CN102303861A - Method for preparing mesoporous carbon material based on natural halloysite as template - Google Patents
Method for preparing mesoporous carbon material based on natural halloysite as template Download PDFInfo
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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 is the method that template prepares mesoporous carbon material with natural halloysite.
Background technology
Mesoporous charcoal 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 charcoal 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 promptly is situated between; Its aperture is controlled easily simultaneously, is an important branch of porous carbon material.Mesoporous carbon material demonstrates the trend that replaces traditional raw material of wood-charcoal material with its higher specific surface area, narrower pore size distribution, fabulous chemistry and thermostability.Since it is born, be the emphasis of material circle research always.
1992; The Beck of U.S. Mobil company etc. uses the nanometer self-assembling technique successfully to synthesize to have regular pore passage structure, aperture to have opened up the new milestone of molecular screen material research at adjustable novel crystallization M41S series silicon oxide (aluminium) ordered mesoporous molecular sieve of 1.0～10.0nm first.Since then, design and exploitation have the type material of meticulous pore passage structure, because it has huge pushing effect to industrial development, are important advanced fields of Materials science research always.
In recent years, inorganic chemists are devoted to the research and development of mesoporous material on molecular sieve synthetic basis, have obtained very big progress, have synthesized a series of mesoporous (2.0～50.0nm) materials.Especially synthetic mesoporous carbon material with nano-pore structure causes the extensive interest of people in recent years, and this type material demonstrates good prospects for application in fields such as absorption, catalysis, electronics.
The synthesis 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 the katalysis to the gasification of carbon of metal and compound thereof; Like patent CN101367514 is structure directing agent with the segmented copolymer; Resin is a carbon matrix precursor; Solid alkali is a catalyzer; Organic/organic double compound the film that in non-aqueous solvent, adopts colloidal sol-gel technique to be assembled into earlier, charing obtains ordered mesoporous carbon then.Though 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 for a short time, 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 catalytic activation legal system is equipped with mesoporous carbon material, and it is inevitably that metal gets into raw material of wood-charcoal material inside, and has a large amount of micropores with the mesoporous charcoal that this method makes.
2. organogel charring
The organogel charring is the organogel of charing by the sol gel reaction preparation; Like 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 charing in advance, go silication to obtain ordered mesoporous carbon material.Though the mesoporous carbon material that synthesizes has regularly arranged pore passage structure, bigger specific surface area, the mesoporous of gained is the space that at least partly links to each other, and expensive and complicated supercritical drying equipment is restricting its commercialization.
3. template
Template is divided into organic formwork method and inorganic template; Through selecting for use a kind of material as template with special pore texture; 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 physics in the preparation process and chemical reaction are regulated and control, finally obtain microcosmic and macrostructure controlled and on traditional sense diverse mesoporous charcoal novel material.The characteristics that template is the most outstanding are to have good controllable structure system property, and it provides one can control and improve the effective means that nanoparticle is arranged in structured material.Prepared in this way material has the constitutional features similar with the template vestibule, if the template that adopts has the aperture of homogeneous, then institute's synthetic nano material also will have uniform structure.All adopt the organic formwork method like the mesoporous material of announcements such as patent CN101279857, CN101417810, CN101462737, CN101362598 and the preparation method of mesoporous carbon material, synthetic through assembling under strong acidic condition.
In sum, template is the effective ways of control mesoporous rate and pore structure, size.Up to the present, be not template, prepare the relevant report of mesoporous carbon material through hydrothermal synthesis reaction with natural halloysite, 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 is the method that template prepares mesoporous carbon material with natural halloysite, and the mesoporous carbon material of this 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: with natural halloysite is the method that template prepares mesoporous carbon material, 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 subsequent use; The halloysite that described natural halloysite powder is a tubular structure, purity >=95wt%;
2) be 5g: 100mL by natural halloysite powder with sour proportioning, choose acid; Be 300 ℃～900 ℃ 3 hours (thermal activation treatment) of insulation down with natural halloysite powder in temperature earlier; Add acid then; 2 hours after-filtration of mechanical stirring, washing were dried by the fire 24～36 hours the halloysite that activated, modification is good to neutral in 85～100 ℃ of baking ovens;
3) halloysite and the carbon source that will activate, modification are good mix, and obtain halloysite/charcoal mixture; Halloysite/charcoal mixture 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
2Carried 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.
The preparation of the said natural halloysite powder of step 1), it comprises the steps:
1) the quality percentage composition with halloysite is made into the suspension-s that concentration is 10-20wt% (quality) (containing the 10-20g raw ore in the expression 100g suspension-s) 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, in suspension-s, adds Sodium hexametaphosphate 99, 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-s, recentrifuge, rotating speed 3000-3800r/min, the time is 5-10min, obtains centrifugal throw out for the second time;
4) get centrifugal throw out for the second time, 80-100 ℃ of oven dry (baking 5-8h), the product after obtaining drying, 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 oven dry, at 70-80 ℃ of following 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 said 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 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%.
With natural halloysite is that template prepares the mesoporous carbon material ultimate principle: adopt methods such as liquid impregnation, vapour deposition, hydro-thermal be synthetic organism evenly to be placed the hole of natural halloysite template; Then mixture is carried out high temperature carbonization; Obtain natural halloysite/charcoal mixture; Remove template, the mesoporous carbon material that promptly obtains having template inorganics network structure characteristic with acid again.The biggest advantage that adopts natural halloysite to make template is that raw material sources are extensive, cheap.
Compared with prior art, the advantage that the present invention has is: it is that template has successfully been synthesized mesoporous carbon material with natural halloysite that the present invention adopts template, and this mesoporous carbon material has higher specific surface area (400m
2/ g～600m
2/ g), illustrate that this mesoporous carbon material has absorption property preferably; 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 spot of micropore and macropore and have triple pore size distributions), and this synthesis 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 the present invention better, further illustrate content of the present invention below in conjunction with instance, but the present invention not only is confined to the following examples.
Embodiment 1:
With natural halloysite is the method that template prepares mesoporous carbon material, and it may further comprise the steps:
1) preparation of natural halloysite powder, it comprises the steps:
1. be that 50% natural halloysite raw ore (the main composition of natural halloysite comprises halloysite, kaolinite, illite, gibbsite, quartz and feldspar, sees Fig. 4) and water are made into the suspension-s that concentration is 20wt% (quality) (containing the 20g raw ore in the expression 100g suspension-s) with the quality percentage composition of halloysite;
2. the add-on by Sodium hexametaphosphate 99 is 0.2% of an ore quality, in suspension-s, adds Sodium hexametaphosphate 99, 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-s, recentrifuge, rotating speed 3800r/min, time 10min obtains centrifugal throw out for the second time;
4. get centrifugal throw out for the second time, 100 ℃ of oven dry (baking 5h), the product after obtaining drying, 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 following 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 do not see other impurity peaks in the collection of illustrative plates, the halloysite product gas purity 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 characteristic 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 earlier places crucible under 700 ℃ temperature, to be incubated 3 hours; Be cooled to room temperature; The HCl that adds 100ml, 2mol/L then; In 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing to neutral (pH is 6～8); 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 the back and move in the 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; Taking out sample then uses concentration to remove the mineral template in 15 hours as the HF washing of 40wt%; With deionized water sample is washed to neutral (pH is 6～8), filters at last; Handled 20 hours in 100 ℃ of oven dry, 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, a diffraction bag near 23 ° and 44 °, all occurs, 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 can find out with natural halloysite to be that template has successfully synthesized mesoporous carbon material with hydrothermal method from Fig. 2 and Fig. 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:
With natural halloysite is the method that template prepares mesoporous carbon material, and it may further comprise the steps:
1) preparation of natural halloysite powder, it comprises the steps:
1. be that 40% natural halloysite raw ore (the main composition of natural halloysite comprises halloysite, kaolinite, illite, gibbsite, quartz and feldspar, sees Fig. 4) and water are made into the suspension-s that concentration is 15wt% (quality) (containing the 15g raw ore in the expression 100g suspension-s) with the quality percentage composition of halloysite;
2. the add-on by Sodium hexametaphosphate 99 is 0.3% of an ore quality, in suspension-s, adds Sodium hexametaphosphate 99, 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-s, recentrifuge, rotating speed 3000r/min, time 5min obtains centrifugal throw out for the second time;
4. get centrifugal throw out for the second time, 100 ℃ of oven dry (5h), the product after obtaining drying, 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 oven dry, at 80 ℃ of following 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 do not see 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 characteristic.
Take by weighing natural halloysite powder (abbreviation halloysite) 5.00g, glucose 10.00g.
The natural halloysite powder (abbreviation halloysite) that 2) will weigh up earlier places crucible under 600 ℃ temperature, to be incubated 3 hours; Be cooled to room temperature; The HCl that adds 100ml, 2mol/L then; In 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing to neutral; 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 the back and move in the 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; Take out sample then and removed the mineral template in 15 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 22 hours in 100 ℃ of oven dry, obtained mesoporous carbon material (the finished product).
By product being carried out XRD and BET analysis with embodiment 1 identical method, 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 find out with natural halloysite to be that template has successfully synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 470m
2/ g.
Embodiment 3:
With natural halloysite is the method that template prepares mesoporous carbon material, and it may further comprise the steps:
1) preparation of natural halloysite powder, it comprises the steps:
1. the natural halloysite raw ore (the main composition 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-s that concentration is 10% (quality) (containing the 10g raw ore in the expression 100g suspension-s);
2. the add-on by Sodium hexametaphosphate 99 is 0.5% of an ore quality, in suspension-s, adds Sodium hexametaphosphate 99, 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-s, recentrifuge, rotating speed 3800r/min, time 5min obtains centrifugal throw out for the second time;
4. get centrifugal throw out for the second time, 80 ℃ of oven dry (baking 8h), the product after obtaining drying, 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 oven dry, at 70 ℃ of following 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 do not see 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 characteristic.
Take by weighing natural halloysite powder (abbreviation halloysite) 5.00g, sucrose 10.00g.
The natural halloysite powder (abbreviation halloysite) that 2) will weigh up earlier places crucible under 700 ℃ temperature, to be incubated 3 hours; Be cooled to room temperature; The HCl that adds 100ml, 2mol/L then; In 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing to neutral; 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 the back and move in the 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; Take out sample then and removed the mineral template in 15 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 20 hours in 100 ℃ of oven dry, obtained 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 find out with natural halloysite to be that template has successfully synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 490m
2/ g.
Embodiment 4:
With natural halloysite is the method that template prepares mesoporous carbon material, and 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) place crucible under 300 ℃ temperature, to be incubated 3 hours the halloysite that weighs up earlier, be cooled to room temperature, add the HNO of 100ml, 2mol/L then
3, to neutral, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing.
3) again that modification is good halloysite and 8.80ml furfuryl alcohol mix in the back 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; Take out sample then and removed the mineral template in 15 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 20 hours in 100 ℃ of oven dry, obtained mesoporous carbon material (the finished product).
By product being carried out XRD and BET analysis with embodiment 1 identical method, 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 find out with natural halloysite to be that template has successfully synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 498m
2/ g.
Embodiment 5:
With natural halloysite is the method that template prepares mesoporous carbon material, and 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) place crucible under 900 ℃ temperature, to be incubated 3 hours the halloysite that weighs up earlier, be cooled to room temperature, add the HSO of 100ml, 2mol/L then
4In in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing to neutral, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good.
3) again that modification is good halloysite and 8.80ml furfuryl alcohol mix in the back 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; Take out sample then and removed the mineral template in 15 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 24 hours in 100 ℃ of oven dry, obtained mesoporous carbon material (the finished product).
By product being carried out XRD and BET analysis with embodiment 1 identical method, 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 find out with natural halloysite to be that template has successfully synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 518m
2/ g.
Embodiment 6:
With natural halloysite is the method that template prepares mesoporous carbon material, and 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) place crucible under 300 ℃ temperature, to be incubated 3 hours the halloysite that weighs up earlier, be cooled to room temperature, add the HNO of 100ml, 0.5mol/L then
3, to neutral, baking is 24 hours in 100 ℃ of baking ovens, the halloysite that activated, modification is good in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing.
3) again that modification is good halloysite and sucrose mix in the back immigration autoclave, and place 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; Take out sample then and removed the mineral template in 15 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 24 hours in 80 ℃ of oven dry, obtained mesoporous carbon material (the finished product).
By product being carried out XRD and BET analysis with embodiment 1 identical method, 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 find out with natural halloysite to be that template has successfully synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 538m
2/ g.
Embodiment 7:
With natural halloysite is the method that template prepares mesoporous carbon material, and 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) place crucible under 900 ℃ temperature, to be incubated 3 hours the halloysite that weighs up earlier, be cooled to room temperature, add the HNO of 100ml, 10mol/L then
3, to neutral, baking is 24 hours in 100 ℃ of baking ovens, the halloysite that activated, modification is good in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing.
3) again that modification is good halloysite and sucrose mix in the back immigration autoclave, and place 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; Take out sample then and removed the mineral template in 15 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 24 hours in 80 ℃ of oven dry, obtained mesoporous carbon material (the finished product).
By product being carried out XRD and BET analysis with embodiment 1 identical method, 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 find out with natural halloysite to be that template has successfully synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 559m
2/ g.
Embodiment 8:
With natural halloysite is the method that template prepares mesoporous carbon material, and 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) place crucible under 300 ℃ temperature, to be incubated 3 hours the halloysite that weighs up earlier, be cooled to room temperature, add the HNO of 50ml, 2mol/L then
3With the HCl of 50ml, 2mol/L, to neutral, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing.
3) again that modification is good halloysite and glucose mix in the back 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; Take out sample then and removed the mineral template in 15 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 24 hours in 100 ℃ of oven dry, obtained mesoporous carbon material (the finished product).
By product being carried out XRD and BET analysis with embodiment 1 identical method, 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 find out with natural halloysite to be that template has successfully synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 563m
2/ g.
Embodiment 9:
With natural halloysite is the method that template prepares mesoporous carbon material, and 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) place crucible under 300 ℃ temperature, to be incubated 3 hours the halloysite that weighs up earlier, be cooled to room temperature, add the HNO of 50ml, 2mol/L then
3H with 50ml, 2mol/L
2SO
4, to neutral, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing.
3) again that modification is good halloysite and glucose mix in the back 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; Take out sample then and removed the mineral template in 15 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 24 hours in 100 ℃ of oven dry, obtained mesoporous carbon material (the finished product).
By product being carried out XRD and BET analysis with embodiment 1 identical method, 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 find out with natural halloysite to be that template has successfully synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 571m
2/ g.
Embodiment 10:
With natural halloysite is the method that template prepares mesoporous carbon material, and 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) place crucible under 300 ℃ temperature, to be incubated 3 hours the halloysite that weighs up earlier, be cooled to room temperature, add the H of 50ml, 2mol/L then
2SO
4With the HCl of 50ml, 2mol/L, to neutral, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing.
3) again that modification is good halloysite and glucose mix in the back 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; Take out sample then and removed the mineral template in 24 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 24 hours in 100 ℃ of oven dry, obtained mesoporous carbon material (the finished product).
By product being carried out XRD and BET analysis with embodiment 1 identical method, 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 find out with natural halloysite to be that template has successfully synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 584m
2/ g.
Embodiment 11:
With natural halloysite is the method that template prepares mesoporous carbon material, and 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) place crucible under 300 ℃ temperature, to be incubated 3 hours the halloysite that weighs up earlier, be cooled to room temperature, add the HNO of 25ml, 2mol/L then
3H with the HCl of 25ml, 2mol/L and 50ml, 2mol/L
2SO
4, to neutral, baking is 24 hours in 85 ℃ of baking ovens, the halloysite that activated, modification is good in 2 hours after-filtration of 60 ℃ of following mechanical stirring, washing.
3) again that modification is good halloysite and sucrose mix in the back 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; Take out sample then and removed the mineral template in 24 hours with the HF washing; With deionized water that the sample washing is extremely neutral at last, filtration were handled 24 hours in 100 ℃ of oven dry, obtained mesoporous carbon material (the finished product).
By product being carried out XRD and BET analysis with embodiment 1 identical method, 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 find out with natural halloysite to be that template has successfully synthesized mesoporous carbon material with hydrothermal method.The specific surface area of this mesoporous carbon material is 591m
2/ g.
Claims (6)
1. be the method that template prepares mesoporous carbon material with natural halloysite, 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 subsequent use; The halloysite that described natural halloysite powder is a tubular structure, purity >=95wt%;
2) be 5g: 100mL by natural halloysite powder with sour proportioning, choose acid; Be 300 ℃～900 ℃ insulations 3 hours down with natural halloysite powder in temperature earlier, add acid then, 2 hours after-filtration of mechanical stirring, washing were dried by the fire 24～36 hours the halloysite that activated, modification is good to neutral in 85～100 ℃ of baking ovens;
3) halloysite and the carbon source that will activate, modification are good mix, and obtain halloysite/charcoal mixture; Halloysite/charcoal mixture 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
2Carried 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. according to claim 1 is the method that template prepares mesoporous carbon material with natural halloysite, it is characterized in that: the preparation of the said natural halloysite powder of step 1), it comprises the steps:
1) the quality percentage composition with halloysite is made into the suspension-s that concentration is 10-20wt% 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, in suspension-s, adds Sodium hexametaphosphate 99, 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-s, recentrifuge, rotating speed 3000-3800r/min, the time is 5-10min, obtains centrifugal throw out for the second time;
4) get centrifugal throw out for the second time, 80-100 ℃ of oven dry, the product after obtaining drying, 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 oven dry, at 70-80 ℃ of following 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 obtains the natural halloysite powder of tubular structure, purity >=95wt%.
3. according to claim 1 and 2 is the method that template prepares mesoporous carbon material with natural halloysite, it is characterized in that: the Chemical Composition of said 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%; The median size of natural halloysite powder is 5.226um.
4. according to claim 1 is the method that template prepares mesoporous carbon material with natural halloysite, it is characterized in that: carbon source is furfuryl alcohol or sucrose or glucose.
5. according to claim 1 is the method that template prepares mesoporous carbon material with natural halloysite, it 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.
6. according to claim 1 is the method that template prepares mesoporous carbon material with natural halloysite, it is characterized in that: the bake out temperature in the step 4) is 80 ℃-100 ℃, and the time is 12～24 hours.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103086396A (en) * | 2012-12-17 | 2013-05-08 | 青岛博益特生物材料有限公司 | Method for preparing mesoporous material by using perlite |
| CN105664848A (en) * | 2016-01-14 | 2016-06-15 | 江苏大学 | Preparation method of lignin hierarchical porous carbon material with endellite as template |
| CN105967167A (en) * | 2016-05-17 | 2016-09-28 | 扬州大学 | Method for preparing one-dimensional carbon nano material |
| CN106044770A (en) * | 2016-05-31 | 2016-10-26 | 江苏大学 | Method for preparing cellulose base hierarchical porous carbon material by adopting halloysite as template |
| 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 |
| CN111285368A (en) * | 2018-12-10 | 2020-06-16 | 河南工程学院 | Preparation method of nitrogen-boron double-doped porous hollow carbon nano-capsule material |
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| CN112004778A (en) * | 2018-04-25 | 2020-11-27 | 杰富意矿物股份有限公司 | Quasi halloysite powder and method for producing same |
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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 |
| CN105967167A (en) * | 2016-05-17 | 2016-09-28 | 扬州大学 | 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 |
| CN106044770A (en) * | 2016-05-31 | 2016-10-26 | 江苏大学 | Method for preparing cellulose base hierarchical porous carbon material by adopting halloysite as template |
| CN112004778A (en) * | 2018-04-25 | 2020-11-27 | 杰富意矿物股份有限公司 | Quasi halloysite powder and method for producing same |
| CN112004778B (en) * | 2018-04-25 | 2023-09-12 | 杰富意矿物股份有限公司 | Quasi halloysite powder and method for producing same |
| CN111285368A (en) * | 2018-12-10 | 2020-06-16 | 河南工程学院 | Preparation method of nitrogen-boron double-doped porous hollow carbon nano-capsule material |
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| CN111285350B (en) * | 2018-12-10 | 2022-09-30 | 河南工程学院 | Preparation method of micro-mesoporous carbon nanocapsule net |
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