CN101134567A - High-stability large aperture ordered meso-porous carbon material and preparation method thereof - Google Patents
High-stability large aperture ordered meso-porous carbon material and preparation method thereof Download PDFInfo
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- CN101134567A CN101134567A CNA2007100442473A CN200710044247A CN101134567A CN 101134567 A CN101134567 A CN 101134567A CN A2007100442473 A CNA2007100442473 A CN A2007100442473A CN 200710044247 A CN200710044247 A CN 200710044247A CN 101134567 A CN101134567 A CN 101134567A
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Abstract
The present invention belongs to the field of advanced nanometer composite material technology, and is especially one kind of macroporous ordered mesoporous carbon material with high stability and its preparation process. Soluble phenolic resin solution in certain concentration and surfactant of block copolymer with strong hydrophilic polyoxyethylene block and weak hydrophilic polyacrylate block are first mixed; and through solvent volatilization to induce self assembly, heating to cure and high temperature carbonization, thick wall macroporous ordered mesoporous carbon material with high stability is obtained. The mesoporous carbon material has large pores of 4-12 nm, thick carbon skeleton wall of 8-16 nm and high stability, and may find wide application in electrode material, etc.
Description
Technical field
The invention belongs to advanced nano composite material technical field, be specifically related to a kind of large aperture ordered meso-porous carbon material and preparation method thereof with thick wall, high stability.
Technical background
In recent years, meso-porous carbon material is because the character of the high-specific surface area of the conductive characteristic of its carbon material self and mesoporous material, in support of the catalyst, and electrode of super capacitor, aspects such as fuel cell are with a wide range of applications.The synthetic method that adopts nanocasting usually of traditional meso-porous carbon material, this method at first synthesizes the Metaporous silicon dioxide material of a fixed structure, in the duct of Metaporous silicon dioxide material, insert the presoma of organic molecule again as carbon, behind high temperature cabonization, remove the silicon-dioxide masterplate, thereby obtain having and the corresponding meso-porous carbon material of synthetic mesoporous silicon oxide (Ryoo, R.; Joo, S.H.; Kruk, M.; Jaroniec, M.Adv.Mater.2001,13,667-680).Recently, Zhao Dongyuan professor seminar has proposed a kind of novel method of utilizing resol resin and tensio-active agent directly to act on the preparation meso-porous carbon material, this kind method is utilized the hydrogen bond action that exists between the resol resin and tensio-active agent in the solution, utilize the principle of organic-organic self-assembly, induce self-assembly (EISA) method to prepare ordered mesoporous carbon material by collosol and gel (sol-gel) method and solvent evaporates, utilize this kind method to avoid the preparation of masterplate mesoporous silicon oxide in the preparation process, saved time and resource.(Meng，Y.；Gu，D.；Zhang，F.Q.；Shi，Y.F.；Yang，H.F.；Li，Z.；Yu，C.Z.；Tu，B.；?Zhao，D.Y.Angew.Chem.，Int.Ed.2005，44，7053-7059；Zhang，F.Q.；Meng，Y.；Gu，D.；Yan，Y.；Yu，C.Z.；Tu，B.；Zhao，D.Y.J?Am.Chem.Soc.2005，127，13508-13509)
Although people have obtained huge progress aspect ordered mesoporous material, yet, the synthetic difficulty that still compares of the meso-porous carbon material of wide aperture, high stability had.Dai seminar utilizes amphipathic nature block polymer PS-b-P4VP as structure directing agent, method by solvent aging (solvent annealing) between itself and the Resorcino is formed mesoscopic structure, and be placed in the formaldehyde steam and solidify with fixing mesoscopic structure, last calcination carbonization removes template with obtain the having ultra-large aperture ordered mesoporous carbon material (Liang of (34nm), C., Hong, K., Guiochon G.A., Mays, J.W., Dai, S., Angew.Chem.Int.Ed., 2004,43,5785-5789).Recently, the first seminar in Zhao east utilizes ultrahigh molecular weight segmented copolymer PEO-b-PS as structure directing agent, the mesoporous silicon (aperture reaches 23nm) and meso-porous carbon material (aperture reaches 31nm) (Deng, Y.H., the Yu that utilize solvent evaporates to induce the method for self-assembly (EISA) successfully to synthesize to have ultra-large aperture, T., Wan, Y., Shi, Y.F., Meng, Y., Gu, D., Zhang, L.J., Huang, Y., Liu, C., Wu, X.J., Zhao, D.Y., J Am.Chem.Soc., 2007,129,1690-1697).Has wide-aperture meso-porous carbon material although utilize PEO-b-PS can synthesize as structure directing agent, but compare its aperture and Yan Eryan, the wall thickness of this kind material (9.9nm) can not provide enough stability of material and physical strength, thereby limited it in many aspects, especially for mechanical strength and the relatively application of harsh aspect of stability.
The present invention is on the basis of the existing work of the first seminar in Zhao east, utilization has the structure directing agent of the copolymer surfactants of polyoxyethylene (PEO) strong hydrophilicity section block and polyacrylate(s) slightly water-wet block as meso-hole structure, utilize the segmented copolymer hydrophobic section hydrogen bond action partly to take place with resol resin, under the condition of identical polyoxyethylene segment length, obtain having the wide aperture, the ordered mesoporous carbon material of thick wall, therefore this material has the stability and the physical strength of more increasing owing to have the wall thickness suitable with the aperture.This material requires to be with a wide range of applications in the more harsh application for mechanical strength numerous.This method method is simple, and raw material is easy to get, and can change the block copolymerization properties as required and adapt to application requiring, can be used for method production.
Summary of the invention
The objective of the invention is to large aperture ordered meso-porous carbon material of a kind of physical strength height, good stability and preparation method thereof.
Large aperture ordered meso-porous carbon material proposed by the invention, be with the presoma of resol resin as the carbon in the meso-porous carbon material, have the structure directing agent of the copolymer surfactants of polyoxyethylene (PEO) strong hydrophilicity section block and polyacrylate(s) slightly water-wet block as meso-hole structure, utilize the segmented copolymer hydrophobic section that the effect of hydrogen bond can partly take place with resol resin, according to the principle that solvent evaporates is induced self-assembly (EISA), make between block copolymer surfactant and the resol resin that forming is situated between and see ordered structure and obtain; In the sight ordered structure that is situated between, since the block copolymer surfactant hydrophobic section also can with certain the combining of the existence between the resol resin, thereby formed Jie sees that resol resin not only is present in the polyoxyethylene blocks in the ordered structure, and is present in the block copolymer surfactant hydrophobic block of a part.This Jie is seen ordered structure baking certain hour make phenolic resin curing crosslinked, under the inert gas atmosphere protection, remove surfactant templates, promptly obtain having the large aperture ordered meso-porous carbon material of thick wall, high stability.The present invention can be by regulating the size of the affinity ability between hydrophobic block and the resol resin, ratio between hydrophilic block polyoxyethylene blocks and the hydrophobic block, ratio between resol resin and the block copolymer surfactant, controllable adjustment meso-porous carbon material aperture is between 4-20nm, and wall thickness is at 8-16nm.
Concrete preparation process of the present invention is as follows:
(1) resol resin and the block copolymer surfactant that contains the polyoxyethylene section are dissolved in the easy volatile solvent.Wherein, the amount of resol resin is 0.5-5wt%, and the amount that contains the block copolymer surfactant of polyoxyethylene section is 0.1-1wt%, and all the other are solvent.
(2) mixing solutions that above-mentioned steps is obtained perhaps simply leaves standstill the shop membrane method and makes the easy volatile solvent evaporates complete by lifting (dip-coating), spin coating (spin-coating).
(3) treat that above-mentioned solvent evaporates fully after, the sample of gained is placed 80-200 ℃ environment baking 12-24h down, make phenolic resin curing with fixing mesoscopic structure.
(4) will solidify the back sample and place the tube furnace high temperature sintering under the protection of inert gas to remove tensio-active agent, calcination temperature is 450 ℃～1200 ℃.Sample is the large aperture ordered meso-porous carbon material with thick wall, high stability after the calcination.
The carbon material presoma that is adopted among the present invention is a resol resin, resol resin can be resole (as low-molecular-weight resol of being obtained by phenol and formaldehyde base catalyzed reactions etc.), also can be to have substituting group resole (as by low-molecular-weight substituted phenolic resin that sulphur phenol and formaldehyde base catalyzed reactions are obtained etc.), also can be their two or more miscellany.
The mesoscopic structure structure directing agent that is adopted among the present invention is the copolymer surfactants with polyoxyethylene (PEO) strong hydrophilicity section block and polyacrylate(s) slightly water-wet block.In this segmented copolymer, the PEO block is by hydrogen bond and resol resin effect, the weak hydrophobic polyacrylic ester block of a part also can with resol resin generation hydrogen bond action.The hydrophobic block of this segmented copolymer can be polyacrylate(s) (as a polyacrylic ester, polymethacrylate, or their multipolymer).
The solvent that is adopted among the present invention can be one or more in the volatile organic solvent of solubilized resol resins such as tetrahydrofuran (THF), dioxane and block copolymer surfactant.
The method of the formation mesoscopic structure that is adopted among the present invention is to make the easy volatile solvent volatilization fully to form orderly mesoscopic structure.This method comprises that the various solvent evaporates of utilizing induce self-assembly (EISA) principle to form the method for orderly mesoscopic structure, comprised and lifted (dip-coating), spin coating (spin-coating), and some simple more methods, for example, the mixing solutions that contains resol resin and block copolymer surfactant can be poured in several culture dish, solvent is volatilized naturally to form mesoscopic structure.
The present synthetic mainly hard template method by nanometer casting (nanocasting) of ordered mesoporous carbon material and utilize two kinds of approach of soft template method of organic-organic self-assembly.Because the each side character of the carbon material that obtains of hard template method all is subjected to the restriction of the template property that adopted, therefore can't be had the ordered mesoporous carbon material of wide aperture and thick wall simultaneously.Utilize organic-organic self-assembling method synthesizing ordered mesoporous carbon material to obtain significant progress in recent years, wherein people utilize PEO-b-PS to synthesize as structure directing agent to have wide-aperture ordered mesoporous carbon material, but its wall thickness can not provide sufficiently high physical strength.The present invention adopts the block copolymer surfactant of macromolecule as structure directing agent, under the condition of short polyoxyethylene blocks, utilize the hydrogen bond action of part between hydrophobic block and the carbon matrix precursor resol resin, increase the wall thickness of ordered mesoporous carbon material, thereby improved the stability and the physical strength of material.Adopt characteristics of the present invention as follows: 1. step is simple, and raw material is easy to get.2. can utilize the size of the action intensity between hydrophobic block of different nature and the resol resin, effectively regulate wall thickness.
Description of drawings
Fig. 1 is the TEM photo with large aperture ordered meso-porous material of thick wall, high stability.
Embodiment
Embodiment 1:
(1) with resole (resol resin) and poly-(oxygen ethene-block-methyl methacrylate) PEO of segmented copolymer
125-b-PMMA
144Be dissolved in the tetrahydrofuran (THF).Wherein, the amount of resole is 0.6wt%, and block copolymer surfactant is 0.15wt%, and all the other are solvent.
(2) the mixing solutions 3.4g in the above-mentioned steps is poured in the culture dish of a 15cm diameter, the solvent 24h that volatilizees naturally under the room temperature is to form mesoscopic structure.
(3) treat that above-mentioned solvent evaporates fully after, the sample of volatilization gained is placed environment time of baking 24h down of 100 ℃, make phenolic resin curing with fixing mesoscopic structure.
(4) will solidify the back sample and place the tube furnace high temperature sintering under the nitrogen protection to remove tensio-active agent, calcination temperature is 900 ℃.Sample is wide aperture (10nm) ordered mesoporous carbon material with thick wall (12nm), high stability after the calcination.
Embodiment 2:
(1) with resole (resol resin) and segmented copolymer PEO
125-b-PMMA
180(tensio-active agent) is dissolved in the dioxane solvent.Wherein, resole content is 0.9wt%, and the block copolymer surfactant that contains the polyoxyethylene section is 0.23wt%, and all the other are solvent.
(2) the mixing solutions 3.4g in the above-mentioned steps is poured in the culture dish of a 15cm diameter, the solvent 12h that volatilizees naturally under the room temperature is to form mesoscopic structure.
(3) treat that above-mentioned solvent evaporates fully after, the sample of volatilization gained is placed environment time of baking 24h down of 120 ℃, make phenolic resin curing with fixing mesoscopic structure.
(4) will solidify the back sample and place the tube furnace high temperature sintering under the nitrogen protection to remove tensio-active agent, calcination temperature is 900 ℃.Sample is macropore (16nm) the footpath ordered mesoporous carbon material with thick wall (12nm), high stability after the calcination.
Embodiment 3:
(1) with resole (resol resin) and poly-(oxygen ethene-block-methyl acrylate) PEO of segmented copolymer
125-b-PMA
134Be dissolved in the tetrahydrofuran (THF).Wherein, A rank phenolic resin content is 0.9wt%, and the block copolymer surfactant that contains the polyoxyethylene section is 0.26wt%, and all the other are solvent.
(2) the mixing solutions 3.0g in the above-mentioned steps is poured in the culture dish of a 15cm diameter, solvent volatilized 1 day naturally under the room temperature, to form mesoscopic structure.
(3) treat that above-mentioned solvent evaporates fully after, the sample of volatilization gained is placed 120 ℃ environment baking 18h down, make phenolic resin curing with fixing mesoscopic structure.
(4) will solidify the back sample and place the tube furnace high temperature sintering under the protection of inert gas to remove tensio-active agent, calcination temperature is 900 ℃.Sample is wide aperture (5.0nm) ordered mesoporous carbon material with thick wall (8.0nm), high stability after the calcination.
Embodiment 4:
(1) mixture and the block copolymer surfactant PEO125-b-PMMA144 with resole and sulfonation resole is dissolved in the tetrahydrofuran (THF).Wherein, resole content is 0.7wt%, and sulfonation resole content is 0.2wt%, and block copolymer surfactant is 0.23wt%, and all the other are solvent.
(2) mixing solutions in the above-mentioned steps is applied on the quartz substrate by lifting (dip-coating) method.
(3) treat that above-mentioned solvent evaporates fully after, the sample of volatilization gained is placed 120 ℃ environment baking 20h down, make phenolic resin curing with fixing mesoscopic structure.
(4) will solidify the back sample and place the tube furnace high temperature sintering under the protection of inert gas to remove tensio-active agent, calcination temperature is 900 ℃.Sample is wide aperture (11nm) ordered mesoporous carbon material with thick wall (13nm), high stability after the calcination.
Claims (4)
1. high-stability large aperture ordered meso-porous carbon material, it is characterized in that it being with the presoma of resol resin as the carbon in the meso-porous carbon material, have the structure directing agent of the copolymer surfactants of polyoxyethylene strong hydrophilicity section block and polyacrylate(s) slightly water-wet block as meso-hole structure, utilize the segmented copolymer hydrophobic section that the effect of hydrogen bond can partly take place with resol resin, induce the principle of self-assembly according to solvent evaporates, make that forming between block copolymer surfactant and the resol resin is situated between and see ordered structure and obtain; The mesoporous material aperture is 4-20nm, and wall thickness is 8-16nm.
2. the preparation method of the large aperture ordered meso-porous carbon material of a high stability is characterized in that concrete steps are as follows:
(1) with resol resin with contain block copolymer surfactant and be dissolved in the easy volatile solvent with polyoxyethylene strong hydrophilicity section block and polyacrylate(s) slightly water-wet block; Wherein, the amount of resol resin is 0.5-5wt%, and the amount of block copolymer surfactant is 0.1-1wt%, and all the other are solvent;
(2) mixing solutions that above-mentioned steps is obtained is by lifting, and spin coating is perhaps simply spread membrane method and made the easy volatile solvent evaporates complete;
(3) treat that solvent evaporates fully after, the sample of gained is placed 80-200 ℃ of baking 12-24h down, make phenolic resin curing with fixing mesoscopic structure;
(4) will solidify the back sample and place the tube furnace high temperature sintering under the protection of inert gas to remove tensio-active agent, calcination temperature is 450 ℃～1200 ℃, and sample is the large aperture ordered meso-porous carbon material with thick wall, high stability after the calcination.
3. the preparation method of high-stability large aperture ordered meso-porous carbon material according to claim 2, it is characterized in that described resol resin is resole or has the substituting group resole, or their two or more miscellany.
4. the preparation method of the large aperture ordered meso-porous carbon material of high stability according to claim 2 is characterized in that employed solvent is tetrahydrofuran (THF) or dioxane.
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