CN1544321A - Preparation method of carbon material with highly ordered nanometer hole of graphite hole wall structure - Google Patents
Preparation method of carbon material with highly ordered nanometer hole of graphite hole wall structure Download PDFInfo
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- CN1544321A CN1544321A CNA2003101088454A CN200310108845A CN1544321A CN 1544321 A CN1544321 A CN 1544321A CN A2003101088454 A CNA2003101088454 A CN A2003101088454A CN 200310108845 A CN200310108845 A CN 200310108845A CN 1544321 A CN1544321 A CN 1544321A
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Abstract
The invention relates to a process for synthesizing highly ordered nano pore carbon material with graphitization pore wall structure, wherein the preparation process comprises the steps of, heating a definite quantity of carbon precursor asphalt to melting, immersing the silicon oxide hole material with ordered pore passages into the precursor, agitating homogeneously and performing high-temperature roasting to the black solid body with nitrogen protection, thus fully carbonizing the material, placing the composite of carbon and silicon oxide into sodium hydroxide or hydrogen fluoride liquid, thereby dissolving the silicon oxide mold plate, and the nano pore carbon material having ordered pore passage structure can be obtained by further filtering, washing and drying.
Description
Technical field
The invention belongs to inorganic advanced material technical field, be specifically related to the preparation method of the nanoporous carbon material of a kind of greying hole wall structure, high-sequential,
Technical background
Flourish along with the mano-porous material field, the nanoporous carbon material also more and more receives scientist and investigator's concern, and this is because this type of material all has special advantages at aspects such as electronics, catalysis and hydrogen storage.Orderly nanoporous carbon material is arranged because of the duct that it has rule, and shows more special nature, has attracted many scientific workers to carry out the synthetic and property research of this type of material.Orderly nanoporous carbon material adopts porous material synthetic as hard template usually.Porous material has the duct of particular arrangement, has the space constraint effect, and carbon is grown in the duct, plays the effect of hard template.Porous material commonly used comprises micro-pore zeolite, aluminum oxide film etc.; SiO 2 mesoporous materials also is used gradually recently.Because the inorganic wall of Metaporous silicon dioxide material is made up of unformed silicon-dioxide, the surface has abundant hydroxyl, easy and organic carbon precursor interacts, and this type of mesoporous material has the duct of high-sequential, and these characteristics are very favorable for synthesizing ordered nanoporous carbon material.
It is carbon matrix precursor that carbon mano-porous material synthetic generally selected sucrose or furfuryl alcohol for use, these organic graphitization temperatures are up to more than 2800 ℃, therefore the hole wall of the synthetic ordered nano hole carbon material that obtains all is amorphous state usually at present, even adopt 1600 ℃ pyroprocessing, also can only make its hole wall surface generation part greying, and higher thermal treatment temp can cause caving in of material structure.This drawback has limited the application of this type of material in battery, electrical condenser, Chu Qing and Industrial Catalysis.
Summary of the invention
The objective of the invention is to propose a kind of synthetic method with ordered nano hole carbon material of greying hole wall structure, pore passage structure height.
The preparation method of the greying hole wall structure that the present invention proposes, the nanoporous carbon material of high-sequential is to adopt pitch as carbon matrix precursor, and directly low temperature is synthetic, and its concrete steps are as follows: at first with carbon matrix precursor pitch heating and melting; The SiO 2 mesoporous materials that will have orderly duct again is immersed in this presoma, stirs, and forms mesopore silicon oxide and carbon matrix precursor mixture, is black solid; Mixture roasting under nitrogen atmosphere with obtaining makes the material carbonization, obtains the mixture of carbonization structure carbon and silicon oxide; The mixture of this carbon and silicon-dioxide is placed sodium hydroxide solution or hydrofluoric acid solution, make original silica template dissolving; At last after filtration, washing, drying, can obtain the nanoporous carbon material of greying hole wall structure, high-sequential.
Among the present invention, the step that obtains molten state bitumencarb presoma is as follows: pitch is heated to it more than softening temperature in oil bath, stirred 0.1-2 hour on magnetic stirring apparatus, form the molten state carbon matrix precursor with high fluidity.Used bituminous softening temperature is 40-280 ℃, and the Heating temperature in the oil bath is 100-300 ℃
Among the present invention, the step that forms Metaporous silicon dioxide material and carbon matrix precursor mixture is as follows: the earth silicon material that will have orderly pore passage structure joins in the prepared molten state bitumencarb of step 1 presoma, and continues to stir 0.1-2 hour; The mass ratio of Metaporous silicon dioxide material and mesophase pitch is 1: 0.5-1: 2;
Among the present invention, the step of mixture that forms carbonization structure carbon and silicon-dioxide is as follows: with Metaporous silicon dioxide material and carbon matrix precursor mixture under nitrogen protection in 600-1300 ℃ of roasting 2-20 hour;
Among the present invention, the silica template agent remove processing, be that the mixture that will obtain places sodium hydroxide solution or hydrofluoric acid solution to stir 10-100 hour.
As the carbon precursor, its softening temperature is between 40-280 ℃ with abundant, the cheap pitch of species in the present invention.Wherein, the most suitable synthetic method proposed by the invention of mesophase pitch that contains big conjugation condensed ring structure.
The present invention has adopted the process of a low-temperature heat, has obtained to have high fluidity and infiltrating molten state carbon matrix precursor.
The present invention has adopted the roasting carbonization process under the inert atmosphere, makes the material to have carbonization structure.
Among the present invention, used template is the SiO 2 mesoporous materials with high-sequential pore passage structure.This type of mould material has different pore passage structure (cube or six sides, as), pore size (5-15nm), wall thickness (1-5nm) and macro morphology (ball, rod, sheet, crystal), structure that can the final carbon material of modulation.Available template has the FDU-5 of co-continuous cubic structure, the FDU-12 of face-centred cubic structure, the SBA-16 of body-centered cubic structure, the SBA-3 of wide-aperture SBA-15 of six sides and six side small-bores etc., or the above-mentioned mesoporous material of metal-doped (Fe, Co, Ni or Al).
Among the present invention, original silicon dioxide hard template can adopt sodium hydroxide solution to remove, and the concentration of using is 1-3molL
-1Also can adopt hydrofluoric acid dissolution to remove, the concentration of use is generally 5-15%.
Among the present invention, mesophase pitch is the hydroxyl effect by condensed ring structure and mesoporous silicon oxide template internal surface, and then enters the duct of Metaporous silicon dioxide material by capillary condensation.
The present invention selects for use the compound with big condensed ring structure as carbon matrix precursor, and under the restriction of nanoporous, its big conjugate ring structure obtains the carbon material of greying structure at a lower temperature by the II-II accumulation.The pitch of forming with difference is the carbon precursor, is template with the Metaporous silicon dioxide material with high-sequential pore passage structure, synthetic greying hole wall structure, the pore passage structure high-sequential nanoporous carbon material of having obtained.
Embodiment
Embodiment 1 synthesis step is as follows: get mesophase pitch 1.3g, be warming up to 140 ℃, mesophase pitch fusing and viscosity diminish, stir after 0.5 hour, add 1g silica mesoporous zeolite SBA-15, after mesophase pitch enters the duct, obtain pale brown look solid, continue to stir 0.5 hour, roasting 6 hours in 1000 ℃ of nitrogen atmospheres then promptly obtains the mixture of carbon and silicon-dioxide.This mixture was stirred 24 hours in 10%HF solution, filter then, wash and drying, obtain the black solid powder.Through PXRD, BET, TEM etc. analyze test shows, and gained is has the greying hole wall structure, the nanoporous carbon material of two-dimentional hexagonal pore passage structure, its aperture is 3.8nm, specific surface area is 390m
2/ g, pore volume are 0.4cm
3/ g.
Embodiment 2 synthesis steps are as follows: in getting with asphalt phase 1g, be warming up to 160 ℃, mesophase pitch fusing and viscosity diminish, stir after 1 hour, add 1g silica mesoporous zeolite SBA-3, after mesophase pitch enters the duct, obtain pale brown look solid, continue to stir 1 hour, roasting 6 hours in 800 ℃ of nitrogen atmospheres then promptly obtains the mixture of carbon and silicon-dioxide.This mixture was stirred 48 hours in 8%HF solution, filter then, wash and drying, obtain the black solid powder.Through PXRD, BET, TEM etc. analyze test shows, and gained is has the greying hole wall structure, the nanoporous carbon material of two-dimentional hexagonal pore passage structure, its aperture is 2.8nm, specific surface area is 450m
2/ g, pore volume are 0.5cm
3/ g.
Embodiment 3 synthesis steps are as follows: get mesophase pitch 1.3g, be warming up to 170 ℃, mesophase pitch fusing and viscosity diminish, after stirring for 1 time, (the initial reaction mass ratio is Si: Fe=25: 1), obtain pale brown look solid after mesophase pitch enters the duct, continue to stir 2 o'clock to add 1g silica mesoporous zeolite Fe-SBA-15, roasting 6 hours in 1000 ℃ of nitrogen atmospheres then promptly obtains the mixture of carbon and silicon-dioxide.With this mixture at 2mol L
-1Stirred 36 hours in the solution, filter then, wash and drying, obtain the black solid powder.Through PXRD, BET, TEM etc. analyze test shows, and gained is has the greying hole wall structure, the nanoporous carbon material of two-dimentional hexagonal pore passage structure, its aperture is 3.5nm, specific surface area is 410m
2/ g, pore volume are 0.5cm
3/ g.
Claims (8)
1, a kind of greying hole wall structure. the preparation method of the nanoporous carbon material of high-sequential, with pitch as carbon matrix precursor, adopt low temperature directly synthetic, it is characterized in that concrete steps are as follows: at first with carbon matrix precursor pitch heating and melting, the SiO 2 mesoporous materials that will have orderly pore passage structure again is immersed in this presoma; After stirring, form the mixture of mesopore silicon oxide and carbon matrix precursor; With the high-temperature roasting under nitrogen atmosphere of this mixture, make the material carbonization, form the mixture of mesopore silicon oxide and carbonization structure carbon; The mixture of this carbon and silicon-dioxide is placed sodium hydroxide solution or hydrofluoric acid, make the silica template dissolving; At last after filtration, washing, drying, promptly obtain having the hole wall of carbonization structure, the nanoporous carbon material of the pore passage structure of high-sequential.
2, preparation method according to claim 1, the step that it is characterized in that carbon matrix precursor pitch heating and melting is as follows: pitch is heated to it more than softening temperature in oil bath, on magnetic stirring apparatus, stirred 0.1-2 hour, form molten state carbon matrix precursor with high fluidity; Used pitch softening temperature is 40-280 ℃, and the Heating temperature in the oil bath is 100-300 ℃.
3, preparation method according to claim 1, the step that it is characterized in that forming Metaporous silicon dioxide material and carbon matrix precursor mixture is as follows: the earth silicon material that will have orderly pore passage structure joins in the molten state bitumencarb precursor, stirs 0.1-2 hour; The mass ratio of SiO 2 mesoporous materials and mesophase pitch is 1: 0.5-1: 2.
4, preparation method according to claim 1, the step of mixture that it is characterized in that forming carbonization structure carbon and silicon-dioxide is as follows: with the Metaporous silicon dioxide material that obtains and carbon matrix precursor mixture under nitrogen protection in 600-1300 ℃ of roasting 2-20 hour.
5, preparation method according to claim 1 is characterized in that placing sodium hydroxide solution or hydrofluoric acid solution to stir 10-100 hour the mixture of gained carbonization structure carbon and mesoporous silicon oxide.
6, preparation method according to claim 1 is characterized in that adopting the mesophase pitch that contains big conjugation condensed ring structure as the carbon precursor.
7, preparation method according to claim 1, the concentration that it is characterized in that sodium hydroxide solution is 1-3mol/L, hydrofluoric acid concentration is 5-15%.
8,, it is characterized in that used SiO 2 mesoporous materials has different pore passage structures, pore size, wall thickness and macro morphology, with the structure of the final carbon material of modulation according to the preparation method of claim 1.
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| US7776779B2 (en) | 2005-11-21 | 2010-08-17 | Samsung Sdi Co., Ltd. | Mesoporous carbon, manufacturing method thereof, and fuel cell using the mesoporous carbon |
| CN1970442B (en) * | 2005-11-22 | 2010-09-22 | 三星Sdi株式会社 | Mesoporous carbon, method of preparing the same, and fuel cell using the carbon |
| CN102247803A (en) * | 2011-05-04 | 2011-11-23 | 中国科学院化学研究所 | Core-shell type magnetic mesoporous nano-microsphere as well as preparation method and application thereof |
| CN101435792B (en) * | 2008-12-17 | 2012-05-30 | 中国科学院上海硅酸盐研究所 | Mesoporous carbon immobilized enzyme biological sensing material doped with nitrogen and preparing method thereof |
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| CN102804464A (en) * | 2009-06-25 | 2012-11-28 | 国立大学法人长崎大学 | Macro-porous graphite electrode material, process for production thereof, and lithium ion secondary battery |
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| US7776779B2 (en) | 2005-11-21 | 2010-08-17 | Samsung Sdi Co., Ltd. | Mesoporous carbon, manufacturing method thereof, and fuel cell using the mesoporous carbon |
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| US7854913B2 (en) | 2005-11-22 | 2010-12-21 | Samsung Sdi Co., Ltd. | Mesoporous carbon, method of preparing the same, and fuel cell using the carbon |
| CN101435792B (en) * | 2008-12-17 | 2012-05-30 | 中国科学院上海硅酸盐研究所 | Mesoporous carbon immobilized enzyme biological sensing material doped with nitrogen and preparing method thereof |
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