CN102303861B - Method for preparing mesoporous carbon material based on natural halloysite as template - Google Patents
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Abstract
The invention relates to a method for preparing a mesoporous carbon material based on natural halloysite as a template. The method for preparing the mesoporous carbon material based on the natural halloysite as the template is characterized by comprising the following steps: 1) selecting natural halloysite powder and a carbon source at a mass ratio of the natural halloysite powder to the carbon source of 1:(1-5), wherein the natural halloysite powder is halloysite which is of a tubular structure, and the purity of the natural halloysite powder is larger than or equal to 95wt%; 2) firstly carrying out heat insulating on the natural halloysite powder for 3 hours at the temperature of 300-900 DEG C, adding acid, stirring, filtering, washing to be neutral, and drying; 3) evenly mixing activated and modified halloysite with the carbon source, and carrying out heat insulating for 6 hours-48 hours at the temperature of 130 DEG C-180 DEG C so as to obtain a precursor; and 4) firing the precursor for 3-6 hours at the temperature of 500 DEG C-900 DEG C in the atmosphere of N2 protection, cooling the product to room temperature after firing is finished along with a furnace, washing with HF to remove the template in the product, washing with deionized water to be neutral, filtering and drying so as to obtain the mesoporous carbon material. The mesoporous carbon material prepared by the method provided by the invention has a high specific surface area, and preparation process is simple.
Description
Technical field
The present invention relates to a kind of method for preparing mesoporous carbon material take natural halloysite as template.
Background technology
Mesoporous carbon is a kind of carbon crystal of stable state, there is mesopore orbit (2.0～50.0nm) in its structure, compare with porous charcoal, the aperture of mesoporous carbon is little, and pore passage structure is more concentrated, porosity is high, pore size distribution is narrow, and structurally has a short distance, be that atomic level is unordered, long-range, the orderly characteristics of the sight level that namely is situated between, its aperture is controlled easily simultaneously, is an important branch of porous carbon material.Mesoporous carbon material presents the trend that replaces traditional Carbon Materials with its higher specific surface area, narrower pore size distribution, fabulous chemistry and thermostability.Since it is born, it has been the emphasis of material circle research always.
1992, the Beck of U.S. Mobil company etc. uses the nanoassemble technology successfully to synthesize to have regular pore passage structure, aperture at adjustable novel crystallization M41S series silicon oxide (aluminium) ordered mesoporous molecular sieve of 1.0～10.0nm, to have opened up the new milestone of molecular screen material research first.Since then, design and development has the type material of meticulous pore passage structure, because it has huge pushing effect to industrial development, is an important Disciplinary Frontiers of Materials science research always.
In recent years, inorganic chemists are devoted to the research and development of mesoporous material on the basis of Zeolite synthesis, make great progress, and have synthesized a series of mesoporous (2.0～50.0nm) materials.Especially synthetic mesoporous carbon material with nano-pore structure causes people's broad interest in recent years, and this class material demonstrates good application prospect in fields such as absorption, catalysis, electronics.
The synthetic method of mesoporous carbon material is divided into catalytic activation method, organogel charring and template etc.
1. catalytic activation method
The catalytic activation method is to utilize metal and compound thereof to the katalysis of Carbon gasification, such as patent CN101367514 take segmented copolymer as structure directing agent, resin is carbon matrix precursor, solid alkali is catalyzer, organic/organic double compound the film that adopts colloidal sol-gel technique to be assembled into first in non-aqueous solvent, then charing obtains ordered mesoporous carbon.Although this method has than the more high stability three-dimensional crosslinked network structure of the synthetic product in the acid system, directly char volume shrinks and subsides littlely, is easier to obtain ordered mesoporous carbon, and shortcoming is to be difficult to accurately mesoporous structure, size and the pore distribution of control.And the standby mesoporous carbon material of catalytic activation legal system, it is inevitably that metal enters Carbon Materials inside, and has a large amount of micropores with the mesoporous carbon that the method makes.
2. organogel charring
The organogel charring is that charing is by the organogel of sol gel reaction preparation, such as patent CN101362598, CN1899959 report all is under certain condition, use sulfuric acid, three block tensio-active agents, tetraethoxy and sucrose mix and stir, through sol-gel, crystallization with pre-charing, go silication to obtain ordered mesoporous carbon material.Although the mesoporous carbon material that synthesizes has regularly arranged pore passage structure, larger specific surface area, the mesoporous of gained is at least part of continuous space, and expensive and complicated supercritical drying equipment is restricting its commercialization.
3. template
Template is divided into organic formwork method and inorganic template, a kind ofly has the material of special hole gap structure as template by selecting, import target material or presoma and it is reacted in the hole of this mould material, utilize the confinement effect of mould material, reach the purpose that the physical and chemical reaction in the preparation process is regulated and control, finally obtain microcosmic and macrostructure controlled and on traditional sense diverse mesoporous carbon novel material.The characteristics that template is the most outstanding are to have good structure controllability, and it provides one can control and improve the effective means that nanoparticle is arranged in structured material.Prepared material has the constitutional features similar to the template vestibule in this way, if the template that adopts has the aperture of homogeneous, the nano material of then being synthesized also will have uniform structure.All adopt the organic formwork method such as the mesoporous material of the announcements such as patent CN101279857, CN101417810, CN101462737, CN101362598 and the preparation method of mesoporous carbon material, synthetic by assembling under strong acidic condition.
In sum, template is the effective ways of control mesoporous rate and pore structure, size.Up to the present, not take natural halloysite as template, prepare the relevant report of mesoporous carbon material by hydrothermal synthesis reaction, the present invention utilizes this new raw material and method to prepare to be different from traditional mesoporous carbon material.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing mesoporous carbon material take natural halloysite as template, the mesoporous carbon material of the method preparation has higher specific surface area, and its preparation technology is simple.
For realizing the object of the invention, technical scheme of the present invention is: prepare the method for mesoporous carbon material take natural halloysite as template, it is characterized in that it may further comprise the steps:
1) mass ratio by natural halloysite powder and carbon source is 1: 1～5, chooses natural halloysite powder and carbon source, and is for subsequent use; The halloysite that described natural halloysite powder is tubular structure, purity 〉=95wt%;
2) proportioning by natural halloysite powder and acid is 5g: 100mL, chooses acid; Be 3 hours (thermal activation treatment) of 300 ℃～900 ℃ lower insulations with natural halloysite powder in temperature first, then add acid, mechanical stirring is filtered after 2 hours, is washed to neutral, dries by the fire 24～36 hours the halloysite that activated, modification is good in 85～100 ℃ of baking ovens;
3) halloysite and the carbon source that will activate, modification are good mix, and obtain halloysite/Carbon composites; Halloysite/Carbon composites is placed (being the tetrafluoroethylene storage tank) in the autoclave, and autoclave places the baking oven case, and insulation is 6h-48h hour under 130 ℃ of-180 ℃ of temperature, obtains presoma;
4) with presoma in 500 ℃～900 ℃, N
2Carry out calcination 3～6 hours under the atmosphere of protection, cool to product with the furnace room temperature after the calcination end, removed template in the product in 15～24 hours with the HF washing, extremely neutral with deionized water wash again, filter, dry, obtain mesoporous carbon material.
Step 1) preparation of described natural halloysite powder, it comprises the steps:
1) the quality percentage composition with halloysite is made into the suspension that concentration is 10-20wt% (quality) (containing the 10-20g raw ore in the expression 100g suspension) at natural halloysite raw ore and the water of 30-50%;
2) add-on by Sodium hexametaphosphate 99 is the 0.2-0.5% of natural halloysite ore quality, adds Sodium hexametaphosphate 99 in suspension, and mechanical stirring 2-4h obtains slurry;
3) slurry after will stirring is put into the whizzer centrifugation, rotating speed 1500-2000r/min, and the centrifugation time is 5-10min; After centrifugal, lower sediment is removed, get upper strata suspension, recentrifuge, rotating speed 3000-3800r/min, the time is 5-10min, obtains for the second time centrifugal throw out;
4) get for the second time centrifugal throw out, 80-100 ℃ of oven dry (baking 5-8h), the product after obtaining drying, for subsequent use;
5) get product after the oven dry, according to natural halloysite raw ore: the mass ratio of hydrochloric acid=1: 30-1: 70 ratio adds concentrated hydrochloric acid in the product after the oven dry, at 70-80 ℃ of lower stirring in water bath 1-10h; With the slurry suction filtration after stirring, to get solid water and be washed till neutrality, 80-100 ℃ of oven dry (drying by the fire 2-4h) obtains the natural halloysite powder of tubular structure, purity 〉=95wt%.
Above-mentioned steps 1): the Chemical Composition of described natural halloysite powder and quality percentage composition are: SiO
2=45.04%, Al
2O
3=38.31%, TFe
2O
3=0.16%, MgO=0.05%, CaO=0.05%, Na
2O=0.05%, K
2O=0.03%, TiO
2=0.04%, P
2O
5=0.02%, MnO
5=0.002%, H
2O
-=2.27%, loss on ignition=17.94%; Halloysite purity is greater than 95wt% in the natural halloysite powder, and the median size of natural halloysite powder is 5.226um.
Above-mentioned steps 1) carbon source in is furfuryl alcohol or the carbon sources such as sucrose or glucose.
Above-mentioned steps 2) acid is HCl, HNO in
3, H
2SO
4Deng in any or several solution by any mixed in molar ratio as properties-correcting agent natural halloysite is carried out modification; The volumetric molar concentration of acid is 0.5mol/L～10mol/L.
Above-mentioned steps 4) bake out temperature in is 80 ℃-100 ℃, and the time is 12～24 hours.
Above-mentioned steps 4) concentration of the HF in is 40wt%.
Prepare the mesoporous carbon material ultimate principle take natural halloysite as template: adopt the methods such as liquid impregnation, vapour deposition, Hydrothermal Synthesis organism evenly to be placed the hole of natural halloysite template, then mixture is carried out high temperature carbonization, obtain natural halloysite/Carbon composites, remove template, the mesoporous carbon material that namely obtains having template inorganics network structure feature with acid again.The advantage that adopts natural halloysite to make the maximum of template is that raw material sources are extensive, cheap.
Compared with prior art, the advantage that the present invention has is: the present invention adopts template successfully to synthesize mesoporous carbon material take natural halloysite as template, and this mesoporous carbon material has higher specific surface area (400m
2/ g～600m
2/ g), illustrate that this mesoporous carbon material has preferably absorption property; Simultaneously, this mesoporous carbon material has a large amount of mesoporous, pore size distribution narrower (not only be rich in a large amount of meso-hole structures, also contain a small amount of micropore and macropore and have triple pore size distributions), and this synthetic method is very simple, raw material sources are abundant, and are cheap.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1 gained mesoporous carbon material;
Fig. 2 is the N of embodiment 1 gained mesoporous carbon material
2The isothermal adsorption collection of illustrative plates;
Fig. 3 is the pore size distribution collection of illustrative plates of embodiment 1 gained mesoporous carbon material.
Fig. 4 is the XRD figure spectrum of natural halloysite raw ore.
Fig. 5 is the XRD figure spectrum of the embodiment of the invention 1 resulting natural halloysite powder.
Fig. 6 is the XRD figure spectrum of the embodiment of the invention 2 resulting natural halloysite powders.
Fig. 7 is the XRD figure spectrum of the embodiment of the invention 3 resulting natural halloysite powders.
Fig. 8 is the field emission scanning electron microscope photo of the embodiment of the invention 1 resulting natural halloysite powder.
Embodiment
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with example, but the present invention not only is confined to the following examples.
Embodiment 1:
Prepare the method for mesoporous carbon material take natural halloysite as template, it may further comprise the steps:
1) preparation of natural halloysite powder, it comprises the steps:
1. be that 50% natural halloysite raw ore (chief component of natural halloysite comprises halloysite, kaolinite, illite, gibbsite, quartz and feldspar, sees Fig. 4) and water are made into the suspension that concentration is 20wt% (quality) (containing the 20g raw ore in the expression 100g suspension) with the quality percentage composition of halloysite;
2. the add-on by Sodium hexametaphosphate 99 is 0.2% of ore quality, adds Sodium hexametaphosphate 99 in suspension, and mechanical stirring 3h obtains slurry;
3. the slurry after will stirring is put into the whizzer centrifugation, rotating speed 2000r/min, and the time is 10min; After centrifugal, lower sediment is removed, get upper strata suspension, recentrifuge, rotating speed 3800r/min, time 10min obtains for the second time centrifugal throw out;
4. get for the second time centrifugal throw out, 100 ℃ of oven dry (baking 5h), the product after obtaining drying, for subsequent use;
5. get the product after the oven dry, according to natural halloysite raw ore: the ratio of the mass ratio of hydrochloric acid=1: 50 adds concentrated hydrochloric acid (concentration of concentrated hydrochloric acid is 36-38%), at 70 ℃ of lower stirring in water bath 10h in the product after the oven dry; With the slurry suction filtration after stirring, to get solid water and be washed till neutrality, 100 ℃ of oven dry (baking 2h) obtain natural halloysite powder.
The XRD figure spectrum of natural halloysite powder can find out that almost have no other impurity peaks in the collection of illustrative plates, the purity of halloysite product is greater than 96% (quality) as shown in Figure 5.The field emission scanning electron microscope photo of natural halloysite powder as shown in Figure 8, visible significantly multilayer hollow tubular structures is typical halloysite microscopic appearance feature among Fig. 8.The median size of natural halloysite powder is 5.226um.
Take by weighing natural halloysite powder (abbreviation halloysite) 5.00g, measure furfuryl alcohol 8.80ml.
The natural halloysite powder (abbreviation halloysite) that 2) will weigh up first places crucible to be incubated 3 hours under 700 ℃ temperature, be cooled to room temperature, then the HCl that adds 100ml, 2mol/L, filter after 2 hours, wash to neutral (pH is 6～8) in 60 ℃ of lower mechanical stirring, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good.
3) halloysite that will activate again, modification is good and 8.80ml furfuryl alcohol mix in the rear immigration autoclave (tetrafluoroethylene storage tank), and place 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N
2Calcination is 4 hours in the atmosphere, after calcination finishes, treat that product (sample) cools to room temperature with the furnace, then take out sample concentration and be the HF washing of 40wt% and removed the mineral template in 15 hours, with deionized water sample is washed to neutral (pH is 6～8), filters at last, in 100 ℃ of drying and processings 20 hours, obtain mesoporous carbon material (the finished product).
Fig. 1 is the XRD diffractogram of the resulting mesoporous carbon material of present embodiment, and as can be seen from Figure 1, the mesoporous carbon material that makes is amorphous amorphous charcoal; Fig. 1 shows, all occurs a diffraction bag near 23 ° and 44 °, respectively correspondence the position of (002) and (101) face diffraction peak of graphite, illustrate some faint graphite microcrystal orderings in 800 ℃ carbonization process, to have occurred.Fig. 2 and Fig. 3 are the N of prepared mesoporous carbon material
2Isothermal adsorption figure and graph of pore diameter distribution have successfully synthesized mesoporous carbon material take natural halloysite as template with hydrothermal method as can be seen from Figures 2 and 3.The specific surface area of this mesoporous carbon material is 468m
2/ g, Langmuir area are 626m
2/ g sees Fig. 2.Have a large amount of mesoporously and have triple mesoporous distributions, be respectively 3.8nm, 9.8nm and 48nm, see Fig. 3.
Embodiment 2:
Prepare the method for mesoporous carbon material take natural halloysite as template, it may further comprise the steps:
1) preparation of natural halloysite powder, it comprises the steps:
1. be that 40% natural halloysite raw ore (chief component of natural halloysite comprises halloysite, kaolinite, illite, gibbsite, quartz and feldspar, sees Fig. 4) and water are made into the suspension that concentration is 15wt% (quality) (containing the 15g raw ore in the expression 100g suspension) with the quality percentage composition of halloysite;
2. the add-on by Sodium hexametaphosphate 99 is 0.3% of ore quality, adds Sodium hexametaphosphate 99 in suspension, and mechanical stirring 2h obtains slurry;
3. the slurry after will stirring is put into the whizzer centrifugation, rotating speed 2000r/min, time 5min; After centrifugal, lower sediment is removed, get upper strata suspension, recentrifuge, rotating speed 3000r/min, time 5min obtains for the second time centrifugal throw out;
4. get for the second time centrifugal throw out, 100 ℃ of oven dry (5h), the product after obtaining drying, for subsequent use;
5. get the product after the oven dry, according to natural halloysite raw ore: the ratio of the mass ratio of hydrochloric acid=1: 30 adds concentrated hydrochloric acid in the product after the oven dry, at 80 ℃ of lower stirring in water bath 5h; With the slurry suction filtration after stirring, to get solid water and be washed till neutrality, 100 ℃ of oven dry (baking 2h) obtain high-purity halloysite (product).
The XRD figure spectrum of natural halloysite powder can find out that almost have no other impurity peaks in the collection of illustrative plates, the purity of natural halloysite powder is greater than 98% (quality) as shown in Figure 6.From the field emission scanning electron microscope photo of natural halloysite powder, visible significantly multilayer hollow tubular structures is typical halloysite microscopic appearance feature.
Take by weighing natural halloysite powder (abbreviation halloysite) 5.00g, glucose 10.00g.
The natural halloysite powder (abbreviation halloysite) that 2) will weigh up first places crucible to be incubated 3 hours under 600 ℃ temperature, be cooled to room temperature, then the HCl that adds 100ml, 2mol/L, filter after 2 hours, wash to neutral in 60 ℃ of lower mechanical stirring, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good.
3) halloysite that will activate again, modification is good and 10.00g glucose mix in the rear immigration autoclave, and place 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N
2Calcination is 4 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 15 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 22 hours, obtain mesoporous carbon material (the finished product).
Product is carried out XRD and BET analyzes by the method identical with embodiment 1, confirm that this product is the mesoporous carbon material that has than bigger serface, pore size distribution is narrower, about 3.9nm.N from prepared mesoporous carbon material
2Isothermal adsorption figure and graph of pore diameter distribution can be found out take natural halloysite as template successfully to have synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 470m
2/ g.
Embodiment 3:
Prepare the method for mesoporous carbon material take natural halloysite as template, it may further comprise the steps:
1) preparation of natural halloysite powder, it comprises the steps:
1. the natural halloysite raw ore (chief component of natural halloysite comprises halloysite, kaolinite, illite, gibbsite, quartz and feldspar, sees Fig. 4) and the water that with the quality percentage composition of halloysite are 30% (quality) are made into the suspension that concentration is 10% (quality) (containing the 10g raw ore in the expression 100g suspension);
2. the add-on by Sodium hexametaphosphate 99 is 0.5% of ore quality, adds Sodium hexametaphosphate 99 in suspension, and mechanical stirring 4h obtains slurry;
3. the slurry after will stirring is put into the whizzer centrifugation, rotating speed 1500r/min, time 10min; After centrifugal, lower sediment is removed, get upper strata suspension, recentrifuge, rotating speed 3800r/min, time 5min obtains for the second time centrifugal throw out;
4. get for the second time centrifugal throw out, 80 ℃ of oven dry (baking 8h), the product after obtaining drying, for subsequent use;
5. get the product after the oven dry, according to natural halloysite raw ore: the ratio of the mass ratio of hydrochloric acid=1: 70 adds concentrated hydrochloric acid in the product after the oven dry, at 70 ℃ of lower stirring in water bath 1h; With the slurry suction filtration after stirring, to get solid water and be washed till neutrality, 80 ℃ of oven dry (baking 4h) obtain natural halloysite powder.
The XRD figure spectrum of natural halloysite powder can find out that almost have no other impurity peaks in the collection of illustrative plates, the purity of natural halloysite powder is greater than 95% (quality) as shown in Figure 7.From the field emission scanning electron microscope photo of natural halloysite powder, visible significantly multilayer hollow tubular structures is typical halloysite microscopic appearance feature.
Take by weighing natural halloysite powder (abbreviation halloysite) 5.00g, sucrose 10.00g.
The natural halloysite powder (abbreviation halloysite) that 2) will weigh up first places crucible to be incubated 3 hours under 700 ℃ temperature, be cooled to room temperature, then the HCl that adds 100ml, 2mol/L, filter after 2 hours, wash to neutral in 60 ℃ of lower mechanical stirring, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good.
3) halloysite that will activate again, modification is good and 10.00g sucrose mix in the rear immigration autoclave, and place 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N
2Calcination is 4 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 15 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 20 hours, obtain mesoporous carbon material.
Product is carried out XRD and BET analyzes by the method identical with embodiment 1, confirm that this product is the mesoporous carbon material that has than bigger serface, pore size distribution is narrower and have a multiple mesoporous distribution.N from prepared mesoporous carbon material
2Isothermal adsorption figure and graph of pore diameter distribution can be found out take natural halloysite as template successfully to have synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 490m
2/ g.
Embodiment 4:
Prepare the method for mesoporous carbon material take natural halloysite as template, it may further comprise the steps:
1) preparation of right halloysite powder (abbreviation halloysite) is with embodiment 1;
Take by weighing halloysite 5.00g, measure furfuryl alcohol 8.80ml.
2) first the halloysite that weighs up is placed crucible under 300 ℃ temperature, to be incubated 3 hours, be cooled to room temperature, then add the HNO of 100ml, 2mol/L
3, filter after 2 hours, wash to neutral in 60 ℃ of lower mechanical stirring, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good.
3) halloysite and 8.80ml furfuryl alcohol that modification is good mixes in the rear immigration autoclave again, and places 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N
2Calcination is 4 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 15 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 20 hours, obtain mesoporous carbon material (the finished product).
Product is carried out XRD and BET analyzes by the method identical with embodiment 1, confirm that this product is the mesoporous carbon material that has than bigger serface, pore size distribution is narrower, about 3.6nm.N from prepared mesoporous carbon material
2Isothermal adsorption figure and graph of pore diameter distribution can be found out take natural halloysite as template successfully to have synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 498m
2/ g.
Embodiment 5:
Prepare the method for mesoporous carbon material take natural halloysite as template, it may further comprise the steps:
1) preparation of right halloysite powder (abbreviation halloysite) is with embodiment 1;
Take by weighing halloysite 5.00g, measure furfuryl alcohol 8.80ml.
2) first the halloysite that weighs up is placed crucible under 900 ℃ temperature, to be incubated 3 hours, be cooled to room temperature, then add the HSO of 100ml, 2mol/L
4In filter after 2 hours, wash to neutral in 60 ℃ of lower mechanical stirring, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good.
3) halloysite and 8.80ml furfuryl alcohol that modification is good mixes in the rear immigration autoclave again, and places 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N
2Calcination is 4 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 15 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 24 hours, obtain mesoporous carbon material (the finished product).
Product is carried out XRD and BET analyzes by the method identical with embodiment 1, confirm that this product is the mesoporous carbon material that has than bigger serface, pore size distribution is narrower, about 3.9nm.N from prepared mesoporous carbon material
2Isothermal adsorption figure and graph of pore diameter distribution can be found out take natural halloysite as template successfully to have synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 518m
2/ g.
Embodiment 6:
Prepare the method for mesoporous carbon material take natural halloysite as template, it may further comprise the steps:
1) preparation of right halloysite powder (abbreviation halloysite) is with embodiment 1;
Take by weighing halloysite 5.00g, measure sucrose 5.00g.
2) first the halloysite that weighs up is placed crucible under 300 ℃ temperature, to be incubated 3 hours, be cooled to room temperature, then add the HNO of 100ml, 0.5mol/L
3, filter after 2 hours, wash to neutral in 60 ℃ of lower mechanical stirring, baking is 24 hours in 100 ℃ of baking ovens, the halloysite that activated, modification is good.
3) halloysite and sucrose that modification is good mixes in the rear immigration autoclave again, and places 130 ℃ baking oven insulation to make presoma in 6 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 500 ℃, N
2Calcination is 3 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 15 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 80 ℃ of drying and processings 24 hours, obtain mesoporous carbon material (the finished product).
Product is carried out XRD and BET analyzes by the method identical with embodiment 1, confirm that this product is the mesoporous carbon material that has than bigger serface, pore size distribution is narrower, about 4.3nm.N from prepared mesoporous carbon material
2Isothermal adsorption figure and graph of pore diameter distribution can be found out take natural halloysite as template successfully to have synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 538m
2/ g.
Embodiment 7:
Prepare the method for mesoporous carbon material take natural halloysite as template, it may further comprise the steps:
1) preparation of right halloysite powder (abbreviation halloysite) is with embodiment 1;
Take by weighing halloysite 5.00g, measure sucrose 25.00g.
2) first the halloysite that weighs up is placed crucible under 900 ℃ temperature, to be incubated 3 hours, be cooled to room temperature, then add the HNO of 100ml, 10mol/L
3, filter after 2 hours, wash to neutral in 60 ℃ of lower mechanical stirring, baking is 24 hours in 100 ℃ of baking ovens, the halloysite that activated, modification is good.
3) halloysite and sucrose that modification is good mixes in the rear immigration autoclave again, and places 130 ℃ baking oven insulation to make presoma in 48 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 900 ℃, N
2Calcination is 6 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 15 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 80 ℃ of drying and processings 24 hours, obtain mesoporous carbon material (the finished product).
Product is carried out XRD and BET analyzes by the method identical with embodiment 1, confirm that this product is the mesoporous carbon material that has than bigger serface, pore size distribution is narrower, about 4.5nm.N from prepared mesoporous carbon material
2Isothermal adsorption figure and graph of pore diameter distribution can be found out take natural halloysite as template successfully to have synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 559m
2/ g.
Embodiment 8:
Prepare the method for mesoporous carbon material take natural halloysite as template, it may further comprise the steps:
1) preparation of right halloysite powder (abbreviation halloysite) is with embodiment 1;
Take by weighing halloysite 5.00g, measure glucose 5.00g.
2) first the halloysite that weighs up is placed crucible under 300 ℃ temperature, to be incubated 3 hours, be cooled to room temperature, then add the HNO of 50ml, 2mol/L
3With the HCl of 50ml, 2mol/L, filter after 2 hours, wash to neutral in 60 ℃ of lower mechanical stirring, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good.
3) halloysite and glucose that modification is good mixes in the rear immigration autoclave again, and places 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N
2Calcination is 4 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 15 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 24 hours, obtain mesoporous carbon material (the finished product).
Product is carried out XRD and BET analyzes by the method identical with embodiment 1, confirm that this product is the mesoporous carbon material that has than bigger serface, pore size distribution is narrower, about 4.6nm.N from prepared mesoporous carbon material
2Isothermal adsorption figure and graph of pore diameter distribution can be found out take natural halloysite as template successfully to have synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 563m
2/ g.
Embodiment 9:
Prepare the method for mesoporous carbon material take natural halloysite as template, it may further comprise the steps:
1) preparation of right halloysite powder (abbreviation halloysite) is with embodiment 1;
Take by weighing halloysite 5.00g, measure glucose 15.00g.
2) first the halloysite that weighs up is placed crucible under 300 ℃ temperature, to be incubated 3 hours, be cooled to room temperature, then add the HNO of 50ml, 2mol/L
3H with 50ml, 2mol/L
2SO
4, filter after 2 hours, wash to neutral in 60 ℃ of lower mechanical stirring, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good.
3) halloysite and glucose that modification is good mixes in the rear immigration autoclave again, and places 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N
2Calcination is 4 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 15 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 24 hours, obtain mesoporous carbon material (the finished product).
Product is carried out XRD and BET analyzes by the method identical with embodiment 1, confirm that this product is the mesoporous carbon material that has than bigger serface, pore size distribution is narrower, about 5.2nm.N from prepared mesoporous carbon material
2Isothermal adsorption figure and graph of pore diameter distribution can be found out take natural halloysite as template successfully to have synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 571m
2/ g.
Embodiment 10:
Prepare the method for mesoporous carbon material take natural halloysite as template, it may further comprise the steps:
1) preparation of right halloysite powder (abbreviation halloysite) is with embodiment 1;
Take by weighing halloysite 25.00g, measure glucose 5.00g.
2) first the halloysite that weighs up is placed crucible under 300 ℃ temperature, to be incubated 3 hours, be cooled to room temperature, then add the H of 50ml, 2mol/L
2SO
4With the HCl of 50ml, 2mol/L, filter after 2 hours, wash to neutral in 60 ℃ of lower mechanical stirring, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good.
3) halloysite and glucose that modification is good mixes in the rear immigration autoclave again, and places 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N
2Calcination is 4 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 24 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 24 hours, obtain mesoporous carbon material (the finished product).
Product is carried out XRD and BET analyzes by the method identical with embodiment 1, confirm that this product is the mesoporous carbon material that has than bigger serface, pore size distribution is narrower, about 6.1nm.N from prepared mesoporous carbon material
2Isothermal adsorption figure and graph of pore diameter distribution can be found out take natural halloysite as template successfully to have synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 584m
2/ g.
Embodiment 11:
Prepare the method for mesoporous carbon material take natural halloysite as template, it may further comprise the steps:
1) preparation of right halloysite powder (abbreviation halloysite) is with embodiment 1;
Take by weighing halloysite 15.00g, measure sucrose 5.00g.
2) first the halloysite that weighs up is placed crucible under 300 ℃ temperature, to be incubated 3 hours, be cooled to room temperature, then add the HNO of 25ml, 2mol/L
3With the HCl of 25ml, 2mol/L and the H of 50ml, 2mol/L
2SO
4, filter after 2 hours, wash to neutral in 60 ℃ of lower mechanical stirring, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good.
3) halloysite and sucrose that modification is good mixes in the rear immigration autoclave again, and places 180 ℃ baking oven insulation to make presoma in 24 hours autoclave.
4) presoma is placed porcelain boat, then porcelain boat is put into tube type high-temperature furnace, in 800 ℃, N
2Calcination is 4 hours in the atmosphere, and calcination treats that sample cools to room temperature with the furnace after finishing, then take out sample and removed the mineral template in 24 hours with the HF washing, at last with deionized water with sample washing to neutral, filter, in 100 ℃ of drying and processings 24 hours, obtain mesoporous carbon material (the finished product).
Product is carried out XRD and BET analyzes by the method identical with embodiment 1, confirm that this product is the mesoporous carbon material that has than bigger serface, pore size distribution is narrower, about 7.8nm.N from prepared mesoporous carbon material
2Isothermal adsorption figure and graph of pore diameter distribution can be found out take natural halloysite as template successfully to have synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 591m
2/ g.
Claims (4)
1. the method for preparing mesoporous carbon material take natural halloysite as template is characterized in that it may further comprise the steps:
1) mass ratio by natural halloysite powder and carbon source is 1:1～5, chooses natural halloysite powder and carbon source, and is for subsequent use;
The preparation of described natural halloysite powder, it comprises the steps:
1. the quality percentage composition with halloysite is made into the suspension that concentration is 10-20 wt% at natural halloysite raw ore and the water of 30-50 %;
2. the add-on by Sodium hexametaphosphate 99 is the 0.2-0.5 % of natural halloysite ore quality, adds Sodium hexametaphosphate 99 in suspension, and mechanical stirring 2-4 h obtains slurry;
3. the slurry after will stirring is put into the whizzer centrifugation, rotating speed 1500-2000 r/min, and the centrifugation time is 5-10 min; After centrifugal, lower sediment is removed, get upper strata suspension, recentrifuge, rotating speed 3000-3800 r/min, the time is 5-10 min, obtains for the second time centrifugal throw out;
4. get for the second time centrifugal throw out, 80-100 ℃ of oven dry, the product after obtaining drying, for subsequent use;
5. get the product after the oven dry, according to natural halloysite raw ore: the ratio of the mass ratio=1:30-1:70 of hydrochloric acid adds concentrated hydrochloric acid in the product after the oven dry, at 70-80 ℃ of lower stirring in water bath 1-10 h; With the slurry suction filtration after stirring, to get solid water and be washed till neutrality, 80-100 ℃ of oven dry obtains the natural halloysite powder of tubular structure, purity 〉=95 wt%;
2) proportioning by natural halloysite powder and acid is 5g:100mL, chooses acid; Be 300 ℃～900 ℃ lower insulations 3 hours with natural halloysite powder in temperature first, then add acid, mechanical stirring is filtered after 2 hours, is washed to neutral, dries by the fire 24～36 hours the halloysite that activated, modification is good in 85～100 ℃ of baking ovens;
3) halloysite and the carbon source that will activate, modification are good mix, and obtain halloysite/Carbon composites; Halloysite/Carbon composites is placed in the autoclave, and autoclave places the baking oven case, and insulation is 6h-48h hour under 130 ℃ of-180 ℃ of temperature, obtains presoma;
4) with presoma in 500 ℃～900 ℃, N
2Carry out calcination 3～6 hours under the atmosphere of protection, cool to product with the furnace room temperature after the calcination end, removed template in the product in 15～24 hours with the HF washing, extremely neutral with deionized water wash again, filter, dry, obtain mesoporous carbon material.
2. the method for preparing mesoporous carbon material take natural halloysite as template according to claim 1, it is characterized in that: carbon source is furfuryl alcohol or sucrose or glucose.
3. the method for preparing mesoporous carbon material take natural halloysite as template according to claim 1 is characterized in that: acid is HCl, HNO
3, H
2SO
4In any or several solution by any mixed in molar ratio; The volumetric molar concentration of acid is 0.5mol/L～10mol/L.
4. the method for preparing mesoporous carbon material take natural halloysite as template according to claim 1 is characterized in that: step 4) in bake out temperature be 80 ℃-100 ℃, the time is 12～24 hours.
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| CN106925284A (en) * | 2015-12-29 | 2017-07-07 | 天津市英派克石化工程有限公司 | A kind of preparation method of high efficiency, low cost desulfurization catalyst of flue gas |
| CN105664848A (en) * | 2016-01-14 | 2016-06-15 | 江苏大学 | Preparation method of lignin hierarchical porous carbon material with endellite as template |
| CN105967167B (en) * | 2016-05-17 | 2018-01-09 | 扬州大学 | A kind of method for preparing one-dimensional carbon nano material |
| CN106044770B (en) * | 2016-05-31 | 2019-08-02 | 江苏大学 | A kind of method that galapectite prepares cellulose base multi-stage porous carbon material for template |
| WO2019208646A1 (en) * | 2018-04-25 | 2019-10-31 | Ｊｆｅミネラル株式会社 | Metahalloysite powder and production method therefor |
| CN111285350B (en) * | 2018-12-10 | 2022-09-30 | 河南工程学院 | Preparation method of micro-mesoporous carbon nanocapsule net |
| CN111285368B (en) * | 2018-12-10 | 2022-05-27 | 河南工程学院 | Preparation method of nitrogen-boron double-doped porous hollow carbon nano-capsule material |
| CN117778116B (en) * | 2024-02-28 | 2024-06-07 | 山东海化集团有限公司 | Preparation method and application of Pickering microemulsion sterilization and decontamination agent |
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| JP昭57-200214A 1982.12.08 |
| 姚七妹等.模板法制备多孔炭材料的研究进展.《炭素技术》.2005,第24卷(第4期),第15-21页. * |
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