CN100556800C - A kind of multilevel ordered mesoporous/macropore complex carbon material and preparation method thereof - Google Patents
A kind of multilevel ordered mesoporous/macropore complex carbon material and preparation method thereof Download PDFInfo
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- CN100556800C CN100556800C CNB2007100379041A CN200710037904A CN100556800C CN 100556800 C CN100556800 C CN 100556800C CN B2007100379041 A CNB2007100379041 A CN B2007100379041A CN 200710037904 A CN200710037904 A CN 200710037904A CN 100556800 C CN100556800 C CN 100556800C
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Abstract
The invention belongs to advanced nano composite material technical field, be specifically related to a kind of mesopore/macropore combined carbon material and preparation method thereof with multilevel ordered structure.The present invention with silicon-dioxide mould colloid crystalline substance as hard template, the block copolymer surfactant of polyoxyethylene section is a soft template, resol resin is a carbon source, by carrying out organic-organic self-assembly in the space of colloidal crystal, synthetic mesopore/macropore combined carbon material with multistage pore canal.This material not only has the macropore of the ordered arrangement that is interconnected, but also has the mesoporous wall of short range order.In addition, such material has the photonic band gap that the colloidal crystal structure is produced, and the forbidden band wavelength is adjustable continuously.This material has broad application prospects at aspects such as optical waveguide, transmitter, support of the catalyst.The inventive method is simple, and raw material is easy to get, and is suitable for amplifying producing.
Description
Technical field
The invention belongs to advanced nano composite material technical field, be specifically related to a kind of multilevel ordered mesoporous/macropore complex carbon material and preparation method thereof.
Technical background
In recent years, meso-porous carbon material is because the conductive characteristic of its carbon material self and the superior character such as high-specific surface area of 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 of nanometer casting (nanocasting) that adopts usually of traditional meso-porous carbon material obtains, 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, the silicon-dioxide masterplate will also further be removed then behind the organic carbon, thereby obtain having meso-porous carbon material replica (Ryoo, R. with the corresponding pore passage structure of mesoporous silicon oxide template; 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 organic-organic self-assembly between resol resin and tensio-active agent, induces self-assembly (EISA) to prepare ordered mesoporous carbon material by solvent evaporates.This kind method has been avoided the use of mesoporous silicon oxide among the traditional preparation process meso-porous carbon material preparation method, has realized direct synthesizing ordered mesoporous carbon material, has developed the synthetic of meso-porous carbon material.(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)
Recently, the mesopore/macropore material with duct on the multiple yardstick is subjected to people's attention.Because having the huge specific surface area and the large pore material of mesoporous material simultaneously, this kind material is easy to carry out molecular diffusion, therefore in support of the catalyst, and biological, chemical sensor, separating substances analysis aspect has broad application prospects.People are by inserting tetraethoxy (TEOS in the colloidal crystal of the mono-disperse polymer microspheres of ordered arrangement, Tetraethyl orthosilicate) and the mixing solutions of polyoxyethylene-poly-oxypropylene polyoxyethylene tensio-active agent, mesopore/macropore earth silicon material (Sen, T. have been prepared with multistage pore canal; Tiddy, G.J.T.; Casci, J.L.; Anderson, M.W.Angew.Chem., Int.Ed.2003,42,4649-4653).But, have the synthetic difficulty that but compares of the mesopore/macropore carbon material of multistage pore canal.Its reason is owing to all relate to synthetic as the mesoporous silicon oxide of masterplate in traditional mesoporous carbon synthetic method, but in mesopore/macropore material synthetic, be difficult to the mesopore/macropore earth silicon material as masterplate synthesising mesoporous/the macropore carbon material.Wherein, Stein seminar adopts mesopore/macropore silicon-dioxide to synthesize the mesopore/macropore carbon material with multistage pore canal as masterplate, its method is as follows: 1. at first at PMMA (polymethylmethacrylate, Poly (methyl methacrylate)) permeates methyl silicate (TMOS, Tetramethyl orthosilicate) and nonionic surfactant Brij 56 (C in the colloidal crystal of microballoon
16H
33-EO
10) acidic sol, mesoscopic structure is formed in the space between the PMMA microballoon.2. the method by calcination is decomposed to obtain Metaporous silicon dioxide material PMMA and tensio-active agent.With mesoporous silicon oxide as masterplate, the resol precursor is inserted in the mesoporous material, remove masterplate after the curing, promptly obtain the mesopore/macropore carbon material.(Wang, Z.; Li, F.; Ergang, N.S.; Stein, A.Chem.Mater.2006,18,5543-5553) shortcoming of this kind method is that step is various, and is too loaded down with trivial details.
The present invention combines organic-organic self-assembling method with the synthetic method of colloidal crystal, with silicon-dioxide mould colloid crystalline substance as hard template, the block copolymer surfactant of polyoxyethylene section is a soft template, resol resin is a carbon source, by in the space of colloidal crystal, carrying out organic-organic self-assembly, synthetic mesopore/macropore combined carbon material with multistage pore canal.This method method is simple, and raw material is easy to get, and is fit to amplify produce.
Summary of the invention
The object of the invention is to propose a kind of mesopore/macropore combined carbon material with multilevel ordered structure and preparation method thereof.
The preparation method of a kind of multilevel ordered mesoporous/macropore complex carbon material that this is proposed by the invention; be to utilize the die version of monodispersed silicon dioxide microsphere colloid crystalline substance as ordered big hole; utilization contains the block copolymer surfactant of polyoxyethylene section as order mesoporous soft mode version; with resol resin as the carbon material presoma; induce the principle of self-assembly (EISA) by solvent evaporates; the composite micelle of tensio-active agent and resol resin is filled in the space of ordered arrangement microballoon; make phenolic resin curing through baking again; carbonization under protection of inert gas then; remove the tensio-active agent masterplate; remove silicon dioxide microsphere with HF solution, thereby prepare the carbon material in the twin-stage duct that has mesoporous and macropore simultaneously.The spherical macropore diameter homogeneous of this carbon material and adjustable continuously between 100nm-500nm is made soft template by using different types of tensio-active agent, can produce aperture mesoporous at ordered arrangement 1-15nm, that the duct symmetry is adjustable at the macropore wall.
Mesopore/macropore combined carbon material with multilevel ordered structure proposed by the invention, it is characterized in that with resol resin as the carbon material presoma, the colloidal crystal of constructing with the silicon dioxide microsphere of ordered arrangement is as the die version, with the block copolymer surfactant that contains the polyoxyethylene section is the soft mode version, wherein silicon dioxide microsphere is formed macropore by HF solution dissolving back, and tensio-active agent decomposes mesoporous to form when high temperature cabonization.Macropore is the face-centered cubic ordered arrangement, and in the mesoporous space that is present between original silicon dioxide microsphere, the mesoporous short range order that presents is arranged.The carbon material degree of graphitization is looked the difference of concrete disposition and is changed.
Concrete preparation process is as follows:
(1) with the silicon dioxide microsphere colloidal crystal of ordered arrangement at 70-130 ℃ of following thermal treatment 6-24 hour, make exist between the silicon dioxide microsphere certain bonding;
(2) the silicon dioxide microsphere colloidal crystal after the thermal treatment be impregnated in resol resin and the solution that contains the block copolymer surfactant of polyoxyethylene section, in the solution, resol resin content is 4wt%-7wt%, the block copolymer surfactant that contains the polyoxyethylene section is 2-5wt%, and all the other are solvent; The needed resol resin that is dissolved with of 1g silicon dioxide microsphere colloidal crystal is 3-5g with the solution that contains the block copolymer surfactant of polyoxyethylene section;
(3) treat that above-mentioned solution evaporation fully after, take out colloidal crystal, 80-150 ℃ of baking 12-24 hour down, under protection of inert gas, will solidify the back sample and calcine 5-24 hour down then at 450-1000 ℃;
(4) to place concentration be that the 5-10wt%HF aqueous solution stirs 12-48h to the colloidal crystal after will calcining, and removes silica template; At last by centrifugal method (with mixed solution in the centrifugal 5-30min of 3000-10000rpm), remove carbon material behind the silicon-dioxide with the deionized water repetitive scrubbing, will be order mesoporous/macropore complex carbon material behind the black solid particle drying that obtain.
Use the silicon dioxide colloid crystal to form the macropore of ordered arrangement as hard template among the present invention, this colloidal crystal is constructed by the simple precipitation method by monodisperse silica microspheres and is obtained, and the suitable particle diameter of monodisperse silica microspheres is between 100-500nm.
Employed carbon material presoma is a resol resin among the present invention, 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.
Employed soft mode version is the block copolymer surfactant that contains the polyoxyethylene section among the present invention, the block copolymer surfactant that contains the polyoxyethylene section can be polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO) tensio-active agent, can be EO
20-PO
70-EO
70(P123), EO
106-PO
72-EO
106(F127) and EO
133-PO
50-EO
133One or more of the tensio-active agent of different molecular weight such as (F108), the block copolymer surfactant that contains the polyoxyethylene section also can be other tensio-active agent that contains polyoxyethylene blocks, can be C
16H
33-EO
10(Brij 56), C
17H
35-EO
10(Brij76), CH
3C (CH
3)
2CH
2C (CH
3)
2C
6H
4-EO
10One or more of (Triton X-100).
Resol resin that is adopted among the present invention and the solvent that contains the block copolymer surfactant solution of polyoxyethylene section, can be ethanol, methyl alcohol, Virahol, solubilized resol resin such as tetrahydrofuran (THF) and contain in the volatile organic solvent of block copolymer surfactant of polyoxyethylene section one or more.
The synthetic at present method with mesopore/macropore carbon material of multistage pore canal mainly is to pass through synthesising mesoporous/macroporous silica earlier as masterplate, then in the mesopore orbit of mesopore/macropore silicon-dioxide, fill the carbon material presoma, make then carbon matrix precursor mesopore/macropore silicon-dioxide as masterplate in charing, obtain the mesopore/macropore carbon material by removing the mesopore/macropore silicon dioxide hard template at last.This kind method steps is loaded down with trivial details, wayward, the use raw material is numerous.Comparatively speaking, method steps proposed by the invention is simple, uses raw material to be easy to get, and the mesopore/macropore carbon material that can have different mesopore orbit structures and duct size by using different tensio-active agents and presoma to obtain.The step of the inventive method is simple, and raw material is easy to get, and pore passage structure and aperture size can be regulated.Material of the present invention not only has the macropore (100-500nm) of the ordered arrangement that is interconnected, but also has the mesoporous wall (Fig. 1) of short range order.In addition, such material has the photonic band gap (Fig. 2) that the colloidal crystal structure is produced, and the forbidden band wavelength is adjustable continuously.This material has broad application prospects at aspects such as optical waveguide, transmitter, support of the catalyst.The inventive method is simple, and raw material is easy to get, and is suitable for amplifying producing.
Description of drawings
Fig. 1: use 240nm silicon-dioxide to be hard template, F127 is the multilevel ordered macroporous/mesoporous carbon material structure photo that soft template obtains.Wherein, the submicron order connected pore channel of a. ordered arrangement, the nano level connected pore channel that the b. short range order is arranged.
Fig. 2: the optical photograph of multilevel ordered macroporous/mesoporous carbon material, use 240nm silicon-dioxide to be hard template, F127 is a soft template, figure is a visible light reflection photo.
Embodiment
Embodiment 1:
With solid content is that the particle diameter of 10wt.% is two weeks of silicon dioxide microsphere dispersion liquid standing sedimentation of 240nm, inhales and removes supernatant liquor, dries naturally then and standby after toasting 12 hours down at 80 ℃.Getting silicon dioxide microsphere colloidal crystal after the 1.0g thermal treatment impregnated in the ethanolic soln that 4.0g contains 0.2g resole and 0.1g F127; at room temperature volatilize behind the 24h; take out colloidal crystal and toast 24h down at 100 ℃; and then be to obtain carbonaceous colloidal crystal in 5 hours in 800 ℃ of following calcinations under the nitrogen gas shiled; place the 10wt%HF aqueous solution slowly to stir 24h the colloidal crystal after the calcining; product is by centrifugation method distilled water repetitive scrubbing and vacuum drying; promptly obtain order mesoporous/macropore carbon material; its macropore diameter is about 230nm; mesoporous aperture is 10nm, and the mesopore orbit structure is three-dimensional cubic Im-3m.
Embodiment 2:
With solid content is that the particle diameter of 10wt.% is two weeks of silicon dioxide microsphere dispersion liquid standing sedimentation of 320nm, inhales and removes supernatant liquor, dries naturally then and standby after toasting 12 hours down at 80 ℃.Getting silicon dioxide microsphere colloidal crystal after the 1.0g thermal treatment impregnated in the ethanolic soln that 5.0g contains 0.2g resole and 0.2g F127; at room temperature volatilize behind the 24h; take out colloidal crystal and toast 8h down at 120 ℃; and then be to obtain carbonaceous colloidal crystal in 6 hours in 900 ℃ of following calcinations under the nitrogen gas shiled; place the 10wt%HF aqueous solution slowly to stir 24h the colloidal crystal after the calcining; product with distilled water repetitive scrubbing and vacuum drying, promptly obtains order mesoporous/macropore carbon material by centrifugation method.Its macropore diameter is about 310nm, and mesoporous aperture is 11nm, and the mesopore orbit structure is two dimension six side P6m.
Embodiment 3:
With solid content is that the particle diameter of 8wt.% is two weeks of silicon dioxide microsphere dispersion liquid standing sedimentation of 450nm, inhales and removes supernatant liquor, dries naturally then and standby after toasting 12 hours down at 100 ℃.Getting silicon dioxide microsphere colloidal crystal after the 1.0g thermal treatment impregnated in the ethanolic soln that 5.0g contains 0.3g resole and 0.15g F108; at room temperature volatilize behind the 24h; take out colloidal crystal and toast 24h down at 100 ℃; and then be to obtain carbonaceous colloidal crystal in 5 hours in 800 ℃ of following calcinations under the nitrogen gas shiled; place the 10wt%HF aqueous solution slowly to stir 24h the colloidal crystal after the calcining; product with distilled water repetitive scrubbing and vacuum drying, promptly obtains order mesoporous/macropore carbon material by centrifugation method.Its macropore diameter is about 435nm, and mesoporous aperture is 12nm, and the mesopore orbit structure is three-dimensional cubic Im-3m.
Embodiment 4:
With solid content is that the particle diameter of 10wt.% is two weeks of silicon dioxide microsphere dispersion liquid standing sedimentation of 240nm, inhales and removes supernatant liquor, dries naturally then and standby after toasting 12 hours down at 100 ℃.Getting silicon dioxide microsphere colloidal crystal after the 1.0g thermal treatment impregnated in the THF solution that 4.0g contains 0.3g resole and 0.12g P123; at room temperature volatilize behind the 24h; take out colloidal crystal and toast 24h down at 100 ℃; and then be to obtain carbonaceous colloidal crystal in 5 hours in 800 ℃ of following calcinations under the nitrogen gas shiled; place the 10wt%HF aqueous solution slowly to stir 24h the colloidal crystal after the calcining; product is by centrifugation method distilled water repetitive scrubbing and vacuum drying; promptly obtain order mesoporous/macropore carbon material.Its macropore diameter is about 225nm, and mesoporous aperture is 5nm, and the mesopore orbit structure is two dimension six side P6m.
Embodiment 5:
With solid content is that the particle diameter of 10wt.% is silicon dioxide microsphere microballoon dispersion liquid two weeks of standing sedimentation of 320nm, inhales and removes supernatant liquor, dries naturally then and standby after toasting 12 hours down at 100 ℃.Getting silicon dioxide microsphere colloidal crystal after the 1.0g thermal treatment impregnated in the THF solution that 5.0g contains 0.3g resole and 0.15g P123; at room temperature volatilize behind the 24h; take out colloidal crystal and toast 24h down at 100 ℃; and then be to obtain carbonaceous colloidal crystal in 5 hours in 800 ℃ of following calcinations under the nitrogen gas shiled; place the 10wt%HF aqueous solution slowly to stir 24h the colloidal crystal after the calcining; product with distilled water repetitive scrubbing and vacuum drying, promptly obtains order mesoporous/macropore carbon material by centrifugation method.Its macropore diameter is about 310nm, and mesoporous aperture is 5nm, and the mesopore orbit structure is three-dimensional cubic Ia-3d.
Claims (6)
- One kind multilevel ordered mesoporous/the macropore complex carbon material, it is characterized in that described carbon material is prepared by following method: with the hard template of monodispersed silicon dioxide microsphere colloid crystalline substance as ordered big hole, with block copolymer surfactant that the polyoxyethylene section is arranged as order mesoporous soft template, with resol resin as the carbon material presoma, induce the principle of self-assembly by solvent evaporates, the composite micelle of tensio-active agent and resol resin is filled in the space of ordered arrangement microballoon, make phenolic resin curing through baking again, charing under protection of inert gas then, remove surfactant templates, remove silicon dioxide microsphere with HF solution, thereby prepare the carbon material in the twin-stage duct that has mesoporous and macropore simultaneously; The spherical macropore diameter homogeneous of this carbon material and adjustable continuously between 100-500nm has aperture mesoporous at ordered arrangement 1-15nm, that duct symmetry is adjustable at the macropore wall.
- One kind multilevel ordered mesoporous/preparation method of macropore complex carbon material, it is characterized in that concrete steps are as follows:(1) with the silicon dioxide microsphere colloidal crystal of ordered arrangement at 70-130 ℃ of following thermal treatment 6-24 hour, make exist between the silicon dioxide microsphere certain bonding;(2) the silicon dioxide microsphere colloidal crystal after the thermal treatment be impregnated in resol resin and the solution that contains the block copolymer surfactant of polyoxyethylene section, in the solution, resol resin content is 4wt%-7wt%, the block copolymer surfactant that contains the polyoxyethylene section is 2-5wt%, and all the other are solvent; The resol resin that is dissolved with that 1g silicon dioxide microsphere colloidal crystal is used is 3-5g with the solution that contains the block copolymer surfactant of polyoxyethylene section;(3) treat that above-mentioned solution evaporation fully after, take out colloidal crystal, 80-150 ℃ down baking 12-24h make sample solidifies, then under protection of inert gas, with the sample after solidifying 450-1000 ℃ of calcining 5-24 hour down;(4) to place concentration be that the 5-10wt%HF aqueous solution stirs 12-48h to the colloidal crystal after will calcining, to remove silica template; By centrifugation method, the carbon material with behind the deionized water repetitive scrubbing removal silicon-dioxide will be order mesoporous/macropore carbon material behind the black solid particle drying that obtain at last.
- 3. according to claim 2 multilevel ordered mesoporous/preparation method of macropore complex carbon material, it is characterized in that adopting the monodisperse silica microspheres colloidal crystal as hard template, the particle diameter of monodisperse silica microspheres is 100-500nm.
- 4. according to claim 2 multilevel ordered mesoporous/preparation method of macropore complex carbon material, it is characterized in that employed resol resin is a resole, or have the substituting group resole, or the miscellany of above-mentioned materials.
- 5. according to claim 2 multilevel ordered mesoporous/preparation method of macropore complex carbon material, it is characterized in that the employed block copolymer surfactant that contains the polyoxyethylene section is the polyoxyethylene-poly-oxypropylene polyoxyethylene tensio-active agent, or EO 20-PO 70-EO 70, EO 106-PO 72-EO 106And EO 133-PO 50-EO 133One or more of tensio-active agent, or C 16H 33-EO 10, C 17H 35-EO 10, CH 3C (CH 3) 2CH 2C (CH 3) 2C 6H 4-EO 10
- 6. according to claim 2 multilevel ordered mesoporous/preparation method of macropore complex carbon material, it is characterized in that the employed solvent that adopts is one or more in ethanol, methyl alcohol, tetrahydrofuran (THF) and the Virahol.
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