CN116037110B - Preparation method of manganese oxide loaded platinum catalyst and catalyst - Google Patents
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 46
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 150000002696 manganese Chemical class 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000011572 manganese Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- 238000005530 etching Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- 229910000510 noble metal Inorganic materials 0.000 abstract description 10
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 71
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention provides a preparation method of a manganese oxide loaded platinum catalyst and the catalyst, wherein the preparation method comprises the following steps: respectively dispersing manganese salt, chloroplatinic acid and mesoporous silicon dioxide in water, carrying out ultrasonic and stirring mixing reaction, cooling to room temperature after the reaction is finished, and cleaning and drying the obtained precipitate to obtain a SiO 2@Mn2+-PtCl6 2‑ precursor; calcining the precursor sample in a muffle furnace, heating the precursor sample in an air atmosphere for reaction, and then switching the precursor sample to a hydrogen atmosphere (10% H 2/Ar) for reaction to prepare the SiO 2@MnO2/Pt catalyst; and (3) etching the SiO 2@MnO2/Pt catalyst by using hot alkali liquor, removing mesoporous silica, filtering and washing the obtained precipitate until the filtrate is neutral, and then drying to obtain the platinum catalyst taking MnO 2 as a carrier. I.e. the catalysts to be protected by the present invention. The invention has simple manufacturing process and cost saving, and is suitable for industrial production. Mass production; the obtained manganese oxide supported platinum catalyst has high intrinsic catalytic activity and rich active sites, and the catalytic activity is superior to that of most of the currently reported manganese-based noble metal catalysts.
Description
Technical Field
The invention belongs to the technical field of formaldehyde catalytic oxidation, and particularly relates to a preparation method of a manganese oxide supported platinum catalyst and the catalyst.
Background
Formaldehyde is one of the most common indoor air pollutants that has the property of binding to amino acids in the body to disrupt the structure of proteins, and thus long-term exposure to low concentrations of formaldehyde will cause irreversible damage to the human body. Meanwhile, formaldehyde is used as an important industrial raw material and is widely applied to indoor decoration and textile manufacturing, so that the formaldehyde is difficult to avoid in daily life. Therefore, the research and development of safe and efficient formaldehyde control technology has important significance. Among various formaldehyde removal technologies, the catalytic oxidation method is recognized as the most promising technical scheme due to the advantages of safety, high efficiency, no toxic byproducts, and the like. Development of efficient and safe formaldehyde oxidation catalysts is a key to promoting the application of catalytic oxidation technology.
The formaldehyde catalytic oxidation technology research has been developed to a great extent, which benefits from the development of material preparation technology and characterization technology, and a complicated catalytic system is formed. Two classes of compositions are available, transition metal oxide catalysts (MnO 2、Co3O4 and CeO 2, etc.) and supported noble metal catalysts (Pt, au, pd and Ag). At present, the transition metal oxide catalyst has lower cost, but is difficult to realize efficient formaldehyde catalysis, and the supported noble metal can realize complete conversion of formaldehyde at room temperature, but has higher cost. In recent years, the design and synthesis of a supported noble metal catalyst with high performance and low cost is a key subject for promoting the application of catalytic oxidation technology.
According to the prior literature report, the common manganese oxide catalyst prepared by the hydrothermal and coprecipitation method has the problems of small specific surface area, poor adjustability and the like, so that the dispersion degree of the supported noble metal is poor, the utilization rate of the noble metal is greatly reduced, and the catalytic activity of formaldehyde is influenced.
Disclosure of Invention
Aiming at the problems of small specific surface area, poor adjustability, poor dispersion degree of supported noble metal and low utilization rate of noble metal of the manganese oxide catalyst in the prior art, the preparation method of the manganese oxide supported platinum catalyst and the catalyst are provided.
The technical scheme of the invention is as follows: a method for preparing a manganese oxide loaded platinum catalyst, which comprises the following steps:
S1, respectively dispersing manganese salt, chloroplatinic acid and mesoporous silicon dioxide in water, carrying out ultrasonic and stirring mixed reaction, cooling to room temperature after the reaction is finished, and cleaning and drying the obtained precipitate to obtain a SiO 2@Mn2+-PtCl6 2- precursor;
S2, calcining the precursor sample obtained in the step S1 in a muffle furnace, heating and reacting in an air atmosphere, and then switching to a hydrogen atmosphere (10% H 2/Ar) for reacting to obtain the SiO 2@MnO2/Pt catalyst;
And S3, etching the sample obtained in the step S2 by using hot alkali liquor, removing mesoporous silica, filtering and washing the obtained precipitate until the filtrate is neutral, and then drying to obtain the platinum catalyst taking MnO 2 as a carrier.
Further, in the step S1, the manganese salt is at least one of manganese nitrate, manganese sulfate and manganese chloride; the concentration of the manganese salt is 0.1-0.5 mol/L, and the mass percentage of Pt in the chloroplatinic acid accounts for 0.05-0.5 wt% of the carrier MnO 2; the dosage of the mesoporous silica is 20-40 g/L.
Further, the ultrasonic time is 1-2 h, and the stirring time is 0.5-1 h; the reaction temperature is 25-60 ℃; the reaction time is 2-18 h.
Further, the cleaning is to clean with ultrapure water and absolute ethanol respectively; the drying temperature is 40-120 ℃ and the drying time is 4-12 h.
Further, in the step S2, the reaction temperature of the air atmosphere is 300-600 ℃, the heating rate is 5 ℃/min, and the reaction time is 2-4 h; the reaction temperature of the hydrogen atmosphere is 300-600 ℃ and the reaction time is 1-2 h.
Further, in the step S3, the hot alkali liquor is at least one of NaOH, KOH and ammonia water; the concentration of the alkali liquor is 3mol/L, and the etching time is 1-6 h.
Preferably, in the step S1, manganese salt is manganese nitrate, and the mass percentage of Pt in chloroplatinic acid is 0.1wt% of carrier MnO 2; the reaction condition is that the reaction is carried out for 12 hours at 50 ℃; drying at 60 ℃ for 4 hours to prepare a SiO 2@Mn2+PtCl6 2- precursor; step S2, calcining for 3 hours at 400 ℃ in the hollow atmosphere, cooling to 300 ℃, and switching the hydrogen atmosphere to calcine for 1 hour; in the step S3, the constant temperature treatment is carried out for 6 hours by using 3mol/L NaOH.
Preferably, in the step S1, manganese salt is manganese nitrate, and the mass percentage of Pt in chloroplatinic acid is 0.05 percent by weight of carrier MnO 2; the reaction condition is that the reaction is carried out for 12 hours at 50 ℃; drying at 60 ℃ for 4 hours to prepare a SiO 2@Mn2+PtCl6 2- precursor; step S2, calcining for 3 hours at 400 ℃ in the hollow atmosphere, cooling to 300 ℃, and switching the hydrogen atmosphere to calcine for 1 hour; in the step S3, the constant temperature treatment is carried out for 6 hours by using 3mol/L NaOH.
Preferably, in the step S1, manganese salt is manganese nitrate, and the mass percentage of Pt in chloroplatinic acid is 0.5wt% of carrier MnO 2; the reaction condition is that the reaction is carried out for 12 hours at 50 ℃; drying at 60 ℃ for 4 hours to prepare a SiO 2@Mn2+PtCl6 2- precursor; step S2, calcining for 3 hours at 400 ℃ in the hollow atmosphere, cooling to 300 ℃, and switching the hydrogen atmosphere to calcine for 1 hour; in the step S3, the constant temperature treatment is carried out for 6 hours by using 3mol/L NaOH.
The invention also provides a manganese oxide supported platinum catalyst, which is prepared by adopting any manganese oxide supported platinum catalyst preparation method.
The invention has the advantages that: according to the method, a manganese oxide precursor with a porous structure and loaded with platinum is directly synthesized by using a one-pot method, and the platinum metal is conveniently reduced in situ by combining a sectional calcination method for switching calcination atmosphere, so that highly dispersed platinum particles are obtained; the method not only greatly simplifies the manufacturing flow of the catalyst and saves the manufacturing cost, but also is suitable for mass production in industrial production.
Meanwhile, the obtained manganese oxide supported platinum catalyst has high intrinsic catalytic activity and rich active sites, and the specific surface area of the carrier manganese oxide is increased and is used as an adsorption site for adsorbing formaldehyde; the highly dispersed platinum particles can be used as active sites, effectively adsorb oxygen molecules on the surface, are rich in oxygen vacancies and promote the continuous progress of the reaction. Can continuously and efficiently catalyze formaldehyde to be oxidized and decomposed at room temperature, has no byproducts, and has catalytic activity superior to that of most of the currently reported manganese-based noble metal catalysts.
Drawings
FIG. 1 is a graph showing the catalytic oxidation performance of formaldehyde of the catalysts prepared in examples and comparative examples.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention adopts a hard template method to combine two steps of impregnation and noble metal loading, and prepares the catalytic material with platinum particles highly dispersed on the manganese oxide carrier with porous structure and high specific surface area, thereby effectively improving the catalytic activity of formaldehyde.
The manganese oxide supported platinum (Pt/MnO 2) catalyst has a porous structure, and the preparation method specifically comprises the following steps:
S1, respectively dispersing manganese salt, chloroplatinic acid (H 2PtCl6) and mesoporous silicon dioxide in water, carrying out ultrasonic and stirring, mixing, reacting, cooling to room temperature after the reaction is finished, and cleaning and drying the obtained precipitate to obtain the SiO 2@Mn2+-PtCl6 2- precursor.
S2, placing the precursor sample obtained in the step S1 into a muffle furnace for calcination, heating and reacting in an air atmosphere, and then switching to a hydrogen atmosphere (10% H 2/Ar) for reacting to obtain the SiO 2@MnO2/Pt catalyst.
And S3, etching the sample obtained in the step S2 by using hot alkali liquor, removing mesoporous silica, filtering and washing the obtained precipitate until the filtrate is neutral, and then drying to obtain the platinum catalyst taking MnO 2 as a carrier.
The manganese salt in the step S1 is at least one of manganese nitrate, manganese sulfate and manganese chloride; the concentration of manganese salt added into water is 0.1-0.5 mol/L, and the mass percentage of Pt in chloroplatinic acid is 0.05-0.5 wt% of carrier MnO 2; the dosage of the mesoporous silica is 20-40 g/L.
The reaction temperature is 25-60 ℃; the reaction time is 2-18 h; the drying temperature is 40-120 ℃ and the drying time is 4-12 h.
The ultrasonic time is 1-2h, and the stirring time is 0.5-1 h; the cleaning is to clean with ultrapure water and absolute ethanol respectively.
The reaction temperature of the air atmosphere in the step S2 is 300-600 ℃, the heating rate is 5 ℃/min, and the reaction time is 2-4 h; the reaction temperature of the hydrogen atmosphere is 300-600 ℃ and the reaction time is 1-2 h.
The hot alkali liquor in the step S3 is at least one of NaOH, KOH and ammonia water; the concentration of the alkali liquor is 3mol/L, and the etching time is 1-6 h.
The technical effects of the present invention will be further described below by way of specific example 1.
Example 1
A catalyst of 0.1wt% Pt/MnO 2 -400 was prepared, the mass percentage of Pt in chloroplatinic acid being 0.1wt% of the carrier MnO 2.
Step S1-synthesis of SiO 2@Mn2+-PtCl6 2- precursor: 1g of mesoporous silica and 2.51g of Mn (NO 3)2·4H2O、0.23mL H2PtCl6 solution (8 wt.% in H 2 O) are taken and placed in 50mL of deionized water, the solution is reacted at a constant temperature of 50 ℃ for 12 hours and then naturally cooled to room temperature, the obtained precipitate is filtered and washed (respectively washed by ultrapure water and absolute ethyl alcohol), and the precipitate is dried at 60 ℃ for 4 hours to prepare the SiO 2@Mn2+-0.1wt％PtCl6 2- precursor.
Step S2-SiO 2@MnO2/Pt catalyst synthesis: the SiO 2@Mn2+-0.1wt％PtCl6 2- precursor is placed in a muffle furnace, heated to 400 ℃ under an air atmosphere for reaction for 3 hours, cooled to 300 ℃ and switched to a hydrogen atmosphere (10% H 2/Ar) for reaction for 1 hour, and cooled to room temperature.
Step S3-synthesis of Pt/MnO 2 catalyst: the SiO 2@MnO2/Pt catalyst is filtered after being treated for 6 hours by 3mol/L NaOH at constant temperature, cleaned (respectively cleaned by ultrapure water and absolute ethanol), and dried to prepare the target catalyst of 0.1wt% Pt/MnO 2 -400.
Example 2
A catalyst of 0.05wt% Pt/MnO 2 -400 was prepared, the mass percentage of Pt in chloroplatinic acid being 0.05wt% of the carrier MnO 2.
The preparation was carried out in the same manner as in example 1 except that the H 2PtCl6 solution (8 wt.% in H 2 O) was added in an amount of 0.115mL in step S1.
Example 3
A catalyst of 0.5wt% Pt/MnO 2 -400 was prepared, the mass percentage of Pt in chloroplatinic acid being 0.5wt% of the carrier MnO 2.
The preparation was carried out in the same manner as in example 1 except that the H 2PtCl6 solution (8 wt.% in H 2 O) was added in an amount of 1.15mL in step S1.
Example 4
A catalyst of 0.1wt% Pt/MnO 2 -300 was prepared, the mass percentage of Pt in chloroplatinic acid being 0.1wt% of the carrier MnO 2.
The preparation method is the same as in example 1 except that in step S2 the calcination temperature of the SiO 2@Mn2+-0.1wt％PtCl6 2- precursor in the air atmosphere is 300 ℃.
Example 5
A catalyst of 0.1wt% Pt/MnO 2 -600 was prepared, the mass percentage of Pt in chloroplatinic acid being 0.1wt% of the carrier MnO 2.
The preparation method is the same as in example 1 except that in step S2 the calcination temperature of the SiO 2@Mn2+-0.1wt％PtCl6 2- precursor in the air atmosphere is 600 ℃.
Comparative example 1
Preparation of 0.1wt% Pt/MnO 2 -P catalyst, compared to the preparation method of example 1, was prepared by a precipitation-calcination method without using mesoporous silica template.
Step S1-synthesis of Mn 2+-PtCl6 2- precipitate: 2.51g of Mn (NO 3)2·4H2O、0.23mL H2PtCl6 solution (8 wt.% in H 2 O) and 6g of NaOH are taken and placed in 50mL of deionized water, the mixture is reacted at a constant temperature of 50 ℃ for 12 hours and then naturally cooled to room temperature, and the obtained precipitate is filtered and washed (respectively washed by ultrapure water and absolute ethyl alcohol) and dried at 60 ℃ for 4 hours to obtain Mn 2+-0.1wt％PtCl6 2- precipitate.
Step S2-synthesis of MnO 2/Pt catalyst: the Mn 2+-0.1wt％PtCl6 2- precursor is placed in a muffle furnace, firstly heated to 400 ℃ under the air atmosphere for reaction for 3 hours, then cooled to 300 ℃, and switched to the hydrogen atmosphere (10% H 2/Ar) for reaction for 1 hour, and cooled to the room temperature; drying to obtain the target catalyst 0.1wt% Pt/MnO 2 -P.
Comparative example 2
Preparation of 0.1wt% Pt/MnO 2 -Air catalyst compared to the preparation method of example 1, no step calcination was used and the sample was calcined only under an Air atmosphere.
And (3) testing formaldehyde catalytic oxidation performance of the obtained platinum-supported manganese dioxide catalyst, wherein the testing method comprises the following steps:
the reaction performance of the catalyst is tested by adopting a continuous flow fixed bed reactor, and the catalyst mainly comprises three functional units of gas distribution, reaction and analysis.
In the gas distribution unit, synthetic air is used as carrier gas and is divided into three paths, wherein two paths respectively pass through formaldehyde solution and aqueous solution, and mass flow meters on all the paths are regulated, so that mixed gas consisting of dry air, wet air and formaldehyde gas is obtained.
The reaction unit consists of a quartz tube and a heating device, and a proper amount of sample powder is taken and placed in the quartz tube with the inner diameter of 6mm in a quartz cotton wrapping manner; and then placing the quartz tube in an oil bath pot, connecting an air passage to ensure the tightness of the air passage, heating to a set temperature, and introducing fully mixed reaction gas. The detection of the gas products and concentrations after the reaction was performed by GC-2014 type gas chromatography equipped with FID.
The test conditions were: 90ppm HCHO, 21vol.% O 2, nitrogen as balance gas, gas flow rate 100mL min -1, space velocity 600L g -1·h-1. The catalysts prepared in each example and comparative example were tested for formaldehyde conversion at 25-80 ℃; the test results are shown in detail in FIG. 1.
As can be seen from the results of FIG. 1, when mesoporous silica is used as a hard template, the supported platinum is 0.1wt%, and the calcining temperature under an air atmosphere is 400 ℃, the obtained catalyst has optimal performance, and the complete oxidation of formaldehyde can be realized at room temperature. In examples 2 to 3, too high or too low platinum loading has an effect on the overall Pt/MnO 2 catalytic activity, but the catalytic effect is still better, and the complete oxidation of formaldehyde can be realized at 50 ℃. The calcination temperature has the most significant effect on the catalytic activity of Pt/MnO 2 compared to the platinum loading.
Compared with comparative example 1, if the template is not used, the formaldehyde activity of the catalyst (0.1 wt% Pt/MnO 2 -P) obtained by the precipitation-calcination method is far lower than that of the target catalyst (0.1 wt% Pt/MnO 2 -400) (25 ℃ to 100% vs. 21%), which means that the specific surface area of the manganese oxide carrier prepared by the template is increased, platinum particles can be effectively dispersed, thereby improving the utilization rate of active components and improving the catalytic activity.
Meanwhile, compared with comparative example 2, it can be seen that in-situ reduction in hydrogen atmosphere generates platinum particles with high dispersion distribution; the highly dispersed platinum particles can be used as active sites, effectively adsorb oxygen molecules on the surface, are rich in oxygen vacancies, promote the continuous progress of the reaction and improve the catalytic activity of formaldehyde.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (8)
1. The preparation method of the manganese oxide loaded platinum catalyst is characterized by comprising the following steps of:
S1, respectively dispersing manganese salt, chloroplatinic acid and mesoporous silicon dioxide in water, carrying out ultrasonic and stirring mixed reaction, cooling to room temperature after the reaction is finished, and cleaning and drying the obtained precipitate to obtain a SiO 2@Mn2+-PtCl6 2− precursor;
S2, calcining the precursor sample obtained in the step S1 in a muffle furnace, heating and reacting in an air atmosphere, and then switching to a hydrogen atmosphere of 10% H 2/Ar for reacting to obtain the SiO 2@MnO2/Pt catalyst;
S3, etching the sample obtained in the step S2 by using hot alkali liquor, removing mesoporous silica, filtering and washing the obtained precipitate until the filtrate is neutral, and then drying to obtain a platinum catalyst taking MnO 2 as a carrier;
The manganese salt in the step S1 is at least one of manganese nitrate, manganese sulfate and manganese chloride; the concentration of the manganese salt is 0.1-0.5 mol/L, and the mass percentage of Pt in the chloroplatinic acid accounts for 0.05-0.5wt% of the carrier MnO 2; the dosage of the mesoporous silica is 20-40 g/L;
step S2, the reaction temperature of the hollow atmosphere is 300-600 ℃, the heating rate is 5 ℃/min, and the reaction time is 2-4 h; the reaction temperature of the hydrogen atmosphere is 300-600 ℃ and the reaction time is 1-2 h.
2. The method for preparing a manganese oxide supported platinum catalyst according to claim 1, wherein the ultrasonic time in the step S1 is 1-2 hours, and the stirring time is 0.5-1 hour; the reaction temperature is 25-60 ℃; the reaction time is 2-18 h.
3. The method for preparing a platinum catalyst supported on oxides of manganese according to claim 2, wherein the washing means washing with ultrapure water and absolute ethanol, respectively; the drying temperature is 40-120 ℃ and the drying time is 4-12 hours.
4. The method for preparing a manganese oxide supported platinum catalyst according to claim 1, wherein: the hot alkali liquor in the step S3 is at least one of NaOH, KOH and ammonia water; the concentration of the alkali liquor is 3mol/L, and the etching time is 1-6 hours.
5. The method for preparing the manganese oxide supported platinum catalyst according to any one of claims 1 to 4, which is characterized by comprising the following steps: in the step S1, manganese salt is manganese nitrate, and the mass percentage of Pt in chloroplatinic acid is 0.1 weight percent of carrier MnO 2; the reaction condition is that the reaction is carried out for 12 hours at 50 ℃; drying 4 h at 60 ℃ to prepare a SiO 2@Mn2+PtCl6 2− precursor; step S2, calcining for 3 hours at 400 ℃ in the hollow atmosphere, cooling to 300 ℃, and switching the hydrogen atmosphere to calcine for 1 hour; in the step S3, the constant temperature treatment is carried out for 6 hours by using 3mol/L NaOH.
6. The method for preparing the manganese oxide supported platinum catalyst according to any one of claims 1 to 4, which is characterized by comprising the following steps: in the step S1, manganese salt is manganese nitrate, and the mass percentage of Pt in chloroplatinic acid is 0.05 percent by weight of carrier MnO 2; the reaction condition is that the reaction is carried out for 12 hours at 50 ℃; drying 4 h at 60 ℃ to prepare a SiO 2@Mn2+PtCl6 2− precursor; step S2, calcining for 3 hours at 400 ℃ in the hollow atmosphere, cooling to 300 ℃, and switching the hydrogen atmosphere to calcine for 1 hour; in the step S3, the constant temperature treatment is carried out for 6 hours by using 3mol/L NaOH.
7. The method for preparing the manganese oxide supported platinum catalyst according to any one of claims 1 to 4, which is characterized by comprising the following steps: in the step S1, manganese salt is manganese nitrate, and the mass percentage of Pt in chloroplatinic acid is 0.5 weight percent of carrier MnO 2; the reaction condition is that the reaction is carried out for 12 hours at 50 ℃; drying 4 h at 60 ℃ to prepare a SiO 2@Mn2+PtCl6 2− precursor; step S2, calcining for 3 hours at 400 ℃ in the hollow atmosphere, cooling to 300 ℃, and switching the hydrogen atmosphere to calcine for 1 hour; in the step S3, the constant temperature treatment is carried out for 6 hours by using 3mol/L NaOH.
8. A manganese oxide-supported platinum catalyst, characterized by being produced by the manganese oxide-supported platinum catalyst production method according to any one of claims 1 to 7.
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| CN106362765A (en) * | 2015-07-24 | 2017-02-01 | 苏州工业园区新国大研究院 | Formaldehyde room temperature oxidation catalyst preparation method and catalyst prepared through method |
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