CN102976305A - Preparation method of mesoporous carbon material with aperture regulated by using template method - Google Patents
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Abstract
The invention relates to a preparation method of a mesoporous carbon material with an aperture regulated by using a template method, and belongs to the technical field of a conducting material. The method comprises the steps of: synthetizing a mesoporous silica ball as a template, taking synthetized phenolic resin as a carbon precursor; preparing a phenolic resin/template compound; and preparing a carbon/template composite material, and further removing the template to prepare the mesoporous carbon material. Ordered mesoporous carbon electrodes with different apertures can be finally obtained by regulating the additive amount of the mesoporous silica ball. The preparation materials used in the method disclosed by the invention are commercially available goods and easily obtained; and according to the preparation method, the preparation process is simple and the operation is convenient, and the mesoporous carbon material which can not be prepared by using the common activation method and has a single aperture can be obtained.
Description
Technical field
The present invention relates to the preparation method of the Mesoporous Carbon Materials in a kind of template regulation and control aperture, belong to the conducting material technical field.
Background technology
The ordered mesoporous Carbon Materials is that a class has regular pore canal arrangement, aperture at 2 ~ 50nm, the Carbon Materials of hole dimension homogeneous.The ordered mesoporous Carbon Materials has the moderate and narrow characteristics of pore size distribution of specific surface area, and has electrochemical stability height, physical strength height and the good characteristics of electroconductibility.Not only separating, adsorbing organic macromolecule, and all having a good application prospect at aspects such as support of the catalyst, ultracapacitor, electro-adsorption demineralization and conducting materials.
International pure chemistry is divided into the aperture of sorbent material with application association: the macropore of aperture W＞50nm; The mesopore of 2nm＜W＜50nm, the micropore of W＜2nm.The gac of conventional physical activation method and chemical activation method preparation is mainly take micropore as main
Template be a kind of method by template in the method for the structure of nanoscale scope internal control charcoal processing presoma, make the large cancellated Carbon Materials of narrow pore size distribution and specific surface area.Because the template charcoal can be good at controlling the aperture, so that it becomes a kind of sorbing material with better prospect.Common activated carbon application is when adsorbing domain, and micropore can't adsorb macromolecular organism.In the electro-adsorption demineralization field, can there be the electrostatic double layer eclipsing effect in micropore, can't form electrostatic double layer in inside, duct, thereby a large amount of micropore can't take full advantage of.Also require in addition Carbon Materials to have flourishing mesopore in fields such as some emerging catalytic carriers and electrostatic double layer energy storage.Therefore, the regulation and control of mesopore are one of gordian techniquies of porous carbon material preparation.
The preparation method about Mesoporous Carbon Materials who has now reported mainly contains: (1) catalytic activation method: sneak into soluble salt (such as nitric acid), transition metal or scarce metallic compound in presoma, then activate, utilize that element reaches the purpose of reaming to the katalysis of the gasification of charcoal under the high temperature, but there is metal residual inevitably in the mesoporous carbon that makes; (2) pore-creating agent method: select two kinds of polymkeric substance with differing thermal stabilities, fully mix, polymerization is carried out charing to mixed polymer again.When pyroprocessing, a kind of unaltered charcoal skeleton of original-shape that is called, another kind is decomposed into gas and leaves matrix, thereby forms central hole structure; (3) high temperature reforming process: existing porous material is carried out physically activated, chemical activation or unites activation, make the pore size distribution after the modification more even, it is little usually the distribution in aperture to be changed amplitude.
Summary of the invention
The objective of the invention is to propose the preparation method of the Mesoporous Carbon Materials in a kind of template regulation and control aperture, simplify the preparation technology of mesoporous carbon, reduce preparation cost, be beneficial to prepare in a large number structurally ordered (single aperture), mesoporous carbon that the aperture is adjustable.
The preparation method of the Mesoporous Carbon Materials in the template regulation and control aperture that the present invention proposes may further comprise the steps:
(1) at room temperature, with polyethers P123(polyoxyethylene-poly-oxypropylene polyoxyethylene) be dissolved in hydrochloric acid soln, the volumetric molar concentration of hydrochloric acid is 2～5 mol/L, make solution temperature rise to 40～60 ℃, added the Three methyl Benzene continuously stirring 2～5 hours, then adding tetraethoxy stirred 10～20 minutes, the mixed solution of making at room temperature aging 24～48 hours, mixed solution is filtered, after water and low-carbon alcohol are cleaned, 600 ~ 900 ℃ of lower calcinings, calcination time is 2～4 hours, obtains the agent of mesoporous silica ball template;
(2) with phenol in molar ratio (10～12): 1 ratio slowly joins in the sodium hydroxide solution that volumetric molar concentration is 2～5 mol/L, and heat to 40 ℃, make the phenol dissolving, be that the formaldehyde solution of 10 mol/L～12 mol/L splashes into volumetric molar concentration, the mol ratio that makes phenol and formaldehyde is 1:(1～3), mixed solution was 60～80 ℃ of stirring reactions 1 hour, after being cooled to room temperature, the pH value of adjusting mixed solution with hydrochloric acid soln is 7.0, under 50～70 ℃, in vacuum, make the mixed solution dehydration, obtain resol;
(3) with polyethers F127(polyethylene oxide-poly(propylene oxide)-polyethylene oxide) be dissolved in the low-carbon alcohol, heat to 40 ℃ and dissolve, add the resol that step (2) obtains, the mass ratio that makes polyethers F127 and resol is 1:(1～2), the mesoporous silica ball template agent that the rear adding step (1) that stirs obtains, make the mass ratio of the agent of mesoporous silica ball template and resol be (0.2～1): 1, in 40 ℃ of lower stirrings 1 hour, with mixing solutions supersound process 15～30 minutes, under 40～70 ℃, stirred 8～12 hours, and 105～130 ℃ of heating 24 hours, obtained resol/silicon oxide mixture;
(4) resol that step (3) is obtained/silicon oxide mixture is inserted charing in the atmosphere furnace, speed with 2～5 liter/mins of clocks passes into high pure nitrogen, temperature rise rate with 2～5 ℃/minute, temperature is risen to 900 ℃, little 900 ℃ of maintenances 2～4, cool to room temperature with the furnace, obtain charcoal/silica composite material;
(5) charcoal/silica composite material that step (4) is obtained, be ground to particle size range at 50 ~ 100 orders, charcoal/silica composite material particle is put into the hydrofluoric acid solution that volumetric molar concentration is 5～10 mol/L, soaked 24 hours 50～60 ℃ of lower water-baths, filter to isolate the charcoal particle, use deionized water wash, namely get Mesoporous Carbon Materials after the drying.
The preparation method of the Mesoporous Carbon Materials in the template regulation and control aperture that the present invention proposes, its advantage is:
1, proposed a kind of method of the mesoporous carbon based on the single aperture of template synthesis among the present invention, raw materials is the commercial goods, obtains easily.Making processes is simple, easy to operate, can obtain the single aperture Mesoporous Carbon Materials that conventional activation method can't make.
2, under the sonic oscillation condition, resol is entered in the duct of mesoporous silica ball fully, the pore size distribution of Carbon Materials and pore volume can be controlled by the ratio that changes template and resol.
3, at first the mesoporous carbon that makes to be ground to particle diameter be 50 ~ 100 orders in the present invention, and less particle diameter is conducive to the inside, duct that HF solution enters Carbon Materials and removes template, is aided with simultaneously certain heating measure, thereby effectively removes template, and then shorten preparation cycle.
Description of drawings
Fig. 1 is among the embodiment 1 of the inventive method, the N of the Mesoporous Carbon Materials that obtains when resol adds different mesoporous silica ball template agent
2Adsorption isothermal line is synoptic diagram relatively.
Fig. 2 is among the embodiment 1 of the inventive method, and the pore size distribution of the Mesoporous Carbon Materials that obtains when resol adds different mesoporous silica ball template agent is synoptic diagram relatively.
Embodiment
The preparation method of the Mesoporous Carbon Materials in the template regulation and control aperture that the inventive method proposes comprises the steps:
(1) at room temperature, with polyethers P123(polyoxyethylene-poly-oxypropylene polyoxyethylene) be dissolved in hydrochloric acid soln, the volumetric molar concentration of hydrochloric acid is 2～5 mol/L, make solution temperature rise to 40～60 ℃, added the Three methyl Benzene continuously stirring 2～5 hours, then adding tetraethoxy stirred 10～20 minutes, the mixed solution of making at room temperature aging 24～48 hours, mixed solution is filtered, after water and low-carbon alcohol are cleaned, 600 ~ 900 ℃ of lower calcinings, calcination time is 2～4 hours, obtains the agent of mesoporous silica ball template;
(2) with phenol in molar ratio (10～12): 1 ratio slowly joins in the sodium hydroxide solution that volumetric molar concentration is 2～5 mol/L, and heat to 40 ℃, make the phenol dissolving, be that the formaldehyde solution of 10 mol/L～12 mol/L splashes into volumetric molar concentration, the mol ratio that makes phenol and formaldehyde is 1:(1～3), mixed solution was 60～80 ℃ of stirring reactions 1 hour, after being cooled to room temperature, the pH value of adjusting mixed solution with hydrochloric acid soln is 7.0, under 50～70 ℃, in vacuum, make the mixed solution dehydration, obtain resol;
(3) with polyethers F127(polyethylene oxide-poly(propylene oxide)-polyethylene oxide) be dissolved in the low-carbon alcohol, heat to 40 ℃ and dissolve, add the resol that step (2) obtains, the mass ratio that makes polyethers F127 and resol is 1:(1～2), the mesoporous silica ball template agent that the rear adding step (1) that stirs obtains, make the mass ratio of the agent of mesoporous silica ball template and resol be (0.2～1): 1, in 40 ℃ of lower stirrings 1 hour, with mixing solutions supersound process 15～30 minutes, under 40～70 ℃, stirred 8～12 hours, and 105～130 ℃ of heating 24 hours, obtained resol/silicon oxide mixture;
(4) resol that step (3) is obtained/silicon oxide mixture is inserted charing in the atmosphere furnace, speed with 2～5 liter/mins of clocks passes into high pure nitrogen, temperature rise rate with 2～5 ℃/minute, temperature is risen to 900 ℃, little 900 ℃ of maintenances 2～4, cool to room temperature with the furnace, obtain charcoal/silica composite material;
(5) charcoal/silica composite material that step (4) is obtained, be ground to particle size range at 50 ~ 100 orders, charcoal/silica composite material particle is put into the hydrofluoric acid solution that volumetric molar concentration is 5～10 mol/L, soaked 24 hours 50～60 ℃ of lower water-baths, filter to isolate the charcoal particle, use deionized water wash, namely get Mesoporous Carbon Materials after the drying.
Below introduce the embodiment of the inventive method:
(1) at room temperature, with polyethers P123(polyoxyethylene-poly-oxypropylene polyoxyethylene) (24g) be dissolved in hydrochloric acid soln, the volumetric molar concentration of hydrochloric acid is 2 mol/L, make solution temperature rise to 40 ℃, the Three methyl Benzene continuously stirring of adding 24g 2 hours, then adding the 92mL tetraethoxy stirred 10 minutes, the mixed solution of making at room temperature aging 24 hours, mixed solution is filtered, after water and ethanol clean, 600 ℃ of lower calcinings, calcination time is 2 hours, obtains the agent of mesoporous silica ball template;
(2) 30g phenol is added in the 12mL sodium hydroxide solution at leisure, the volumetric molar concentration of sodium hydroxide solution is 2.5 mol/L, and 40 ℃ of thawings.After phenol melts fully, be that the formaldehyde solution of 12 mol/L splashes into the 52mL volumetric molar concentration, mixing solutions was 70 ℃ of stirring reactions 1 hour, after being cooled to room temperature, the pH value of adjusting mixed solution with hydrochloric acid soln is 7.0, makes the mixed solution dehydration under 50 ℃ in vacuum, obtains resol;
(3) with 24g polyethers F127(polyethylene oxide-poly(propylene oxide)-polyethylene oxide), be dissolved in the ethanol of 300mL, heat to 40 ℃ and dissolve, the resol resin (24g) that step (2) is obtained joins in the mentioned solution, rear adding 24g mesoporous silica ball stirs, and in 40 ℃ of lower stirrings 1 hour, with mixing solutions supersound process 15 minutes, vapor away in the stirring of 40 ℃ of lower ethanol by medium tenacity, volatilize after 12 hours, 105 ℃ were heated 24 hours in baking oven, obtained resol/template composite;
(4) mixture that step (3) is obtained is inserted in the atmosphere furnace, carries out high temperature carbonization and processes, and whole carbonization process carries out under nitrogen protection.Detailed process is as follows: mixture is put into the atmosphere furnace charing, speed with 2 liter/mins of clocks passes into high pure nitrogen, with 2 ℃/minute temperature rise rate, temperature is risen to 900 ℃, keep 900 ℃ of constant temperature to be cooled to room temperature after 2 hours, obtain charcoal/template matrix material by above process;
(5) charcoal that step (4) is obtained/template matrix material, be ground to particle size range at the 50-100 order, 50 ℃ of immersions of water-bath are 24 hours in hydrofluoric acid solution, the volumetric molar concentration of hydrofluoric acid is 5 mol/L, filtering separation, use deionized water wash, namely get Mesoporous Carbon Materials, the specific surface area 740m of the Mesoporous Carbon Materials that obtains after the drying
2/ g, pore volume 2.101cm
3/ g, mean pore size 11.35nm.
From Fig. 1 curve as can be known, mesoporous carbon is to N
2To be adsorbed on the high pressure area just saturated gradually, illustrate that the mesopore of the Mesoporous Carbon Materials that makes is very abundant.
Among Fig. 2, the pore size distribution curve of mesoporous carbon shows that when the mass ratio of silicon oxide and resol was 1:1, the aperture of Mesoporous Carbon Materials mainly concentrated on 2 ~ 50nm, and its pore volume of other several Carbon Materials is maximum relatively, and mean pore size is also maximum.
Embodiment 2
(1) at room temperature, with polyethers P123(polyoxyethylene-poly-oxypropylene polyoxyethylene) (24g) be dissolved in hydrochloric acid soln, the volumetric molar concentration of hydrochloric acid is 5 mol/L, make solution temperature rise to 40 ℃, the Three methyl Benzene continuously stirring of adding 24g 2 hours, then adding the 92mL tetraethoxy stirred 15 minutes, the mixed solution of making at room temperature aging 24 hours, mixed solution is filtered, after water and vinylcarbinol clean, 900 ℃ of lower calcinings, calcination time is 2 hours, obtains the agent of mesoporous silica ball template;
(2) 30g phenol is added in the 12mL sodium hydroxide solution at leisure, the volumetric molar concentration of sodium hydroxide solution is 3 mol/L, and 40 ℃ of thawings.After phenol melts fully, be that the formaldehyde solution of 10 mol/L splashes into the 52mL volumetric molar concentration, mixing solutions was 70 ℃ of stirring reactions 1 hour, after being cooled to room temperature, the pH value of adjusting mixed solution with hydrochloric acid soln is 7.0, makes the mixed solution dehydration under 60 ℃ in vacuum, obtains resol;
(3) with 24g polyethers F127(polyethylene oxide-poly(propylene oxide)-polyethylene oxide), be dissolved in the propyl alcohol of 300mL, heat to 40 ℃ and dissolve, the resol resin (24g) that step (2) is obtained joins in the mentioned solution, rear adding 12g mesoporous silica ball stirs, and in 40 ℃ of lower stirrings 1 hour, with mixing solutions supersound process 15 minutes, vapor away in the stirring of 40 ℃ of lower vinylcarbinols by medium tenacity, volatilize after 12 hours, 120 ℃ were heated 24 hours in baking oven, obtained resol/template composite;
(4) mixture that step (3) is obtained is inserted in the atmosphere furnace, carries out high temperature carbonization and processes, and whole carbonization process carries out under nitrogen protection.Detailed process is as follows: mixture is put into the atmosphere furnace charing, speed with 3 liter/mins of clocks passes into high pure nitrogen, with 3 ℃/minute temperature rise rate, temperature is risen to 900 ℃, keep 900 ℃ of constant temperature to be cooled to room temperature after 4 hours, obtain charcoal/template matrix material by above process;
(5) charcoal that step (4) is obtained/template matrix material, be ground to particle size range at the 50-100 order, 50 ℃ of immersions of water-bath are 24 hours in hydrofluoric acid solution, the volumetric molar concentration of hydrofluoric acid is 6 mol/L, filtering separation, use deionized water wash, namely get Mesoporous Carbon Materials, the specific surface area 390m of the Mesoporous Carbon Materials that obtains after the drying
2/ g, pore volume 0.956cm
3/ g, mean pore size 9.81nm.
From Fig. 1 curve as can be known, mesoporous carbon is to N
2To be adsorbed on the high pressure area just saturated gradually, illustrate that the mesopore of the Mesoporous Carbon Materials that makes is abundanter.
Among Fig. 2, the pore size distribution curve of mesoporous carbon shows, when the mass ratio of silicon oxide and resol was 0.5:1, the aperture of Mesoporous Carbon Materials mainly concentrated on 2 ~ 50nm, and its pore volume and mean pore size are the mesoporous carbon that 1:1 makes less than the mass ratio of silicon oxide and resol.
Embodiment 3
(1) at room temperature, with polyethers P123(polyoxyethylene-poly-oxypropylene polyoxyethylene) (24g) be dissolved in hydrochloric acid soln, the volumetric molar concentration of hydrochloric acid is 4 mol/L, make solution temperature rise to 40 ℃, the Three methyl Benzene continuously stirring of adding 24g 2 hours, then adding the 92mL tetraethoxy stirred 15 minutes, the mixed solution of making at room temperature aging 24 hours, mixed solution is filtered, after water and butanols clean, 800 ℃ of lower calcinings, calcination time is 3 hours, obtains the agent of mesoporous silica ball template;
(2) 30g phenol is added in the 12mL sodium hydroxide solution at leisure, the volumetric molar concentration of sodium hydroxide solution is 4 mol/L, and 40 ℃ of thawings.After phenol melts fully, be that the formaldehyde solution of 11 mol/L splashes into the 52mL volumetric molar concentration, mixing solutions was 70 ℃ of stirring reactions 1 hour, after being cooled to room temperature, the pH value of adjusting mixed solution with hydrochloric acid soln is 7.0, makes the mixed solution dehydration under 70 ℃ in vacuum, obtains resol;
(3) with 24g polyethers F127(polyethylene oxide-poly(propylene oxide)-polyethylene oxide), be dissolved in the butanols of 300mL, heat to 40 ℃ and dissolve, the resol resin (24g) that step (2) is obtained joins in the mentioned solution, rear adding 6g mesoporous silica ball stirs, and in 40 ℃ of lower stirrings 1 hour, with mixing solutions supersound process 15 minutes, vapor away in the stirring of 40 ℃ of lower butanols by medium tenacity, volatilize after 12 hours, 130 ℃ were heated 24 hours in baking oven, obtained resol/template composite;
(4) mixture that step (3) is obtained is inserted in the atmosphere furnace, carries out high temperature carbonization and processes, and whole carbonization process carries out under nitrogen protection.Detailed process is as follows: mixture is put into the atmosphere furnace charing, speed with 4 liter/mins of clocks passes into high pure nitrogen, with 4 ℃/minute temperature rise rate, temperature is risen to 900 ℃, keep 900 ℃ of constant temperature to be cooled to room temperature after 3 hours, obtain charcoal/template matrix material by above process;
(5) charcoal that step (4) is obtained/template matrix material, be ground to particle size range at the 50-100 order, 50 ℃ of immersions of water-bath are 24 hours in hydrofluoric acid solution, the volumetric molar concentration of hydrofluoric acid is 7 mol/L, filtering separation, use deionized water wash, namely get Mesoporous Carbon Materials, the specific surface area 541m of the Mesoporous Carbon Materials that obtains after the drying
2/ g, pore volume 0.473cm
3/ g, mean pore size 3.49nm.
From Fig. 1 curve as can be known, mesoporous carbon is to N
2To be adsorbed on the mesohigh district just saturated gradually, illustrate that the mesopore of the Mesoporous Carbon Materials that makes is slightly abundant.
Among Fig. 2, the pore size distribution curve of mesoporous carbon shows that when the mass ratio of silicon oxide and resol was 0.25:1, the aperture of Mesoporous Carbon Materials mainly concentrated on 2 ~ 10nm, when its pore volume and mean pore size are respectively 0.5:1 and 1:1 less than the mass ratio of silicon oxide and resol, the mesoporous carbon that makes.
Embodiment 4(comparative example)
(1) at room temperature, with polyethers P123(polyoxyethylene-poly-oxypropylene polyoxyethylene) (24g) be dissolved in hydrochloric acid soln, the volumetric molar concentration of hydrochloric acid is 5 mol/L, make solution temperature rise to 40 ℃, the Three methyl Benzene continuously stirring of adding 24g 2 hours, then adding the 92mL tetraethoxy stirred 15 minutes, the mixed solution of making at room temperature aging 24 hours, mixed solution is filtered, after water and butanols clean, 850 ℃ of lower calcinings, calcination time is 3 hours, obtains the agent of mesoporous silica ball template;
(2) 30g phenol is added in the 24mL sodium hydroxide solution at leisure, the volumetric molar concentration of sodium hydroxide solution is 2 mol/L, and 40 ℃ of thawings.After phenol melts fully, be that the formaldehyde solution of 10 mol/L splashes into the 52mL volumetric molar concentration, mixing solutions was 70 ℃ of stirring reactions 1 hour, after being cooled to room temperature, the pH value of adjusting mixed solution with hydrochloric acid soln is 7.0, makes the mixed solution dehydration under 70 ℃ in vacuum, obtains resol;
(3) with 24g polyethers F127(polyethylene oxide-poly(propylene oxide)-polyethylene oxide), be dissolved in the butanols of 300mL, heat to 40 ℃ and dissolve, the resol resin (24g) that step (2) is obtained joins in the mentioned solution, vapor away in the stirring of 40 ℃ of lower butanols by medium tenacity, volatilize after 12 hours, 130 ℃ were heated 24 hours in baking oven, obtained the resol mixture;
(4) mixture that step (3) is obtained is inserted in the atmosphere furnace, carries out high temperature carbonization and processes, and whole carbonization process carries out under nitrogen protection.Detailed process is as follows: mixture is put into the atmosphere furnace charing, speed with 4 liter/mins of clocks passes into high pure nitrogen, with 4 ℃/minute temperature rise rate, temperature is risen to 900 ℃, keep 900 ℃ of constant temperature to be cooled to room temperature after 3 hours, obtain carbon composite by above process;
(5) charcoal that step (4) is obtained/template matrix material is ground to particle size range at the 50-100 order, and filtering separation is used deionized water wash, namely gets Carbon Materials, the specific surface area 649m of the Carbon Materials that obtains after the drying
2/ g, pore volume 0.429cm
3/ g, mean pore size 1.73nm.
Present embodiment 4 is the comparative example, does not add the agent of mesoporous silica ball template among this embodiment, and the Carbon Materials mean pore size that obtains only is 1.73nm, and its aperture is significantly less than the Mesoporous Carbon Materials that adds the preparation of mesoporous silicon ball.
From Fig. 1 curve as can be known, mesoporous carbon is to N
2To be adsorbed on the low pressure nip just saturated, illustrate that the mesopore of the Carbon Materials that makes does not enrich.
Among Fig. 2, the pore size distribution curve of charcoal shows that when the mass ratio of silicon oxide and resol was 0:1, the aperture of Carbon Materials mainly concentrated on 0 ~ 2nm, the mesoporous carbon that its pore volume and mean pore size make as template much smaller than the interpolation silicon oxide.
Contrast 4 embodiment, the consumption along with the mesoporous silica template is larger as can be known, and its pore volume of the Carbon Materials that makes and mean pore size are larger, can realize by the consumption of template the regulation and control in aperture.
Above-mentioned embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (1)
1. the preparation method of the Mesoporous Carbon Materials in template regulation and control aperture is characterized in that the method may further comprise the steps:
(1) at room temperature, polyethers P123 is dissolved in hydrochloric acid soln, and the volumetric molar concentration of hydrochloric acid is 2～5 mol/L, makes solution temperature rise to 40～60 ℃, added the Three methyl Benzene continuously stirring 2～5 hours, then add tetraethoxy and stirred 10～20 minutes, the mixed solution of making at room temperature aging 24～48 hours filters mixed solution, after water and low-carbon alcohol are cleaned, 600 ~ 900 ℃ of lower calcinings, calcination time is 2～4 hours, obtains the agent of mesoporous silica ball template;
(2) with phenol in molar ratio (10～12): 1 ratio slowly joins in the sodium hydroxide solution that volumetric molar concentration is 2～5 mol/L, and heat to 40 ℃, make the phenol dissolving, be that the formaldehyde solution of 10 mol/L～12 mol/L splashes into volumetric molar concentration, the mol ratio that makes phenol and formaldehyde is 1:(1～3), mixed solution was 60～80 ℃ of stirring reactions 1 hour, after being cooled to room temperature, the pH value of adjusting mixed solution with hydrochloric acid soln is 7.0, under 50～70 ℃, in vacuum, make the mixed solution dehydration, obtain resol;
(3) polyethers F127 is dissolved in the low-carbon alcohol, heat to 40 ℃ and dissolve, add the resol that step (2) obtains, the mass ratio that makes polyethers F127 and resol is 1:(1～2), the mesoporous silica ball template agent that the rear adding step (1) that stirs obtains, make the mass ratio of the agent of mesoporous silica ball template and resol be (0.2～1): 1, in 40 ℃ of lower stirrings 1 hour, with mixing solutions supersound process 15～30 minutes, under 40～70 ℃, stirred 8～12 hours, and 105～130 ℃ of heating 24 hours, obtained resol/silicon oxide mixture;
(4) resol that step (3) is obtained/silicon oxide mixture is inserted charing in the atmosphere furnace, speed with 2～5 liter/mins of clocks passes into high pure nitrogen, temperature rise rate with 2～5 ℃/minute, temperature is risen to 900 ℃, little 900 ℃ of maintenances 2～4, cool to room temperature with the furnace, obtain charcoal/silica composite material;
(5) charcoal/silica composite material that step (4) is obtained, be ground to particle size range at 50 ~ 100 orders, charcoal/silica composite material particle is put into the hydrofluoric acid solution that volumetric molar concentration is 5～10 mol/L, soaked 24 hours 50～60 ℃ of lower water-baths, filter to isolate the charcoal particle, use deionized water wash, namely get Mesoporous Carbon Materials after the drying.
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| 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 20101115 李强 介孔氧化硅基材料水热稳定性的研究以及新型介孔碳基材料的合成与应用 第B020-66页 , 第11期 * |
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| CN103523871B (en) * | 2013-09-29 | 2015-04-22 | 北京国环清华环境工程设计研究院有限公司 | Preparation method of mesoporous carbon electrode for electric adsorption desalination |
| CN103523871A (en) * | 2013-09-29 | 2014-01-22 | 北京国环清华环境工程设计研究院有限公司 | Preparation method of mesoporous carbon electrode for electric adsorption desalination |
| CN105907743A (en) * | 2016-06-23 | 2016-08-31 | 陕西师范大学 | Preparation and application of hollow spherical-segment-shaped mesoporous silica/chloroperoxidase nanoreactor |
| CN105907743B (en) * | 2016-06-23 | 2019-05-14 | 陕西师范大学 | The preparation and application of hollow segment-shaped mesoporous silicon oxide/chloroperoxidase nano-reactor |
| CN109896512A (en) * | 2017-12-08 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of method that low cost prepares ion exchange resin base porous carbon material |
| CN109896513A (en) * | 2017-12-08 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of preparation method of ion exchange resin base porous carbon material |
| CN109012596A (en) * | 2018-09-06 | 2018-12-18 | 青岛科技大学 | The resource utilization method of absorption resin is discarded in a kind of production of resorcinol |
| CN109012596B (en) * | 2018-09-06 | 2021-03-09 | 青岛科技大学 | Resource utilization method of waste adsorption resin in resorcinol production |
| CN111498844A (en) * | 2019-01-31 | 2020-08-07 | 山东欧铂新材料有限公司 | Mesoporous activated carbon material and preparation method and application thereof |
| CN111498844B (en) * | 2019-01-31 | 2023-05-16 | 山东欧铂新材料有限公司 | Mesoporous activated carbon material and preparation method and application thereof |
| CN113637462A (en) * | 2021-08-19 | 2021-11-12 | 中国科学院广州能源研究所 | Preparation method of chemical heat storage material based on ordered porous carbon base |
| CN113637462B (en) * | 2021-08-19 | 2023-10-10 | 中国科学院广州能源研究所 | Preparation method of chemical heat storage material based on ordered porous carbon base |
| CN114307960A (en) * | 2021-12-29 | 2022-04-12 | 无锡凡锡环保科技有限公司 | Preparation method and application of cation pi-effect synergistic mesoporous carbon material |
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