of the lower atomic weight _IDING element reacts to reduce the metal ion, the metal oxyanion and/or the metal sulfide anion. In some cases, direct-IDING occurs without simultaneous metal oxidative reduction, for example Certain Vulcanization Treatments Typical gas phase-IDING reagents include, but are not limited to, hydrogen sulfide, methyl mercaptan and dimercaptosulfur (vulcanization reagent), ammonia (nitride reagent), methane, ethane, and other light hydrocarbons ( Carbonization reagents. These gas phase-IDINCH agents can be directly reacted with IEX-2 treated substrates under ambient pressure or under pressure, or mixed with inert gas or hydrogen. The gas reacts with the substrate treated with ΙΕχ_2 to produce the corresponding sulfide, carbide or nitride. Possible 126422.doc -50- 200843852 Part of the catalytic effect - IDED product (including sulfur oxides, carbon oxidation And oxynitride) can also be produced by a substrate that is received/obtained as such, an integrated substrate treated with IEX-2, a calcined substrate treated with IEX_2, or a reduced substrate treated with IEX-2. Incomplete reaction. Metal phosphide can be produced by two ion exchange (two IEX-2 treatment) reduction treatments. One of the IEX-2 treatments is one or more transition metal ions, and the other is IEX. -2 treatment is a phosphate ion. Preferably, the two IEX-2 processes can be performed in sequence. Alternatively, the metal phosphide can be produced using a gas phase phosphating reagent such as, but not limited to, phosphine (PH3) to produce the desired metal phosphide. For example, a single ion-exchanged substrate (matrix treated with a single oxime-2) with the desired transition metal in the appropriate oxidation state can be further treated with PH3 to produce the desired metal scaly. i Solution phase treatment can be used to produce metal sulfides, metal borides and metal phosphide catalytic components. Typical solution treatments for the production of metal sulfides include, but are not limited to, in the range of temperatures up to the reflux temperature, and treatment of the metal-ion-integrated matrix treated with ruthenium-2 at an effective concentration of an organic solution of hexamethyl-sulfonane, for a period of time The time is sufficient to produce a catalytically effective amount of catalytic component on and/or within the surface of the base. Typical solution phase treatments for the production of the compound include, but are not limited to, for the metal-ion-integrated substrate of the deuterated-2 treatment, at room temperature to reflux temperature: between the effective time of the acid or the aqueous solution. Producing a typical solution of phosphide, &amp; not a lifetime, the combined / night phase treatment includes in the range of room temperature to reflux 'for the full detachment treated by IEX 2; 敫 &lt; Meng gen - ion - integrated matrix for hypophosphorous acid Sodium solution treatment is sufficient to produce a catalytically effective amount of catalytic component on the surface of and/or in the base of 126422.doc • 51-200843852. The ν·catalytic active region indicates that the catalytically active region resulting from any of the above substrate treatments will have an average thickness of (i) less than or equal to about 30 nm, preferably about 2 〇 nanometers, more preferably about 10 s. Nano, and (ii) catalyzing an effective amount of at least one catalytic component. Preferably, XPS spectroscopy is used to determine the average thickness of the catalytic region, and XPS spectroscopy uses a layered etching technique called a sputter depth profile (described in more detail below in the analysis method provided in the Examples below). However, other analytical techniques known to those skilled in the art can be used to determine the approximate location of the substrate surface associated with the catalytic component. Therefore, the average thickness of the matrix catalytic region can be determined using, for example, but not limited to, transmission electron microscopy (TEM) or scanning TEm (STEM, also described in more detail below). Those skilled in the art have a thorough understanding of XPS or TEM programs. It should be understood that in the extreme case, regardless of whether the catalytically active region is produced by IEX_i treatment or IEX-2 treatment (with or without BIX treatment), for any catalyst composition of the present invention C, the thickness of the catalytically active region - (4) does not substantially pass through the surface area of the substrate or (b) does not exceed the surface of the substrate by about 3 nanometers thick, preferably no more than about 2 nanometers thicker, more preferably no more than (7) nanometers. thickness. With regard to the localization of one or more catalytically active regions on and/or within the treated substrate, it is also understood that the catalytically active regions may: (a) be on the outer surface of the substrate, and in the presence of any pores, on the pore wall surface of the substrate (9) in the surface area of the substrate, that is, below the outer surface of the base f (4) not meters, preferably about 20 nm below the outer surface of the substrate, more preferably below the outer surface of the base 126422.doc -52- 200843852 〇 too half · no water, § in the presence of any pores, about 30 nm below the surface of the substrate pore wall, preferably on the surface of the substrate pore wall to scoop the rice, more preferably about 10 nm below the surface of the matrix pore wall, But above or below the surface of the substrate; (4) above or above the outer surface of the substrate, when there are any pores, partially on or above the surface of the substrate pore wall, and partially in the surface region of the matrix, or (4)(4), (b) and (4) Combination. , ^..., which is a type 1 component or a type 2 component, and the amount of the catalytic component may be about 2 wt·/. It is between about 5 wt.%, preferably between about wt2 wt% and about 2 wt.%, more preferably between about 〇5 %% and about 1. Moreover, the catalytically active regions of the catalyst compositions of the present invention can be continuous or discontinuous. Without being bound by theory, it is believed that the catalyst composition covered with the discontinuous catalytically active region is at least as effective as the catalytic component substantially covered by a continuous or broader range of catalytically active regions, And in some cases it is more effective. The extent to which the catalytically effective region covers the outer surface of the substrate can range from as low as 〇·〇〇〇1% coverage to as high as 1% coverage. Preferably, the extent of surface coverage outside the catalytically active region is about Between 0.0001% and about 10%, more preferably between about 0 0001 〇 / 〇 to about. However, without being bound by theory, it is believed that the catalyst composition, especially with a lower catalytic component wt, % loaded catalyst composition, is likely to be more catalytically effective because of the treated substrate The upper and/or inner catalytically active regions become more dispersed (i.e., more widely distributed and separated between the catalytically active regions). 126422.doc -53- 200843852 The catalytically active regions and other characteristics of the above-described catalyst compositions are based on the best available information from the inventors regarding the state of the catalyst composition prior to entering the steady state reaction conditions. The degree to which one or more of the described characteristics can vary is not certain and is largely unpredictable. Nevertheless, without being bound by theory, it is believed that the functional surface activity of the catalyst compositions described herein will permit the charge and/or charge of the catalytic component integrated with the matrix as the catalyst composition promotes its intended process reaction. Geometric positioning and other component characteristics vary significantly. Thus, it is to be understood that the scope of the invention described herein extends to all of the catalyst compositions produced by the claimed compositions under steady state reaction conditions. EXAMPLES The invention will now be described in more detail in connection with the following examples which illustrate or analogize various aspects of the practice of the invention. It is to be understood that all changes that come within the spirit of the invention are intended to be protected, and thus the invention is not to be construed as limited to the examples. Alkali-Resistant (AR) Glass Matrix Catalyst Composition Example 1 AR glass was obtained from an AR glass Cem-FIL Anti-CrakTM HD sample manufactured by Saint-Gobain Vetrotex, a glass fiber having an average diameter of about 17 to 20 microns. . In the first step, the AR glass sample received as it is is subjected to calcination heat treatment. In this treatment, the AR glass was calcined for 4 hours in an air atmosphere having an air flow rate of 1 L/hr and a temperature of 600 °C. In the second step, the simmered AR glass is subjected to acid leaching treatment. Place 25 grams of 126422.doc -54- 200843852 calcined AR glass and 3 liters of 5·5 wt.% nitric acid in 4 liter plastic wide-mouthed. Place the plastic container in a ventilated box at °C for one hour and shake it slightly with your hand every 15 minutes. After the acid leaching treatment was completed, the sample was filtered using a Whatman 541 filter, paper Buchner funnel, and washed with about 7.6 liters of deionized water. Then, at 11 〇. The acid leached sample was dried for 22 hours at a temperature of 〇. The second step is to perform ion exchange (ΙΕχ) on the acid-immersed ar glass. In this example, 'Polyoxy-oxytetramine palladium [pd(NH3)4](〇H)2 was used to prepare a 803⁄4 liter·〇 wt.% palladium solution for ion exchange ("ΙΕχ solution,"). 4 g of AR glass is added to the ion exchange solution glass/ion exchange mixture,). 罝 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃 玻璃Inside the container. Place the beta plastic barn in a 〇 通风 ventilated oven for 2 hours, shaking it slightly by hand every 3 minutes. After the ion exchange process is completed, filter the glass with a Buchner funnel with Whatman 541 filter paper / Ion exchange mixture, (sub-use about 3.8 liters of deionized water for cleaning. Then, at 温度(7), the ion-exchanged glass is dried for 22 hours. The fourth step is to reduce the ion-exchanged glass, the ion-exchanged glass is first in the air. The air atmosphere at a flow rate of 2 L/hr and the temperature at 300 ° C are calcined for 2 hours, and then reduced under a hydrogen (Η. atmosphere at a flow rate of 2 L/hr of hydrogen (out) and at a temperature of 3 ° C). 4 hours. Light and electricity by inductance -Atomic Emission Spectroscopy (ICP-AES) analysis of the sample mouth is paid to about 0 · 〇1 6 wt _ % | bar concentration. ^ Ps '贱 depth distribution method (described below) for sample analysis, such as I26422 .doc -55- 200843852 The presence of a large amount of palladium detected by this method is shown in Figure 1. The results show that the thickness of the area is about 10 nm. Example 2 The order of the AR glass and the Lingyi 1 And preparing an AR glass Cem_FlL AnU core akTM rib sample produced by Saint-G〇bairi vetr〇tex, that is, a glass fiber having an average diameter of about 17 to 20 μm. Sample analysis by AES yields about 〇·wt·% Palladium concentration. Sample analysis by XPS sputtering depth distribution method (described below), as shown in Figure 1, shows that the thickness of the region where the large amount of palladium detected by the method is about 1 〇 Example 3. Example 3

Acquired AR glass by Saint_Gobain Vetrotex Cem-FIL

Anti-CrakTM HD samples, glass fibers with an average diameter of approximately 17 to 2 microns. In the first step, the AR glass sample received as it is is subjected to calcination heat treatment. In this treatment, the AR glass was calcined for 4 hours in an air atmosphere having an air flow rate of 1 L/hr and a temperature of 600 °C. In the second step, the simmered AR glass is subjected to acid leaching treatment. Place 25 g of simmered AR glass and 3 liters of 5.5 wt.% nitric acid in 4 liter plastic wide-mouth containers. Place the plastic container in a ventilated oven at 60 ° C - hourly, shaking it slightly by hand every 15 minutes. After the acid leaching process was completed, 126422.doc •56- 200843852 The sample was filtered using a Buchner funnel with π Whatman 541 filter paper and rinsed with approximately 7.6 liters of deionized water. Then, the acid immersed sample was dried at a temperature of 110 ° C for 22 hours. The second step is an ion exchange treatment of the acid immersed AR glass. In the present example, 4 〇ml of a 0.1 wt% palladium solution was prepared using dichlorotetramine palladium [Pd(NH3)4](cl) 2 for ion exchange (, hydrazine solution,). 4 grams of glass was added to the ion exchange solution ("glass/ion exchange mixture,"). The pH of the glass/ion exchange mixture was measured to give a pH of about 7. 7. Then, the mixture was transferred to 1 Torr. The milliliter plastic wide-mouth container was placed in a 5 ° ° C ventilated oven for two hours and shaken slightly by hand every 3 minutes. After the ion father treatment was completed, 'Use the Buchner funnel filter glass with Whatman 54 1 filter paper. / Ion exchange mixture, and washed with about 3 8 liters of deionized water. Then, the ion exchange glass sample is dried for 22 hours at 1HTC temperature. The fourth step is to reduce the ion exchange glass sample, wherein the ion exchange glass First calcined in an air atmosphere at an air flow rate of 2 L/hr and at a temperature of 30 (rC for 2 hours, and then reduced in hydrogen gas at a hydrogen atmosphere of 2 L/hr and a temperature of 300 ° C for 4 hours. Sample analysis by ICP-AES yielded a concentration of 〇〇〇12 wt.% | Bar Example 4

Acquired AR glass by Saint-Gobain Vetrotex Cem-FIL

Anti-CrakTM tiD sample, glass with an average diameter of approximately 17 to 2 microns. 126422.doc -57- 200843852 Fiber. The first step is to perform a calcination heat treatment on the AR glass sample received as it is. In this treatment, the AR glass was calcined for 4 hours in an air atmosphere having an air flow rate of i L/hr and a temperature of 600 °C. In the second step, the calcined AR glass is subjected to acid leaching treatment. Approximately 5 么 克 克 克 烧 烧 AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR AR Place the plastic container at 9 inches. Shake it gently for 30 minutes every 30 minutes in a ventilated oven. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. Then, at 11 〇. The acid leached sample was dried for 22 hours at a temperature of 〇. In the third step, the acid-impregnated Ar glass is subjected to reverse ion exchange (''Na-BIX') treatment. The acid leached sample from the second step is separated from 4 liters of 3 mol/L sodium chloride (NaCl). Mix the solution (&quot;glass/sodium chloride mixture"). Measure the pH of the glass/NaCl mixture. As needed, about 4 〇 wt % of tetrapropylammonium hydroxide was added dropwise continuously, and the mixture was used? The value of 11 is adjusted to be greater than 10 (in this example, the pH obtained is about u.o). The glass/gasified sodium mixture was transferred to a 4 liter plastic wide mouth container. The container was then placed in a ventilated oven at % °C for 4 hours with a slight shake of the hand every 30 minutes. After Na_BIX treatment, the glass/sodium chloride mixture was filtered using a Brinell filter with Whatman 54 1 filter, paper and the Na_BIX/AR glass sample was collected and then washed with about 7.6 liters of deionized water. The Na-BIX/AR glass sample was then dried for 22 hours at the temperature of it. In the fourth step, a second ion exchange of 126422.doc -58 - 200843852 ΓΙΕΧ-2") was performed on the Na-BIX/AR glass sample. In this example, dichlorotetramine palladium [Pd(NH3)4] was used. (Cl) 2 A 3 liter 〇·〇ι wt·% palladium solution was prepared for ion exchange (&quot;IEX-2 solution). 42 grams of glass was added to the positive 12 solution (glass/IEX-2 mixture). The pH of the glass/IEX-2 mixture was measured to give a pH of about 8. 5. Then, the mixture was transferred to 4 liters. Inside the plastic wide-mouth container. Place the container in K10 (22 hours in a rc ventilated oven) and shake it slightly by hand during the 22-hour heating process. ΙΕχ_2 After treating το, then use the Buchner funnel with whatman 541 filter paper. Filter the glass/IEX-2 mixture and collect the ΙΕχ·2 glass sample, then rinse with about 7 6 liters of dilute ammonium hydroxide (ΝΗ4〇Η) solution. The diluted ΟΗ4ΟΗ solution is made by adding 10 gram of 29.8 Wt·% thick The NHUOH solution was prepared by mixing with about 3.8 liters of deionized water. Then, the ΙΕΧ-2 glass sample was dried for 22 hours at a temperature of 11 (rc). In the fifth step, the IEX-2 glass sample was subjected to reduction treatment, wherein the sample was sampled. The hydrogen (H2) flow rate was 2 L/hr in a hydrogen atmosphere at a temperature of 3 Torr for 4 hours. Sample analysis by ICP-AES gave a palladium concentration of about 15 wt%. The sample depth analysis method (described below) performs sample analysis. 1, the results show that the presence of the thickness by the method to detect a large amount of palladium is about 1 billion nm region. On the glass of Example 5 AR

Obtained the ar glass produced by Saint-Gobain Vetrotex Cem_FIL 126422.doc -59- 200843852

Anti-CrakTM HD samples, glass fibers with an average diameter of approximately 17 to 2 microns. In the first step, the AR glass sample received as it is is subjected to calcination heat treatment. In this treatment, the AR glass was calcined for 4 hours in an air atmosphere having an air flow rate of L/hr and a temperature of 600 °C. The first step is to subject the calcined AR glass to acid leaching. Place 9 〇, 〇 3 gram of AR glass and 4 liters of 5.5 wt·% nitric acid in a 4 liter plastic wide-mouth container. Place the plastic container in a 9 °c ventilated oven for two days, and shake it slightly with your hand for 15 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. The acid leached sample was then dried for 22 hours at a temperature of n〇t:. The second step is to subject the acid-impregnated AR glass to ion exchange (Ι)Εχ. In this example, 2000* liters of a 0.1 wt.% palladium solution was prepared using dihydrooxytetraamine palladium [Pd(NH3)4](〇H)2 for ion exchange (,, ΙΕχ solution. 80.06 gram AR glass is added to the ion exchange solution ("glass/ion exchange mixture Ί. Measure the value of 131_1 of the glass/ion exchange mixture to obtain the value of 11 and the spoon is 1 〇·6. Then, the mixture is transferred to 4,000 ml. The plastic container is filled with tears. Place the plastic container in a 5 (rc ventilated oven for 72 hours, shake it slightly by hand every 3 minutes. After the ion exchange treatment is completed, use the Whatman 54 1 filter paper. The Buchner funnel filter glass/ion exchange mixture is sub-used with about 7·6 liters of dilute NH4〇H solution. The diluted ΝΗβΗ solution is obtained by adding 10 gram of 29.8 wt·% concentrated NH4〇H solution to about 3.8 liters. Ionized water is mixed and prepared. Then, the ion exchange glass sample 126422.doc -60-200843852 is dried for 22 hours at a temperature of 11 ° C. The fourth step is to reduce the ion exchange glass, wherein the ion exchange glass is in hydrogen (H2) hydrogen atmosphere at a flow rate of 2 L/hr and 3 Torr At a temperature of c further the original 4 hours. By ICP-AES for sample analysis, approximately square 〇19 wt ·% of the concentration. On the glass of Example 6 AR

Acquired AR glass by Saint-Gobain Vetrotex Cem-FIL

Anti-CrakTM HD samples, glass fibers with an average diameter of approximately 17 to 2 microns. The first step is to perform a calcination heat treatment on the AR glass sample received as it is. In this treatment, the AR glass was satin-sintered for 4 hours in an air atmosphere having an air flow rate of 1 L/hr and a temperature of 600 °C. The second step of the brother's acid leaching treatment of the AR glass. 250 grams of simmered AR glass and 3 liters of 5.5 wt.% of sulphuric acid were placed in a 1 liter glass wide mouth container. The open plastic container is heated on a c〇rning hot plate for two hours so that the bottom of the container reaches a temperature of 90-1 〇〇 ° C, and the top of the container P reaches a temperature of at least 7 5 C. The thermocouples in each place were measured; since there was evaporation of the solution during the treatment, 5.5 wt.% of nitric acid was added to keep the volume at 3 liters. After the acid leaching treatment was completed, the sample was filtered using a 200 mesh stainless steel screen and washed with about 15 liters of deionized water. The acid immersed sample is then dried for several hours at a temperature of 1 °C. 126422.doc -61 - 200843852 In the second step, the acid-impregnated AR glass is subjected to ion exchange (ΐΕχ) treatment. In this example, 2000 g of 〇·ι wt% of a palladium solution was prepared for the ion exchange (, ΐΕχ solution) using dihydrooxoamine palladium [Pd(NH 3 ) 4 ](〇H) 2 . The yttrium AR glass is added to the ion exchange solution (, glass/ion exchange mixture). Measuring glass/ion exchange mixture? 11 value, get it? The value of 11 is about 9.4. Then, the mixture is transferred into a 4000 ml plastic wide-mouth container. Place the &quot;Hai plastic barn in a ventilated oven at 50 °C for 2 hours, shaking it slightly by hand every 3 minutes. . After the ion exchange process is completed, use

Whatman 541 filter paper Buchner funnel filters the glass/ion exchange mixture and rinses with a few liters of deionized water. Then, the ion exchange glass was dried for 22 hours at a temperature of 丨丨〇t. In the fourth step, the ion-exchanged glass was subjected to a reduction of 4 hours in a hydrogen atmosphere at a hydrogen flow rate of 2 L/hr and a temperature of 3 Torr. The sample was analyzed by ICP-AES to obtain about 〇〇. The concentration of palladium at 19 wt%. V is also analyzed by the sputtering depth distribution method (described below), as shown in Figure 1. The results show the thickness of the region where the large amount of palladium is detected by the method. About 10 nm. Example 7 Surface on AR glass

Acquired AR glass by Saint-Gobain Vetrotex Cem-FIL

Anti-Crak HD samples, glass fibers having an average diameter of about 17 to 20 microns. In the first step, the AR glass sample is received as it is subjected to a heat treatment. 126422.doc -62 - 200843852 is an air atmosphere of 1 L/hr and in this treatment, the AR glass is calcined at a temperature of 600 ° C for 4 hours. In the second step, the satin-fired AR glass is treated with acid, diced, and text. Approximately 160 grams of calcined AR glass and 12 liters of 5.5 wt% of sulphuric acid were placed in a W liter round bottom flask, and a speed of 9 (TC) was used at 9 (TC). Mechanically (four) two hours while heating down. After the acid leaching treatment, use the Buchner funnel with Whatman 5411 paper to pass the sample 'and use about 7.5 liters of chopped water to clean. _, at the temperature of ιι〇1, The acid leached sample was dried for 22 hours, and then the acid immersion sample was ground into a fine powder by passing through a small hammer mill in one step. The third step was to ion exchange the ground and acid immersed eight-foot glass. Treatment. In this example, 1 liter of a 0.3 wt.% platinum solution was prepared for the ion exchange ("ΙΕχ solution,") using tetrachlorotetramine platinum [pt(NH^4](cl)2.) about 158 g. The milled and acid immersed ar glass is added to the ion exchange solution (η glass/ion exchange mixture π). The pH of the glass/ion exchange mixture is measured. As needed, continuous addition of about 29.8 wt.% is added dropwise. Ammonium hydroxide (NH4〇H), the pH of the mixture is adjusted to greater than 1 〇 (in In this example, the pH was obtained to be about 10.6). The glass/ion exchange mixture was then transferred to a 4 liter beaker and heated at 50 °C for two hours while using a stainless steel paddle mixer at 300 to 500. Continuous mechanical agitation at rpm. After heating for one hour, measure the pH again and adjust the pH to greater than 1 再次 using approximately 29.8 wt.% NH4OH solution as needed. Completed in two hours of heating. After that, the pH of the glass/ion exchange mixture is measured again, and the measured pH is about 1 〇·1. After the ion exchange is completed, the glass/ion exchange mixture is filtered, and the belt is used. Ion exchange-glass samples were collected from a Buchner funnel with Whatman 541 filter paper and washed with approximately 7.6 liters of dilute NH4OH solution by diluting 10 grams of 29.8 wt.% concentrated NH4OH solution with approximately 3.8 liters of deionized water. Prepared by mixing. Then, the ion exchange glass sample was dried for 22 hours at a temperature of 110 ° C. In the fourth step, the ion exchange glass sample was subjected to reduction treatment, wherein the ion exchange sample Reduction was carried out for 4 hours under a hydrogen atmosphere at a hydrogen (H2) flow rate of 2 L/hr and at a temperature of 300 ° C. Sample analysis by ICP-AES gave a platinum concentration of about 0.0033 wt.%. A sample of AR glass Cem_FIL Anti-CrakTM HD produced by Saint-Gobain Vetrotex, a glass fiber having an average diameter of about 17 to 20 microns, was obtained. The younger step is to receive the A R glass sample as it is for the calcination heat treatment. In this treatment, the AR glass was calcined for 4 hours in an air atmosphere having an air flow rate of 1 L/hr and a temperature of 600 °C. In the second step, the simmered AR glass is subjected to acid leaching treatment. Approximately 30 grams of calcined AR glass and 4 liters of 5.5 wt.% nitric acid were each placed in a 4 liter plastic wide mouth container. The plastic container was placed in a ventilated oven at 90 ° C for two hours and shaken slightly by hand every 30 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 54 1 filter paper, and washed with about 7.5 liters of deionized water at 126422.doc -64-200843852. Then, at 110. . The acid leached sample was dried for 22 hours at the temperature. In the step = step, the acid-impregnated AR glass is subjected to ion exchange treatment. In the present example, 3 liters of a ?0% platinum solution was prepared for ion exchange (&quot;IEX solution,) using dichlorotetramine [Pt(10)3)4 chest 2 . Add about 15 〇 1 gram of d 戌 treated AR glass to the ion exchange solution ("glass / ion exchange / bar",). Measure the pH of the glass / ion exchange mixture. About 29.8 wt% of ammonium hydroxide (NH 4 〇H) was added dropwise continuously, and the pH of the mixture was adjusted to be greater than 1 〇 (in the present example, an ipH value was obtained, the force was 10.6). Transfer the ion exchange mixture to a 4 liter plastic wide-mouth container. Place the plastic container in a 5 (rc ventilated oven for 2 hours, shake it slightly by hand every 3 minutes). After heating - hour, measure the pH again. And, if necessary, again using a solution of about 29.8 correction % to adjust the pH to greater than i 〇. After the two-hour heating process is completed, the pH of the glass/ion exchange mixture 2 is measured again to obtain the value. Approximately I 1 〇 19. After completion of the ion exchange treatment, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 541 filter paper and the ion exchange _ glass sample was collected and washed with a 7.6 liter diluted NEUOH solution. NHaOH/Valley is made by using 1〇克克29·8 The wt·% concentrated NH40H solution was prepared by mixing with about 3.8 liters of deionized water. Then, the ion exchange glass sample was dried at u (rc temperature for 22 hours. The fourth step was to reduce the ion exchange glass, where ion exchange The glass was hydrogen (HO gas flow rate of 2 L / hr hydrogen atmosphere and 30 (TC temperature reduction for 4 hours. 126422.doc -65- 200843852 by ICP-AES sample analysis, to obtain a platinum concentration of about 0.0032 wt.% Example 9 The AR glass was first obtained from the Saint-Gobain Vetrotex AR glass Cem-FIL Anti-CrakTM HD sample, which is a glass fiber with an average diameter of about 17 to 20 microns. The first step is to receive the AR glass as it is. The sample was subjected to a calcination heat treatment. In this treatment, the AR glass was calcined for 4 hours in an air atmosphere having an air flow rate of 1 L/hr and a temperature of 600 ° C. The second step was to carry out acid leaching of the calcined AR glass. Dispose of about 30 grams of simmered AR glass and 4 liters of 5.5 wt% of nitric acid in a 4 liter plastic wide-mouth container. Place the plastic container in a 90 ° C ventilated oven for two hours. Shake it slightly with your hand for 30 minutes. After the immersion treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.5 liters of deionized water. Then, the acid immersed sample was dried at 110 ° C for 22 hours. Step, the ion-exchanged treatment of the acid-impregnated AR glass. In this example, 3 liters of a 0.01 wt.% platinum solution is prepared for the ion using tetrachlorotetramine platinum [Pt(NH3)4](Cl)2. Exchange (ΠΙΕΧ solution). About 9.8 gram of the acid leached AR glass was added to the glass/ion exchange mixture '' in the ion exchange solution'). The pH of the glass/ion exchange mixture was measured. As needed, about 40 wt.% of tetrapropylammonium hydroxide was continuously added dropwise, and the pH of the mixture was adjusted to be greater than 10 (in the present example, the pH obtained was about 126422.doc-66-200843852 was 11.3. 8). The glass/ion was dragged and dropped, and the mixture was transferred to a 4 liter plastic wide-mouth container. Place the plastic container in a ventilated oven at 1 〇 (ΓΓ 、, 3, iUUC for 22 hours, shake it slightly by hand every 30 minutes. After the treatment of the early six ionic fathers is completed, use the money with owman 541 The Buchner funnel passes through the surface/ion exchange mixture and collects the ion exchange-glass sample and is washed with a solution of about 76 liters of dilute nH4 〇h. The solution of the simplification is added by 1 gram wt.% concentrated NH4 〇H The solution was prepared by mixing with about 3.8 liters of deionized water. After that, the ion exchange glass sample was subjected to a 22 hour temperature at 110 C. In the fourth step, the ion exchange glass sample was subjected to reduction treatment, and the ion exchange glass was hydrogen (H2). A hydrogen atmosphere at a flow rate of 2 L/hr and 3 Torr. Reduction at 〇 temperature for 4 hours. Sample analysis by ICP-AES gave a platinum concentration of about 38 wt%. Example 10 A sample of Ar glass Cem_FIL Anti-CrakTM HD produced by Saint-Gobain Vetrotex, a glass fiber having an average diameter of about 17 to 2 micrometers was obtained. In the first step, the AR glass sample was subjected to a heat treatment by sintering as it is. Medium, AR The glass is calcined for 4 hours in an air atmosphere with an air flow rate of L/hr and a temperature of 600 ° C. The second step is to carry out acid leaching of the calcined AR glass. And 4 liters of 5.5 wt.% of the acid are placed in a 4 liter plastic wide-mouth container. Place the plastic container at 9 〇. 通风 ventilated oven 126422.doc -67- 200843852 2 hours, every 30 minutes Shake it slightly by hand. After the acid leaching process is completed, the sample is filtered using a Buchner funnel with Whatman 541 filter paper and rinsed with about 7.5 liters of deionized water. Then, at a temperature of 丨丨〇.〇, The acid leached sample was dried for 22 hours. In the second step, the acid-treated AR glass was subjected to ion exchange treatment. In this example, tetrafluorotetramine platinum [pt(NH3)d(cl)2 was used to prepare 3 Litre 0.01 wt·% of platinum&gt; trough liquid is used for ion exchange ("ΙΕχ solution,"). About 8 79 g of acid-impregnated AR glass is added to the ion exchange solution (,, glass/ion The parent exchanges the mixture. The value of the mouth 11 of the glass/ion exchange mixture is measured. Add about 29.8 wt% ammonium hydroxide (NH 4 〇 h), adjust the pH of the mixture to greater than 10 (in this example, the value of 11 is about 10.4). Move the glass/ion exchange mixture into 4 Liter plastic wide-mouth container. Place the plastic container in HKTC's ventilated oven for 22 hours; shake it by hand every 30 minutes. After ion exchange treatment, filter the glass with Buchner funnel with Whatman 54 filter paper/ Ion exchange mixed I and collect ion exchanged-glass samples and rinsed with approximately 7.6 liters of dilute NHUOH solution. The dilute NH4〇h solution is obtained by (7) grams of π′′ wt·. /. A concentrated NH40H solution was prepared by mixing with about 3. 8 liters of deionized water. The ion exchange glass samples were then dried for 22 hours at a temperature of 110 °C. In the fourth step, the ion-exchanged glass sample was subjected to a reduction treatment in which the ion-exchanged glass was reduced in a hydrogen (h2) flow rate of 2 L/(iv) hydrogen atmosphere and then at a temperature of t for 4 hours. Sample analysis by ICP-AES gave a platinum concentration of about 22 wt%. 126422.doc -68 - 200843852 Example 11 The beginning of AR glass

Acquired AR glass by Saint-Gobain Vetrotex Cem-FIL

Anti-CrakTM HD samples, glass fibers with an average diameter of approximately 17 to 2 microns. In the first step, the AR glass sample is received as it is subjected to a calcination heat treatment. In this treatment, the AR glass was calcined for 4 hours in an air atmosphere having an air flow rate of 1 L/hr and a temperature of 600 °C. In the second step, the simmered AR glass is subjected to acid leaching treatment. Approximately 3 gram of calcined AR glass and 4 liters of 5.5 wt.% citric acid were placed in a 4 liter plastic wide-mouth container. Place the plastic container at 9 inches. Shake it in your hand in a ventilated oven for 2 hours every 30 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.5 liters of deionized water. Then, at 11 〇. The acid leached sample was dried for 22 hours at a temperature of 〇. In the second step, the acid-impregnated AR glass is subjected to ion exchange treatment. In this example, cobalt hexahydrate (n) c〇(N〇3)2.6H2〇 was used to prepare a 0.1 wt.% cobalt solution for ion exchange (,, hydrazine solution,). The formation of enthalpy bubbles in the Ellenmeyer flask was carried out by means of 丄 liters of deionized water 3 〇 deduction to prepare the ion-parent exchange solution, minimizing the amount of air present, so as not to record the addition of I to change the oxidation state. The hexahydrate is then added to the purified deionized water. 4 The secondary value of the progeny exchange solution. According to the results, about 29.8 wt% ammonium hydroxide (Nh4〇h) was added dropwise, and the pH of the mixture was adjusted to be greater than 1 〇 (in this example, the value obtained was 11 126422.doc) -69- 200843852 is approximately 10.2). The ion exchange solution was then transferred to a 1 liter plastic wide mouth container. About 20 grams of acid-impregnated AR glass was added to the ion exchange solution (', glass/ion exchange mixture). The plastic container was placed in a 5 ° C ventilated oven for 2 hours, every 30 minutes. The hand was shaken slightly. After the ion exchange treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 54 1 filter paper. The mother liquor was collected and the pH was measured (in this example, the pH was about 9.70). The filtered glass was then washed with about 6 liters of dilute NEUOH solution. The dilute ηη4ΟΗ solution was prepared by mixing 10 gram of a concentrated 29.8 wt.% NHUOH solution with about 3.8 liters of deionized water. Then, at 110°. The ion-exchanged glass sample was dried for 16 hours at C temperature. Sample analysis by ICP-AES gave a concentration of about 〇·64 wt·%. Example 12 AR glass was obtained by Saint-Gobain Vetrotex. AR glass Cem-FIL Anti-CrakTM HD sample, which is a glass fiber with an average diameter of about 17 to 2 μm. In the first step, the AR glass sample is subjected to a calcination heat treatment as it is. In the treatment towel, the AR glass is The air flow rate is 空气-the air atmosphere and calcined for 4 hours at a temperature of 600 ° C. The second step is to carry out acid leaching treatment on the calcined AR glass. The Yoshikawa gram calcined AR glass and 4 liters 5·5 Each of the nitric acid was placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a 9-year-old ventilated oven at 126422.doc -70-200843852 for 2 hours, shaking it slightly by hand every 30 minutes. After completion, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.5 liters of deionized water. Then, the acid immersed sample was dried for 22 hours at a temperature of n ° ° C. 'Ion exchange treatment of acid-impregnated AR glass. In this example, a cobalt solution of 0 liters of 0·1 wt·% was prepared using cobalt (II) nitrate hexahydrate (N〇3) 2 · 6H20. Ion exchange (&quot;IEX solution,,). Prepare the ion exchange solution by forming A bubble through i liter of deionized water for 30 minutes in the Ehrlich flask, and minimize the amount of air present to avoid cobalt addition. After changing the oxidation state, then the hexahydrate Cobalt acid is added to the deionized water purified by hydrazine. The pH of the ion exchange solution is measured. As needed, about 29.8 wt% ammonium hydroxide (NH 4 〇h) is continuously added dropwise, and the pH of the mixture is adjusted to More than 1 〇 (in this example, the pH obtained is about 10.24). Then, the ion exchange solution is transferred into a plastic wide-mouth container of 丨 liter. About 20 grams of acid-impregnated eight-foot glass is added to the ion exchange solution. { Medium (glass/ion parent for mixture π). The plastic container was placed in a ventilated oven for 5 minutes, and after 25 minutes, it was shaken slightly by hand. After the ion exchange treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with whatman 541 遽 paper. Collect mother liquor and measure it? 11 value (in this example, the pH is about 9.88). The filtered glass is then washed with about 6 liters of a thin pick solution. The dilute NH4〇h solution was prepared by mixing 298 wt% of NH4〇H solution of ι〇g with about 3.8 liters of deionized water and then drying the ion exchange glass sample for 17 hours at the litre temperature. Cobalt concentration of wt·% The sample analysis by ICP-AES yielded approximately 〇15 126422.doc -71 - 200843852 degrees. Example 13 Tungsten on AR Glass

Acquired AR glass by Saint-Gobain Vetrotex Cem-FIL

Anti-CrakTM HD samples, glass fibers with an average diameter of approximately 17 to 2 microns. In the first step, the AR glass sample is received as it is subjected to a calcination heat treatment. In this treatment, the AR glass was calcined for 4 hours in an air atmosphere having an air flow rate of 1 L/hr and a temperature of 600 °C. In the second step, the calcined AR glass is subjected to acid leaching treatment. Approximately 3 ounces of simmered AR glass and 4 liters of 5.5 wt.% nitric acid were placed in 4 liter plastic wide-mouth containers. Place the plastic container in a 9 (rc ventilated oven for two hours, shaking it slightly by hand every 30 minutes. After the acid leaching process is completed, use a Buchner funnel with Whatman 541 filter paper to filter the sample and use about 7. 5 The aliquot of deionized water is washed. Then, the acid leached sample is dried for 22 hours at a temperature of 110 ° C. In the third step, the acid leached AR glass is subjected to ion exchange treatment. Ammonium tungstate preparation ^ liter 〇 〇 5 wt·% tungsten solution for ion exchange ("ΙΕχ solution"). About 1 5 · 01 a gram of acid leached ar glass is added to the ion exchange solution (" Glass/ion exchange mixture,,). Measure the pH of the glass/ion exchange mixture. Add about 29.8 wt% of cesium hydroxide (NH4〇H) continuously as needed, and exchange the glass/ion exchange The pH of the mixture was adjusted to 8 〇 and the glass/ion exchange mixture was transferred to a 4 liter plastic wide-mouth container. 126422.doc -72- 200843852 Place the plastic container in 5 (rc ventilation box... hand shake slightly - Under. Two hours of heating process ^' The mother used 30 minutes of Whatman 541 滹 paper right 戌, Kun, 丨, 口束日守' use with collected ion exchange = wash. Then, once under: ion ^ hours. Also change the glass sample dry 22 where ion exchange Calcination at temperature 4 In the fourth step, the ion-exchanged glass is calcined. The glass is subjected to an air atmosphere at an air flow rate of 2 L/hr and 5 〇〇 ^ hr. The concentration of the sample is analyzed by ICP-AES. 0·〇1 wt·% of 镌A glass matrix catalyst composition example 14 A-06F glass uranium

A-06F glass fiber produced by Lauscha Fiber International with an average diameter of about 500-600 nm was obtained. First, the A_〇6F glass sample which was received as it was and which was not calcined was subjected to acid leaching treatment. Approximately 21 grams of A-06F glass and 4 liters of 5.5% of the acid were placed in a 4 liter plastic wide mouth container. The plastic container was placed in a ventilated oven at 90 ° C for 2 hours and shaken slightly by hand every 30 minutes. After the acid leaching treatment was completed, the sample was filtered using a Brinell flask with Whatman 54 1 filter, paper, and washed with about 7.6 liters of deionized water. The acid leached sample was then dried for 22 hours at a temperature of 110 °C. In the second step, the ion exchanged A-06F glass is subjected to ion exchange at 126422.doc -73 - 200843852. In this example, 1 liter of a 0.01 wt.% platinum solution was prepared using ion tetramethylene chloride [Pt(NH3)4](Cl)2 for ion exchange ("ΙΕχ solution,"). Chuankeke A-06F The glass is added to the ion exchange solution ("glass/ion exchange mixture,"). The pH value of the glass/ion exchange mixture was measured. As needed, about 29.8 wt· was added continuously dropwise. /. Ammonium hydroxide (ΝΗ4〇Η), what is the mixture? The value of 1^ is reduced to more than 1 〇 (in this example, the value of ρ is about 丨丨·丨). Transfer the glass/ion parent blend to a 2 liter plastic wide-mouth container. Place the vessel in a 10 (TC ventilated oven for 23 hours. Shake it several times during the 23 hours of heating. After the ion exchange treatment is complete, filter with a Buchner funnel with ... (10) 54 1 filter paper. The glass/ion exchange mixture was collected and the ion-parent-glass sample was collected and washed with approximately 76 liters of dilute Nh4〇h solution. Dilute NH: 4 〇H solution was obtained by adding 10 gram of 29·8 wt% concentrated NH4〇H The solution was prepared by mixing with about 3.8 liters of deionized water. Then, the ion exchange glass sample was dried for 22 hours at the temperature of u〇CJc. In one step, the ion parent glass sample was subjected to reduction treatment, wherein the ion I parent was changed ρσ Reduction was carried out for 4 hours in a hydrogen atmosphere at a flow rate of 2 L/hr of atmospheric air (H2) and at a temperature of 3 Torr. Sample analysis by ICP-AES yielded a platinum concentration of about 〇·96 wt%. Example 15 A The -06F glass is obtained from A-06F glass fiber produced by Lauscha Fiber International with an average diameter of about 500-600 nm. First of all, 'for the A-06F glass sample received as it is, the acid is 126422.doc - 74- 200843852 Dip treatment. Will be about 50 grams A-06F The glass and 4 liters of 5.5 wt% nitric acid were placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a 9 〇t air-dried phase for 2 hours' shaking with a hand every 3 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. Then, the sample was acid immersed for 22 hours at a temperature of 丨丨〇.〇. In the second step, the acid-impregnated A-06F glass sample was subjected to ion exchange treatment. In this example, 3 ml of o.ool was prepared using palladium hydroxide (pd(NH3)4](〇H)2. The wt_% solution was used for ion exchange (,, hydrazine solution,). About 10 g of A-06F glass was added to the ion exchange solution (, glass/ion exchanged compound). Measurement of glass/ion The mixture is exchanged. As needed, about 29.8 Wt·% of ammonium hydroxide (ΝΗ4〇η) is continuously added dropwise, and the pH of the mixture is adjusted to be greater than 1 〇 (in this example, the value is about 1 〇· 5) Transfer the glass/ion exchange mixture into a 4 liter plastic wide-mouth container. Place the container in a 5 (rc ventilated oven for two hours, shake it with a slight hand rub in every 3 files. After the ion exchange process is complete, filter the glass/ion exchange mixture using a Buchner funnel with Whatman 541 filter paper and Obtain the filter cake, re-mix it with about 3 liters of dilute solution and then filter again. Repeat the steps of re-mixing/filtering twice. The diluted NH4〇H solution is made by adding 29.8 wt of ίο • A % concentrated NH40H solution was prepared by mixing with about 3 8 liters of deionized water. The ions were then exchanged for glass for 22 hours at the temperature of the helium. In the first step, the ion-exchanged glass sample is subjected to a reduction treatment in which the ions and the decomposed cations are reduced in hydrogen gas at a hydrogen atmosphere of pjj at a flow rate of 2 L/hr and at a temperature of 3 (10) c 126422.doc -75 - 200843852 for 4 hours. Sample analysis by ICP-AES yielded a palladium concentration of approximately 纠62%. 实例 Example 16 A-06F glass was known to be produced by Lauscha Fiber International with an average diameter of about 500-600 nm. A-06F glass fiber. First, the A_〇6F glass sample received as received and uncalcined was subjected to acid leaching treatment. About 51 g of A-06F glass and 4 liters of 5·5 % of nitric acid were placed in 4 In a liter plastic wide-mouth container, place the plastic container in a ventilated oven at 901: for 2 hours, shake it slightly by hand every 30 minutes. After the acid leaching process, filter the sample using a Buchner funnel with Whatman 541 filter paper. And use about 7. 6 liters of deionized water to clean. Then, the acid leached sample is dried for 22 hours at a temperature of 11 ° C. The second step is to treat the acid leached eight -06] glass. Na\reverse ion exchange (nNa-BIXn) treatment was carried out. The acid leached sample from the first step was mixed with 4 liters of a 3 mol/L sodium chloride (NaCl) solution ("glass/gasified sodium mixture"). The pH of the glass/NaCl mixture was measured. , about 40 wt.% of tetrapropylammonium hydroxide was added dropwise continuously, and the ipH value of the glass/NaCl mixture was adjusted to be greater than 1 〇 (in the present example, the pH was about 10.9). The sodium chloride mixture was transferred to a 4 liter plastic wide-mouth container. The plastic container was then placed in a 50 ° C ventilated oven for 4 hours, and shaken slightly by hand every 30 minutes. After Na-BIX treatment was completed, use Whatman 541 filter paper Buchner funnel filter glass / sodium chloride mixture and collect Na-BIX / A- 126422.doc -76- 200843852 06F sample, and use about 7. 6 liters of deionized water to wash. Then, in ιι〇 ° The Na-BIX/A-06F glass sample was dried for 22 hours at a temperature of C. In the third step, a second ion exchange ΓΙΕΧ-2") treatment was performed on the Na-BIX/A-06F glass sample. In this example Preparation of 1 liter of 〇·〇ι wt % palladium solution for ion exchange using dichlorotetramine palladium [Pd(NH3)4](Cl)2 IEX-2 &gt; liquid valley ''.) 35 g A-06F glass ieX-2 was added a solution of ( 'glass / IEX-2 mixture "). Measuring glass/ΙΕΧ-2 mixture? The value of 11 is about 8.5. The glass/IEX-2 mixture was transferred to a 2 liter plastic wide mouth container. The plastic container was placed in a 5 通风 ventilated oven for 4 hours and shaken slightly by hand every 30 minutes. After the ion exchange treatment was completed, the glass/ΙΕχ-2 mixture was filtered using a Buchner funnel with Whatman 541 filter paper and the IEX-2 glass sample was collected and washed with about 7.6 liters of dilute hydroxide. The dilute NH4〇H solution was prepared by mixing 1 〇g of 29·8 wt% concentrated NEUOH solution with about 3.8 liters of deionized water. Then, the i〇n-x2 sample was dried at a temperature of 110 ° C for 22 hours. In the fourth step, the IEX-2 glass sample was subjected to a reduction treatment in which the sample was subjected to a rat atmosphere of 300 L at an idle speed of 2 L/hr. Restore at room temperature for 4 hours. Sample analysis by ICP-AES gave a palladium concentration of about 9 wt%. Sample analysis was carried out by XPS sputtering depth distribution method (described below), as shown in Fig. 2, and the results showed that the thickness of the region where a large amount of palladium was detected by the method was about 15 nm. Example 17 126422.doc -77- 200843852 A-06F glass-on-glass A-〇6F glass fiber produced by Lauscha Fiber International with an average diameter of about 500-600 nm was obtained. In the first step, the A-06F glass fiber was subjected to ion exchange treatment. In this example, 2 liters of a palladium solution of 〇〇〇ι wt·% was prepared using palladium dihydrooxytetraamine [Pd(NH3)4](〇H) 2 for ion exchange (ί, ΙΕχ solution,). Add about 5.4 grams of _06F glass to the ion exchange solution (π glass/ion exchange mixture). "Measure the positive value of the glass/ion exchange mixture. Add about 29.8 Wt·% continuously as needed. Ammonium hydroxide (ΝΗ4〇Η), the value of the mixture was adjusted to be greater than 1 〇 (in this example, the 2ρ Η value was approximately ι〇ι). The glass/rhodium mixture was transferred into a 4 liter glass beaker container. And placed on a hot plate. The container was mechanically stirred in an oven for 591 for 2 hours. After 70% of the ion exchange treatment, the glass %/ion parent exchange mixture was filtered using a Buchner funnel with Whatman 54 丨 filter paper, and a filter cake was obtained. Remix it with about 3 liters of dilute NH4〇H solution and filter again. Repeat the two steps of remixing/i filtering. The diluted 〇4〇ί^8 solution is made by adding 10 gram of 29·8 wt·% thick The leg 4 is discharged from the liquid and mixed with about 3 8 liters of deionized water. Then, the ion exchange glass sample is dried for 22 hours at a temperature of 100 C. In the second step, the ion exchange glass sample is subjected to reduction treatment, wherein Ion exchange - glass #品在氢(η2) A gas atmosphere having a flow rate of 2 L/hr and a reduction of 3 Torr at a temperature of rc for 4 hours. Sample analysis by ICP-AES yielded a palladium concentration of about 〇.〇35 _ %. Splash by xps The depth profile method (described below) was used for sample analysis, as shown in Figure 2 of 126422.doc-78-200843852. The results show that the thickness of the region present by the method is approximately 15 nm. 18 A-06F Glass is obtained from A-06F glass fiber produced by Lauscha Fiber International with an average diameter of approximately 500-600 nm. The first step is for a sample of A-06F glass that is received as received and not calcined. Acid immersion treatment: Place about 50 grams of A-06F glass and 4 liters of 5.5 wt.% nitric acid in a 4 liter plastic wide-mouth container. Place the plastic container in a ventilated oven at 90 °C for 2 hours. Shake it by hand for 30 minutes. After the acid leaching process, the sample was filtered using a Buchner funnel with Whatman 54 1 filter paper and rinsed with approximately 7.6 liters of deionized water. Then 'at a temperature of 110 ° C, The acid leached sample was dried for 22 hours. The second step was to acid. The immersed eight_0617 glass sample was subjected to ion exchange treatment. In this example, 3 liters of a 0.001 wt.% palladium solution was prepared using palladium hydroxide (p3(NH3W(〇H)2) for ion exchange (" ΙΕχ solution,,). Add 10 grams of A-06F glass to the ion exchange solution (, glass/ion exchange mixture). i / then glass / ion parent exchange mixture only. As needed, continuously add about 29.8 wt,% ammonium hydroxide (NH4〇H), the pH of the mixture was adjusted to greater than 10 (in this example, the ipH value was about Η) 5). Transfer the glass/ion exchange mixture to a 4 liter plastic wide mouthpiece. Place the plastic container in a 5 (TC ventilated oven for two hours, shaking it slightly by hand every (10) minutes. After the ion exchange treatment is completed, use a cloth with: Whatman (4) filter paper with a bucket (4), a face/material exchange mixture and 126422. Doc -79- 200843852 Get the filter cake, remix it with about 3 liters of dilute NH4〇H solution and then repeat the two steps of remixing/filtering. Dilute νη4οιι solution is hunted by 2 gram of 2 gram The wt%mNH4〇I^S solution was prepared by mixing with about 3·8 liters of deionized water. Then, the ion exchange glass sample was dried at 110 ° C for 22 hours. The second step was to reduce the ion exchange glass sample. Treatment, in which the ion father replaces the glass first in an air atmosphere with an air flow rate of 2 L/hr and at a temperature of 3 Torr, and then burns X for 2 hours, and then at a hydrogen (out) flow rate of 2 (H2) gas. Gas and reduction at a temperature of 300 ° C for 4 hours. Sample analysis by ICP-AES gave a palladium concentration of about 59. Sample analysis was performed by XPS sputtering depth profile (described below), such as As shown in Figure 2, the results indicate that it is detected by the method. The thickness of the region where a large amount of palladium is present is about 15 nm. Example 19 A-06F glass fiber was obtained from Lauscha Fiber International, and A-06F glass fiber having an average weight of about 500-600 nm was obtained. For the acid leaching treatment of the A-06F glass sample received as received and not calcined. About 8.43 grams of A-06F glass and L5 liters of 5 5 wt% of nitric acid were placed in a 2 liter glass beaker and used. The stainless steel purple mixer was mechanically dispensed at a speed of 300 to 500 rpm at 22 ° C for 3 〇 8. After the acid leaching treatment, the sample was filtered using a Buchner funnel with Whatman 541 paper, and used approximately 7 · 6 Literated deionized water cleaning. Miao, 126422.doc -80 - 200843852 The second sample was dried for 22 hours at UG ° C. The first v was subjected to acid leaching of A-06F glass samples. Ion exchange treatment In this μ case, a palladium solution of 5 〇〇 wt wt wt 1 wt.% was prepared using ion dihydrogen tetraamine palladium [pd(NH3)4](〇H) 2 for ion exchange (, , ΐΕχ solution"). Add 4.2 metric gram glass to the ion exchange solution (&quot;glass/ion exchange In the case of mixing the mixture, the value of the glass/ion parent is changed. If necessary, wt.〇/〇^A^,b|,(NH4〇H), the pH value of the substance is up to more than 1〇 ( In the present example, the pH obtained was approximately ΐ〇·2). The glass/ion exchange mixture was transferred to a beaker of liters and stirred at a temperature of 5 °C for 2 hours. After the ion exchange treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 541 filter paper, and washed with about 7.6 liters of deionized water. Then, the ion-exchanged glass sample was dried at u (rc temperature for 22 hours. In the second step, the ion-exchanged glass sample was subjected to a reduction treatment in which the ion-exchanged glass was first placed in an air atmosphere having an air flow rate of 2 L/hr and 3 Torr. The mixture was calcined at a temperature of 2 hours, and then reduced at a hydrogen gas flow rate of 2 centimeters of hydrogen (8) at a temperature of 300 ° C for 4 hours. Sample analysis by ICP-AES gave a palladium concentration of about 57. / Example 20 A-06F glass on the surface A-06F glass fiber produced by Lauscha Fiber International with an average diameter of about 500-600 nm is known. First, for the A_〇6F glass sample received as received and uncalcined, 126422.doc • 81 - 200843852 仃 acid leaching treatment. It will be about 3 ounces of A_〇6F glass and 4 liters of 55 wt. / ❶ 硝 酸 酸 Each is placed in a 4 liter plastic wide mouth container. The plastic container was placed in a 90 C ventilated oven for 2 hours, and shaken slightly by hand every 3 minutes. After the essay/process, the sample was filtered using a Brinell filter with Whatman filter paper and rinsed with approximately 7.6 liters of deionized water. The acid leached sample was then dried for 22 hours at a temperature of 1 μC. The second step is to carry out ion exchange treatment on the acid-impregnated A_〇6F glass. In this example, 3 liters of 0.01 wt.% is prepared using tetrachlorotetramine platinum [Pt(NH3)4](Cl)2. Platinum solution is used for ion exchange (&quot;ΙΕχsolution&quot;). Add Η" grams of acid-impregnated A-06F glass to the ion exchange solution (,, glass / ion exchange mixture). Measure the value of the glass / ion exchange mixture? 11 as needed, continuously add about 29.8 wt .% ammonium hydroxide (ΝΗ4〇Η), the pH of the mixture is adjusted to greater than 1 〇 (in this example, the value is about 10.07). The glass / ion exchange mixture is transferred into a 4 liter plastic wide mouth container Place the plastic container in a 5 (rc ventilated oven for two hours. Shake it gently with the hand every 3 minutes. After the ion exchange process is completed, filter it with a Buchner funnel with Whatman 541 filter and paper. The glass/ion exchange mixture was collected and the ion exchange-glass sample was collected and washed with approximately 76 liters of dilute nh4 〇h solution. The dilute NH4 〇h solution was prepared by adding ι〇g μg.% concentrated NH4QH solution to approximately 3.8 liters. The ion-exchanged glass sample was dried for 22 hours at a temperature of llGt. In the third step, the ion-exchanged glass sample was subjected to (iv) original treatment, wherein the sample was subjected to a flow rate of 2 in the wind (Η2). L/hr preparation, 〇nr and reduction at a temperature of 300 ° C for 4 hours. 126422.doc -82- 200843852 Sample analysis by ICP-AES yielded a surface of approximately 〇·33 wt·%, and curvature. Example 21 The average diameter of the surface on the A-06F glass was approximately the A-06F glass fiber produced by Lauscha Fiber International at 500-600 nm. The first step was to receive the glass without the satin. The sample was subjected to acid leaching treatment. About 30 g of A-06F glass and 4 liters of 5·5 wt% of nitric acid were placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a ventilated oven at 90 °C. After an hour, shake it slightly by hand every 30 minutes. After the fork is finished, filter the sample using a Buchner funnel with Whatman 54 丨 filter paper and wash it with about 7.6 liters of deionized water. Then, at a temperature of 110 C The acid leached sample was dried for 22 hours. In the second step, the acid leached A_06F glass was subjected to ion exchange treatment. In the present example, dichlorotetramine _t(NH3)4](cl)2 was used. Prepare 3 liters of 〇·〇1 wt·% platinum solution for ion exchange (ΠΙΕχ solution. • 3 grams of acid-impregnated A-06F glass is added to the ion exchange solution ("glass/ion exchange mixture"). Measure the value of the glass/ion exchange mixture by 11. If necessary, add about 40 wt.% continuously. The tetramethylammonium oxide is oxidized, and the pH of the mixture is adjusted to be greater than 1 〇 (the pH value of this (4) is about 2 〇 7). The glass/ion exchange mixture is transferred into a 々 liter plastic wide mouth container. in. The plastic macro ^ j n n. It was placed in a 100 c ventilated oven for 22 hours. Every 30 minutes, the hand is slightly shaken _ τ six sudden, _ ^ month U shakes the lower valley. After the ion exchange treatment is completed, use a Buchner funnel with a Whatman 541 filter paper to filter the glass/ion exchange I26422.doc • 83 - 200843852 and use about 7.6 liters of thin

The mixture was collected and the ion exchange-glass sample was washed with NEUOH solution. Dilute NH4〇H^^ Original 4 hours.

Example 22 A-06F glass top surface U4 is an A-06F glass fiber produced by Lauscha Fiber International with an average straightness of about 500-600 nm. The first step is to perform acid leaching on the A-06F glass sample received as it is and not satin-burned. 30 g of A-06F glass and 4 liters of 5·5 wt·% of nitric acid were placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a 9 ° C ventilated oven for 2 hours and shaken slightly by hand every 30 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 crepe paper and washed with about 7.6 liters of deionized water. The acid leached sample was then dried for 22 hours at a temperature of ii 〇 °C. In the second step, the acid-impregnated A-06F glass is subjected to ion exchange treatment. In the present example, 3 liters of a platinum solution of 〇.1 wt.% was prepared for ion exchange ("IEX solution") using dioxetamine platinum [Pt(NH3)4](Cl)2. Add 21 grams of acid-impregnated A-06F glass to the ion exchange solution ("glass/ion exchange 126422.doc -84-200843852 for mixture"). Measure the glass/ion exchange mixture _. According to the two, continuous Add about 29.8 wt.% ammonium hydroxide (nh4〇h) dropwise, and the pH of the mixture (four) to more than 1G (in the actual shot, the value obtained is 1〇.38). Transfer the mixture into the plastic wide-mouth container of the instrument. Place the plastic container in a 10 (rc ventilated oven for 22 hours. Use the container under the hand for 3 minutes. After the ion exchange treatment is completed, use the -541 paper. The Brinell funnel was passed through a glass/ion exchange mixture and an ion exchange-glass sample was collected and washed with a solution of about 76 liters of dilute nH4 〇h. The diluted NH4 〇h solution was 298 wt.% thick by 1 gram. The NH4〇H solution was prepared by mixing with about 3.8 liters of deionized water. Then, the ion exchange glass sample was dried for 22 hours at a temperature of 110 C. In the third step, the ion exchange glass sample was subjected to a reduction treatment in which the sample was in hydrogen gas ( H2) Hydrogen atmosphere with a flow rate of 2 L/hr and 3 Torr Reduction at a temperature of c for 4 hours. Sample analysis by ICP-AES gave a platinum concentration of about 〇71 wt%. Example 23 Palladium and copper on A-06F glass were obtained from Lauscha Fiber International, with an average diameter of about A-06F glass fiber of 500-600 nm. Firstly, acid immersion treatment is carried out on the A _ 〇6 F glass sample which is received as received and not calcined. 15 g of A-06F glass and 4 liters of 5.5 wt· The % acid is placed in a 4 liter plastic wide-mouth container. Place the plastic container in a 9 ° C ventilated oven for 2 hours and shake it slightly by hand every 30 minutes. 126422.doc -85- 200843852 After the acid leaching treatment was completed, the sample was filtered using a cloth with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. Then, the acid immersed sample was dried at a temperature of 11 〇C for 22 hours. In the second step, the acid-leached A-06F glass is subjected to double ion six-shift treatment. In this example, 3 liters of 0.0005 wt.% total metal solution is used for double ion exchange ("double ion exchange solution"). Ion exchange solution Prepared by mixing 1·5 liter 〇·00 〇 5 wt·% palladium solution and 15 liters of r 〇·0005 wt.% copper solution. In this example, 1 5 5 liter 〇·〇 was prepared using dihydro oxytetramine.溶液 5 wt% of the solution and 15 liters of 0.0005 wt.% copper solution were prepared using nitric acid steel. About 14 g of A-〇6F glass was added to the double ion exchange solution (, glass/ion exchange mixture). Measure the pH of the glass/ion exchange mixture. About 298 wt.% of ammonium hydroxide (NH 4 〇H) was added dropwise as needed, and the pH of the mixture was adjusted to be greater than 1 Torr (in this example, 2 pH was about 1 〇.9). The glass/ion exchange was transferred into a 4 liter plastic wide mouth container. Place the plastic container in a ventilated oven at 5 两 for two hours, shaking it slightly by hand every 3 。 minutes. After the double ion parent is replaced by a treatment element, use a Buchner funnel with Whatman 54 1 filter paper to filter the glass / The mixture was rubbed and the double ion exchange_glass-like mouth was collected with a solution of about 7.6 liters of dilute hydroxide (NEUOH). The diluted NEUOH solution was obtained by applying 1 〇g to 29·8 wt〇/( ^NH4〇H liquid is prepared by mixing with about 3.8 liters of deionized water. Then, the double ion exchange-glass sample is dried for 22 hours at a temperature of 1 Torr. First step, for double ion exchange _ The glass sample was subjected to reduction treatment, in which the heavy ion parent-breaking glass sample was reduced in hydrogen gas at a temperature of 2 L/hr of hydrogen 126422.doc -86 - 200843852 gas and 300 ° C for 4 hours. Sample analysis by ICP-AES yielded a concentration of about 19 wt.% and a copper concentration of about 0. 02 wt. %. Example 24 Silver on A-06F glass was produced by Lauscha Fiber International. A-06F glass fiber with an average straight diameter of about 500-600 nm. Step, for the acid immersion treatment of the eight-〇61? glass sample received as it is, without satin burning. Place about 51 grams of A-06F glass and 4 liters of 5.5 pairs of nitric acid in 4 liters of plastic wide mouth. Inside the container, place the plastic container in a 9 (TC ventilated oven for 2 hours, and shake it slightly by hand every 3 minutes. After the acid leaching process is completed, filter the sample using a Buchner funnel with Whatman 541 filter paper, and It is washed with about 7.6 liters of deionized water, and then the acid is immersed in the sample for 22 hours at a temperature of 110 C. In the second step, the acid-impregnated A_〇6F glass is subjected to ion exchange treatment. In this example, 4 liters of 〇. 〇〇 1 wt% silver solution was prepared using silver nitrate for ion exchange ("IEX solution"). 1 〇g of A_〇6F glass was added to the ion parent exchange solution (, 'glass/ Ion exchange mixture,,). Measure the pH of the glass/ion exchange mixture. Add about 29.8 % of ammonium hydroxide (νΗ4〇η) continuously as needed, and adjust the pH value of the mixture to be larger than u (in this example, the pH obtained is about lh5). The sub-exchange mixture was transferred to a 4 liter plastic wide-mouth container. The plastic container was placed in a ventilated oven for 5 hours, and shaken by hand every 30 minutes. After the ion father was replaced, the use was carried out. Μ 1 filter paper Brinell 126422.doc -87 - 200843852 : Consider the glass / ion exchange mixture and collect ion exchange _ glass, mouth ^ use about 7.6 liters of thin muscle 〇H solution to clean. The dilute NH40H solution was prepared by mixing 1 Gg of a 29.8 wt.% concentrated NKUOH solution with about 3.8 liters of deionized water. Then, the ion exchange glass sample is dried for 22 hours at U (rc temperature. In the second step, the ion exchange glass sample is subjected to reduction treatment, which will be separated

The glass was again subjected to a hydrogen gas (H2) flow rate of 2 in a chlorine atmosphere and at a temperature of ° C for 4 hours. Sample analysis by ICP-AES gave a silver concentration of about 53 wt%. Example 25 A-06F glass fiber A-06F glass fiber produced by Lauscha Fiber International having an average diameter of about 500-600 nm was obtained. In the first step, acid immersion treatment is performed on the uncut calcined gossip glass sample as received. Will be about 100 grams of A-〇6F glass and 4 liters of 5·5 〇 〇. The nitric acid is placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a 90 C ventilated oven for 2 hours and shaken slightly by hand every 30 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 54 1 filter paper and washed with about 7.6 liters of deionized water. The acid leached sample was then dried for 22 hours at a temperature of 110 °C. In the second step, the acid-impregnated A-06F glass is subjected to ion exchange treatment. In this example, 3 liters of 0.016\¥1% platinum solution was prepared for the ion exchange (&quot;chemical solution) using tetrachlorotetramine platinum [Pt(NH3)4](Cl)2. Will be 48.17 126422. Doc -88 - 200843852 The addition of ions to the A-06F glass is also b + 丄 丄 又 又 又 又 ” ” (" glass / ion exchange mixture π). Measure the glass/ion exchange, and the human I ^ and change the pH of the compound. According to the need, the succession added about 2 9 · 8 wt % of helium from / wi · /. Ammonium telluride (NH4〇h), the pH of the mixture was adjusted to greater than 10 (in this example, the positive value was about 10.06). Transfer the glass-enhanced/ion parent-changing mixture to a 4 liter plastic wide-mouth container. The container was placed in a 5th generation ventilated oven for two hours. Shake it slightly by hand every 30 minutes - lower container. After the ion exchange treatment was completed, the glass/ion exchange mixture was filtered using a Buchner funnel with Whatman 541 filter paper and the ion exchange-glass sample was collected and washed with about 76 liters of a dilute N^OH solution. The dilute NH4〇H solution was obtained by using 298 wt· of 1 gram. /. A concentrated NH4〇H solution was prepared by mixing with about 3.8 liters of deionized water. The ion exchange glass samples were then dried for 22 hours at a temperature of 110 C. In the third step, the ion-exchanged glass sample was subjected to a reduction treatment in which the sample was reduced in a hydrogen (H2) atmosphere at a hydrogen flow rate of 2 L/hr and at a temperature of 500 ° C for 4 hours. Sample analysis by ICP-AES gave a platinum concentration of about 147 wt%. Example 26 A-06F glass top surface A-06F glass fiber produced by Lauscha Fiber International having an average diameter of about 500-600 nm was obtained. In the first step, the eight-061^ glass sample received as it is and not calcined is subjected to acid leaching. Approximately 21 grams of A-06F glass and 4 liters of 5·5 wt% of the acid were each placed in a 4 liter plastic wide-mouth container. Place the plastic container in 126422.doc •89- 200843852 for 2 hours in a 90 C ventilated oven and shake it slightly by hand every 30 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 6 liters of deionized water. The acid leached sample was then dried for 22 hours at a temperature of 110 °C. In the first step, the acid-impregnated A-06F glass is subjected to ion exchange treatment. In the present example, 4 liters of a 0.02 wt% platinum solution was prepared for ion exchange (, ΙΕχ solution π) using dioxetamine platinum. Approximately 21 grams of acid leached A-06F glass was added to the ion exchange solution (, glass/ion and milk exchange). $ Measure the mouth of the glass / ion exchange mixture ^ ^ value. About 29.8 wt.% of ammonium hydroxide (ΝΗ4〇Η) was added dropwise as needed, and the pH of the mixture was adjusted to be greater than 1 Torr (in this example, the ?11 value was about 10.90). The glass/ion exchange mixture was transferred to a 4 liter plastic wide-mouth container. Place the plastic container at 1 inch. . In the ventilated oven for 22 hours, shake it slightly with your hands every 30 minutes. After the completion of the treatment of the tank, the use of Whatman 54 1 minus the yue Taijiang, p, 丨, „heart A Buchner funnel filter glass / ion exchange mixture and collect ion exchange - glass choose η Jing Xiao The sample was cleaned with a solution of about 7·6 liters of dilute 〇Η4〇Η. The dilute 〇Η4〇Η,, &, and #丄合液系精精为10克克29.8 wt·% concentrated NH40H solution with about 3.8 The ionized water was mixed and prepared. Then, the ion exchange glass sample was dried for 22 hours at 110 C. The second step was to uncover the ion exchange glass, and the sample flow rate was 2 at the hydrogen flow rate. L/hr hydrogen (η2) Oxygen Hydrazine and reduction at 300 C for 4 hours. Sample analysis by ICP-AES was carried out to a platinum concentration of approximately 0.67 wt·%. Example 27 126422 .doc -90- 200843852 Unleached E-06F glass with E-06F glass fiber produced by Lauscha Fiber International with an average diameter of approximately 500-600 nm. First step, unleached E-06F glass sample Ion exchange treatment is carried out. In this example, dioxetane tetraamine palladium is used. [Pd(NH3)4](〇H)2 Prepare 2 liters of 0.00008 wt.% solution for ion exchange (&quot;ΐΕχsolution&quot;). Add 15.45 g of £-06? glass to the ion exchange solution (&quot ; glass / ion exchange mixture"). Measuring glass/ion exchange mixture? 11 values. About 29.8 wt.% of ammonium hydroxide (NH 4 〇 h) was added dropwise as needed, and the pH of the mixture was adjusted to be greater than 10 (in this example, the positive value was about 1 〇 99). The glass/ion exchange mixture was transferred to a 4 liter plastic wide-mouth container. Place the plastic container in a 5 (rc ventilated oven for two hours. Shake it slightly by hand every 30 minutes - under the container. After ion exchange treatment, use a Brinell funnel with Whatman 541 filter paper 叩8/office + filter glass / Ion exchange mixture and collect ion exchange - glass sample port two mouths and use about 7.6 liters of ί NH4OH solution to clean. Dilute NH4 〇 H dissolved , 4, combined, night hunting by 10 grams of 29.8 The wt·% concentrated NH4OH solution was prepared by mixing with about 3.8 wells of Fengchugongba open-mouth ion water. Then, at 110 C, the ion-crossing fish was changed to a glass sample and dried for 22 hours. Ion-exchange glass-like cutting mouth into the original processing, which will leave

The sub-exchange glass was reduced in a rolling atmosphere at a hydrogen (H2) flow rate of 2 L/h A h and at a temperature of 300 ° C for 4 hours. Sample analysis by ICP-AES, 曲, 、, 、, spoon is 〇· 014 wt · % I 巴 辰 辰 0 Example CH. 126422.doc -91 - 200843852 Analytical method re/XPS sputtering, SARCNa , Xenon point (IEP) and S·A.N2-BET or S·A.Kr-BET determination X-ray photoelectron spectroscopy (XPS) sputter depth distribution method using 1486.7 eV microfocus monochromator Α1 Κα X-ray source PHI Quantum 200 Scanning ESCA MicroprobeTM (Physical Electronics) obtained an xps sputtering depth profile. In this instrument, in the light. The double neutralization capacity of the low-energy electrons and cations to provide charge compensation is standard in the daily mining. XPS缙 is usually measured under the following conditions: - X-ray beam diameter 1 〇 2 〇〇 μηι - X-ray beam power 2-40 W - Sample analysis area 10-200 μη - The electron emission angle is 45 with the sample normal. The mouth area = XPS spectrum and the attenuation depth distribution map are recorded at room temperature. The sample is not included in the sample. The exception is to introduce the sample into the XPS instrument vacuum environment by alternating several cycles of the sample surface spectrum. Acquisition, 'then 2kvAr+ sputtering for 15 msec on each week = sample surface to remove surface material to generate a radiant depth profile. The depth of sputtering is simulated using a layer of known thickness of the stone. / Insult film by taking Pd 3d3, 2 and Si 2p peak P heart area for their respective sensitivity factors and analyzer transfer function into "$ Hf ^ 仃乜 is shown in Figures 1 and 2 Pd and S1 atomic concentration values. Those who are familiar with XPS analysis should understand that the measurement of the 贱/衣度 parameter is affected by the mechanical error of 126422.doc -92- 200843852, and the combination of the two may be caused by the xps 'spray taste distribution. Each reported value of the sputter depth determined by the technique results in an uncertainty of about 25/〇. Therefore, this uncertainty is expressed in the depth values shown in Figs. This inaccuracy is common throughout the Xps analysis technique. However, for the average thickness and other material properties of the catalytically active regions disclosed herein, this inaccuracy is not sufficient to hinder the combination of catalysts described herein. Distinguishing the matter does not affect the differentiation of the compositions from other compositions not described and claimed herein. Transmission Electron Microscopy (TEM) Analysis Transmission electron microscopy (TEM) sample detection was performed using a JEOL 3000F field emission scanning transmission electron microscope (STEM) instrument operating at 3 〇〇 kV accelerating voltage. The instrument is equipped with an lnca X-ray spectrometer system from Oxford Instruments, which performs a local chemical analysis using an energy dispersive spectrometer. Sample Preparation The sample material is first embedded in a standard epoxy embedding agent known to those skilled in TEM analysis. After curing, the epoxy-embedded sample material was cut using an ultra-thin microtome to produce a slice of about 8 Å nanometers thick. The sections were collected on a thin-film carbon carrier and were not further processed and properly positioned in the electron beam field of the above STEM instrument for detection and analysis. Those familiar with TEM analysis techniques should be aware that the use of TEM analysis to determine the position of the target analyte and the average thickness of the relevant region relative to the surface of the substrate are both subject to human error and mechanical errors, depending on the image resolution of the sample. Factors such as the physicochemical properties of the target analyte and the sample morphology may cause an uncertainty of about ±20% of the TEM vertical depth measurement (relative to a specific reference point of 126422.doc -93- 200843852) and about ± 5% of the lateral measurement results (relative to a specific reference point) uncertainty. Because of &amp;, this non-metric performance is distinguished between the measured composition and the sample matrix. The distinction between the media compositions is common throughout the TEM analysis. The distance of the face. This is not 'but not enough to prevent the touch SARCi measurement, SARCi empty sample and related statistical analysis f. Due to the above 4 ringing reasons, the surface area change rate (, 3尬^,,) is reported as the volume of Na〇H titrant. ratio. According to the above SARC cardiac program, the SARC service of each sample port specified in the following examples was determined. An empty sample was prepared by preparing a 3.5 Μ NaC1 solution (i.e., adding 30 gram of NaC1 in (10) ml of deionized water), which contained no matrix sample. However, in order to solve the statistical variability in the experimental procedure, four independent empty samples should be titrated, and the concentration used to obtain ^ and ~15 (also W) (0.01 N in this example) titration Each matrix sample sar was adjusted (i.e., corrected) to determine the drop used. T* volume The empty sample pH was adjusted according to the same procedure as the above sARC&amp; assay, and the empty sample was titrated, but also contained no matrix. , and the calculation of each sample and their respective mean and standard deviation (or V total σ) analysis test results in the table to report the statistics of the empty sample titer 5 '篆 also reported due to their respective V The overall statistical fluctuations corresponding to the respective titrations 5 V10 and Vl5. From the statistical point of view 'use statistics t public; #τ, +, near the average, the value outside the specified confidence interval can be greedy B,, by, #亚非 derived from the inherent deviation of the experimental method itself Up to 95%. Therefore, the v-initial and vt values measured by the sister in the confidence interval near the mean value of the sample are considered to be statistically different from the empty samples. Therefore, such samples do not calculate the SARCw value. Isoelectric Point (IEP) Measurement The isoelectric point (&quot;IEP" of each sample given below was determined according to the following procedure.

A Mettler Toledo SevenMulti meter with a pH mv/ORP module was used with a Mettler Toledo INLAB 413 pH composite electrode for ΙΕρ measurement. Calibrate the meter with standard pH buffer solutions at pH 2, 4, 7, and 10 throughout the relevant IEP. The IEP of each sample is determined by wetting the sample with 16 ΜΩ deionized water (at about 25 ° C), one of which is sufficient to bring the sample to its incipient state, which results in a relatively thick slurry or paste mixture. This incipient wet state allows liquid contact between the glass electrode and its reference electrode contact surface and the liquid (in this example, a slurry or paste mixture) that contacts the solid sample under test. Depending on the form of the sample (e.g., glass microfibers, granulated powder, chopped fibers, etc.) and its porosity (if any), the process requires a different amount of water. In all cases, however, the amount of water added should be sufficient to allow sufficient liquid to contact the glass electrode and the reference electrode. In other words, adding water to the sample to be tested should avoid making the sample exceed the initial humidity as much as possible. In all cases, the electrode tip was used and the solid sample was mixed by hand with silk water (added for generating incipient wetness) until the measured pH was stable, and the resulting pH was read from the meter. I BET or Kr βΕΤ Surface Area (S.A.) Measurement According to the ASTM procedure mentioned above, the S.A.N2_BET or S.A.Kr-BET assay is suitably performed for each of the samples given below. As discussed more fully above, for higher surface area measurements (eg, about 3 to 6: g), N2 BET is likely to be compared to the method described in 126422.doc -95-200843852 ASTM D3663-03 Good surface area measurement technology. For lower surface area measurements (e.g., 3 m2/g), core BET may be a preferred surface area measurement technique in accordance with the method described in ASTM D4780-95 (''S_A.〇_Mrf'). SARCNaS sample measurement and statistic for correction of SARCNJ^ value. Sample size Dilute NaOH Titration concentration (N) SAN2- ΒΕΤ (m2/g) In NaOH titration, used to make the pH value from 4.0 The initial value is adjusted to 9.0, and the titration volume (ml) required to maintain the pH at 9.0 at t5, t10 and t15 (V5M5) V total = ν initial ~ ls V initial 0 minutes Vs 5 minutes Vio 10 minutes Vis 15 minutes Vs, 15 sum and empty sample A 0.01 Not applicable 1.5 0.3 0.1 0.2 0.6 Empty sample B 0.01 Not applicable 2.2 0.1 0.1 0.2 Empty sample C 0.01 Not applicable 2.4 0.1 0.1 0.1 Empty sample D 0.01 Not applicable 2.2 0.1 0.2 0.1 Empty sample Average 0·01 Not applicable 2.075 0.15 0.125 0.15 Empty sample standard deviation 0.01 Not applicable 0.3947 0.1 0.05 0.0577 ^2708^ Empty sample 95% Trust interval 1.45-2.70 Example CH-2 E Glass-SARCNa Obtained E produced by Lauscha Fiber International -06F breaks away from the sample, ie glass fibers with an average diameter of 500 to 600 nm. Sample A-1 was an E glass sample received as received, and A-2 was an E glass that was received as it was prepared but not leached. Samples A -1 and 八_2, non-leached E glass samples were subjected to heat treatment. During this treatment, the non-leached E glass was calcined for 4 hours at an air atmosphere having an air flow rate of 1 liter/hour and a temperature of 6 Torr. The ratio of 126422.doc-96-200843852 was compared with the sample Comp-B by acid immersion treatment of the non-calcined E glass received as received. For the comparative sample Comp-B, about 15 g of E-glass and 1.5 liters of 9 wt.% of nitric acid were each placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a ventilated oven at 95 °C for 4 hours and shaken slightly by hand per minute. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. Then, the acid immersed sample was dried at a temperature of 110 ° C for 22 hours. Samples A-1, A-2 and Comp-B were analyzed by the above-described analytical method for determining SARC-. The results are shown in the table below. Sample No. Sample Describes the concentration of dilute NaOH titrant in NaOH titration, used to adjust the pH to t0 (the initial value of V* is adjusted to 9.0, and the titration required to maintain the pH at 9.0 at t5, 劬 and 彳5彳) The actual rhyme of the liquid,) from the time of 4·〇[V5 to 15) t product—(N) V first 0 minutes v5 5 minutes Vi〇10 minutes Vis I 15 minutes V total vw early ==^===== ===========^ The average value of the empty sample 1 0.01 2.1 0.15 0.125 0.15 Not connected to the star __ A-1 Received as it is E-06F 0.01 20.5 0.5 0.4 0.3 21.7 1.2 A-2 Calcination E-06F 0.1 0.7 0 0.1 0 0.8 0.1 Comp-B Leach E-06F 0.1 22.6 1.9 0.9 0.4 25.8 3.2__ Sample No. - 丨丨 - Sample Description SAN2-BET For SARCa^, the volume of titration solution (ml) Λ__ SARQva (V total - V initial) / V initial - P not applicable ΙΕΡ (m2 / g) V initial 0 minutes v5 5 minutes Vio 10 minutes Vis 15 minutes V total An empty sample is not applicable Not applicable 2.1 0.15 0.125 0.15 2.5 ------- Amendment A-1 ^ J IH. Received as received 8.9 2.7 18.4 0.35 0.25 0.15 19.2 0.04 Uncorrected A-2* iZ/^uor E-06F &lt;7 0.7 0 0.1 0 0.8 〈~0.2* Uncorrected Comp-B * Leaching Ε-06F —~.—a 4.1 ^--^1 161 22.6 1.9 0.9 0.4 25.8 <~0.2* 126422.doc -97- 200843852 *Because the empty sample correction value is obtained using 0.01 N NaOH titrant concentration, Instead of waiting for the special sample SARCw analysis, the 〇1 N NaOH titration solution' is therefore not used to correct the sample titration. Example CH-3 AR Glass - SARCNa

Acquired AR glass by Saint-Gobain Vetrotex Cem-FIL

Ant BurkTM HD samples, i.e., glass fibers having an average diameter of about 17 to 2 microns. In this example, the glass was used for samples A, b, and c. An ARG 6S-750 glass sample as produced by Nippon Electric Glass was obtained, i.e., a glass fiber having an average diameter of about 13 microns. In this example, the glass was used for samples D and E. Samples A and D were prepared by separately receiving AR glass and ARG glass by satin burning. For samples a and D, AR glass and ARG glass samples were subjected to calcination heat treatment. In this treatment, AR glass and Arg glass were calcined for 4 hours in an air atmosphere having an air flow rate of 1 liter/hr and a temperature of 600 °C. Samples B, C and E were prepared by acid leaching of the as-received, non-calcined Ar glass and ARG glass, respectively. For samples B and C, approximately 101 grams of AR glass and 4 liters of 5.5 wt.0/〇 acid were each placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a 90 C ventilated oven for 2 hours and shaken slightly by hand every 3 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. The acid leached sample was then dried for 22 hours at a temperature of 11 °C. Similarly, for sample E, approximately 5 8 grams of ARG glass and 4 liters of 5 · 5 126422.doc • 98- 200843852 wt·% of nitric acid were each placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a ventilated oven at 90 ° C for 2 hours and shaken slightly by hand every 15 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. The acid leached sample was then dried at a temperature of 11 0 C for 22 hours. Samples A-E were analyzed by the above analytical method for determining SARCw. The results are shown in the table below. Sample No. Sample Description Dilute NaOH Titration Concentration (N) In titration, used to adjust the initial value from 4.0 to 9.0 at t〇 (V initial), and at t5, ί1() &amp; ί15(ν5Μ5 The actual volume of the titrant required to maintain the pH at 9.0 (ml) ___ V first minute ^=================== 2.1 V5 5 minutes 0 15 Vio 10 minutes 0.125 Vl5 15 minutes IV螅-V headspace sample average value — 0.01 — a 0.15 2.5 a 'not applicable -- a null sample 95% confidence interval statistical confidence interval — ======= 1.44- 2.7 〇V/ · X _ 2:07- 2.93 A Calcined AR 0.01 2.4 〇0 0.1 2.5 0.1 B Leaching AR 0.01 2.2 0.1 0.1 0.1 2.5 0.3 _ ------ C Leaching AR 0.01 --2 1.7 0.1 0.1 0.1 2.0 0.3 D Calcined ARG 6S-750 0.01 1.6 0.4 0.3 0.4 2.7 1.1 —--- E Leaching ARG 6S-750 0.01 2.1 0.2 0.1 0.1 2.5 0.4 126422.doc 99- 200843852 —^__ Sample No. Sample IEP SAKr· BET (m2 /g) Correction of titration volume in milliliters (10) Description V initial 0 minutes v5 5 minutes vr 10 minutes 0.125 Vis o.is ———— Vtotal empty sample - empty sample average does not apply uncomfortable 2.1 0.15 2.5 Corrected—A Calcined AR 9.9 〇·13 0.30 -0.15 -0.13 -0.05 Modified B Leaching AR 9.6 0.16 0.10 -0.05 ------ -0.03 ------ -0.05 0 Corrected C Leaching AR i measurement 0.16 — — -0.40 -0.05 ------— -0.03 —^— -0,05 -0.5 Modified D Calcined ARG 6S-750 Not determined 0.11 -0.50 0.25 0.18 ^·-0.2 Corrected E leaching ARG 6S-750 not determined 0.12 0.0 0.05 -0.025 Ό.05 ----- -- 0 Red SARQya initial) / V is not applicable within 1 room, so the SARCva value is considered statistically

"/Q straw area /, the two average values are no different. Therefore, the SARC-determination is considered to be not used for the samples. Example CH-4 A-Glass-SARCNa is obtained from Lauscha Fiber International, and the A_06F glass fiber is about 500-600 nm. . In this example, 螭 螭 螭 is used for samples A, B and C ° to obtain α·26ρ granules produced by Lauscha Fiber International, ie glass fibers with an average diameter of 2.6 μm. In this example, glass was used for sample D. 126422.doc -100 - 200843852 Sample A is an A-06F-glass fiber sample received as received. Samples B and C were prepared by acid immersion treatment of the non-calcined A-06F-glass received as received. For samples B and C, approximately 58.5 grams of A-06F-glass and 4 liters of 5.5 wt.% nitric acid were each placed in a 4 liter plastic wide-mouth container. The plastic container was placed in a ventilated oven at 90 ° C for 2 hours and shaken slightly by hand every 30 minutes. After the acid leaching treatment was completed, the sample was filtered using a Buchner funnel with Whatman 541 filter paper and washed with about 7.6 liters of deionized water. Then, the acid immersed sample was dried at a temperature of 110 ° C for 22 hours. A-26F glass fibers having an average diameter of about 2.6 microns (2600 nm) produced by Lauscha Fiber International were obtained. In the present example, the glass was used as it was for sample D. The sample 87 was analyzed by the above analysis method for measuring SARC#a. The results are shown in the table below. The sample number sample describes the concentration of the dilute NaOH titration solution to 9. (Bu' is used to adjust the pH from the initial value of 4.0 at t〇 (V initial)) and the pH is at ts, t1G and t15 (V5M5) The value is kept in the actual volume of the titration solution (ml) (N) V initial minute v5 5 minutes Vl 〇 clock Vis 15 minutes V extinction - V initial sample average control average - 0.01 --- _ 2.1 0.15 0.125 0.15 2.5 Not applicable A Receive A-06 as received Γ 0.01 16.7 &quot;-------- 1.5 1.2 0.5 ___ 19.9 3.2 B Leach A-06 0.01 15.4 L4 〇ο 1 〇18.7 3.3 C Leach A-06 — Mil 15.7 ——— 2.3 1.2 1 -Vy 13 20.5 4.8 D A-26F as it is 0.01 5,4 ^-- 0.5 0.3 6.9 1.5 126422.doc -101 - 200843852 Sample number ============ == Sample IEP SAKr-I for correction of SARQva determination volume of titration solution (ml) SARc^a W々初)/V first description BET (m2/g) V first minute v5 5 minutes Vi〇10 minutes Vis 15 minutes open sample average control average not applicable Not applicable 0.15 0.125 0.15 ir=^=a='~ , 2.5 Not applicable Correction A ---~,—— A-06 Receive as received 10.1 3.1 14.6 1.35 1.075 0. 35 1 17.4 ^ 0.19 Modified B Leaching A-06 10.6 3.1 13.3 1.25 0.775 0.85 16.2 0.18^^ Corrected __C Leaching A-06 Not determined 3.1 13.6 2.15 1.075 1.15 18.0 0.32^ Corrected—D A-26F Not determined &lt;5 3.3 0.55 0.375 0.15 4·4 0.25^ Although in the foregoing embodiments, the invention has been described in accordance with certain preferred embodiments of the invention, and for the purposes of illustration It will be apparent to those skilled in the art that the present invention is susceptible to other embodiments and that some of the details recited herein may vary widely without departing from the basic principles of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an XPS sputtering depth profile corresponding to each of four samples including palladium on/in an AR-type glass substrate, wherein the sputtering depth profile is PHI Quantum 200 Scanning ESCA (Chemistry) The analytical photoelectron spectrometer was obtained by Microprobe (Physical Electronics, Inc.), which has a microfocus, monochromated Α1 Κα X-ray source operating at 1486.7 electron volts (eV). Figure 2 is an XPS sputter depth profile corresponding to one of 126422.doc -102-200843852 of three samples comprising palladium on/in a bismuth-type glass substrate, wherein the sputter depth profile is PHI Quantum 200 Scanning ESCA ( Chemical analysis was obtained using a photoelectron spectrometer, MicroprobeTM (Physical Electronics, Inc.), which has a microfocus, monochromated Α1 Κα X-ray source operating at 1486.7 electron volts. / 126422.doc 103 -

Claims (1)

200843852 X. Patent application scope: 1. A catalyst composition comprising: - a substantially non-porous substrate having an outer surface, a surface region and a subsurface region, - at least one catalytic component, and - at least one catalytic activity a region comprising the at least one catalytic component, wherein (a) the substantially non-porous matrix has a method of grouping a group of samarium freely S. Amw, 8. october lamps, and combinations thereof;总·〇1 m2/g to melon 2々 total surface area; and Π) a predetermined isoelectric point (IEP) obtained within a range of greater than 0 but less than or equal to 142ΡΗ; (b) the at least one catalytically active region May be continuous or discontinuous, and having i) an average thickness of less than or equal to about 30 nanometers; and π) a catalytically effective amount of the at least one catalytic component; and (c) the position of the at least one catalytically active region is substantially i On the outer surface, ii) in the surface region, (1)) a portion on the outer surface, and a portion in the surface region, or a combination of iv) (4) (1), (ii), and (out). 2. The composition of U item 1 wherein the at least one catalytic component is selected from the group consisting of: Bronsted or Louise (Bronsted or Bruce) or Lewis base, precious metal cations and expensive Gold 126422.doc 200843852 Heterocations and anions, transition metal cations and transition metal complex % ions and anions, transition metal oxyanions, transition metal chalcogenides anions, main preparations, 2 虱 anions, halides, rare earth ions , rare earth misregistered % ions and anions, noble metals, transition metals, transition metal oxygen species, transition metal sulfides, transition metal oxysulfides, transition metal analytic transition metal nitrides, transition metal deletions, transition metal scalides, Rare earth hydroxides, rare earth oxides, and combinations thereof. The composition of the sergeant 1 wherein the at least one catalytic component is a first catalyzed prior to the catalyst composition being in a steady state reaction condition, having (a) a first pre-reactive oxidation state, and (b) And a first pre-reaction interaction with the substrate selected from the group consisting of ionic charge interactions, electrostatic charge interactions, and combinations thereof. 4. The composition of claim 3 wherein the first catalytic component is selected from the group consisting of acids, assays, chalcogenides, and combinations thereof. 5. The composition of claim 3, wherein at least a portion of the first catalytic component is modified or substituted to form a second catalytic component prior to the catalyst composition being in a steady state reaction condition, having (4) a second pre-reacted oxidation state, and (b) a second pre-reaction interaction with the substrate: 'the second pre-reactive oxidation state of the second catalytic component is less than, greater than 6. or equal to the first catalytic component The first pre-reactive oxidation state. The composition of claim 5, wherein the second limiting component is selected from the group consisting of: 126422.doc 200843852, pin, bismuth, silver, bismuth, starving, copper, silver, gold, bismuth, bismuth A composition comprising the composition of claim 1, wherein the substrate is a glass composition having a SARCNa of less than or equal to about 〇·5. The composition of claim 1, wherein the at least one catalytically active region is substantially concentrated in a region having an average thickness of less than or equal to about 2 nanometers. 9. The composition of claim 1, wherein the substantially non-porous matrix is selected Free AR glass, rare earth citrate glass Boron aluminum silicate glass, E glass, boron-free E glass, s glass, R glass, rare earth silicate glass, Ba_Ti_ silicate glass, nitride glass, A glass, C glass and CC glass and 10. The composition of claim 1, 10. The composition of claim 1, wherein the IEP obtained by the substantially non-porous substrate is greater than or equal to about 6 〇 but less than 14 before or after the first leaching treatment. 126422.doc