CN102718204A - Preparation method for three-dimensional ordered macroporous porous carbon - Google Patents
Preparation method for three-dimensional ordered macroporous porous carbon Download PDFInfo
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- CN102718204A CN102718204A CN2011100771212A CN201110077121A CN102718204A CN 102718204 A CN102718204 A CN 102718204A CN 2011100771212 A CN2011100771212 A CN 2011100771212A CN 201110077121 A CN201110077121 A CN 201110077121A CN 102718204 A CN102718204 A CN 102718204A
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Abstract
The invention relates to a preparation method for a three-dimensional ordered macroporous porous carbon which is characterized by including the following steps: firstly, spherical silica carbon particles of 250 nm with fluorescence are synthesized via a hydrolysis method by taking tetraethyl orthosilicate as a silicon source. Later, the prepared spherical silica carbon particles are treated to form a water solution of spherical silica carbon particles. Then, the prepared water solution is added to silicone oil which is stirred forcefully. Thereafter, the turbid solution prepared by step (3) is placed still and distilled to dry. Then, the product prepared by step (4) is washed and separated with n-hexane to obtain a silica photonic crystal. Finally, the three-dimensional ordered macroporous porous carbon is obtained after a high-temperature curing by taking the silica photonic crystal as a template and being cooperated with a carbon source. Therefrom, the whole preparation process is characterized by easy and convenient operation, regular and uniform carbon spheres, and three-dimensional and ordered channels. And, the pore size of the carbon spheres can be adjusted through the particle size of the silica particles. The method is worthy to be popularized.
Description
Technical field
The present invention relates to a kind of preparation method of porous carbon, relate in particular to a kind of preparation method of three-dimensional ordered macroporous porous carbon.
Background technology
At present, porous carbon has the extensive concern that the aperture of high specific surface area, homogeneous, big pore volume, high mechanical stability and good electrical conductivity have attracted people.Porous carbon has great importance for catalysis, absorption and electrochemical applications with the preparation of the nano material of other metals or metal oxide nanoparticles.Along with going deep into of research, irregular porous material has been difficult to satisfy the demand of each discipline development, and under this background, three-dimensional ordered macroporous carbon nanomaterial arises at the historic moment.Compare with irregular porous carbon materials; Three-dimensional ordered macroporous nano material has the advantage of regularity and three-dimensional porous structure simultaneously; Can realize simultaneously that big catalyzer fully contacts and reduce the multiple functions such as resistance in reactant turnover duct with reactant; Have good application prospects, received showing great attention to of area research persons such as materialogy, biology, medical science.
Preparation of nanomaterials is varied, such as the gas delivery method, and laser ablation method, high temperature injection method, hydro-thermal solvent method and template etc.The gas transport method is to be used for extraction and the purge process that some are prone to the distillation compound the earliest.Its method is with alloy or compound heating evaporation in certain carrier gas atmosphere; (typical document comprises: Pan Z to form ultrafine powder in the low-temperature region condensation; Dai Z; Wang Z.Nanobelts of Semiconducting Oxides [J] .Science, 2001,291 (5510): 1947～1949.).The laser ablation method is a plasma effect of utilizing laser radiation on target body, to produce; Directly article on plasma gas carries out vacuum cooling or feeds reactant gases synthesizing porous nano material that (typical document comprises: Hu J; Odom T W; Lieber C M.Chemistry and Physics in OneDimension:Synthesis and Properties of Nanowires and Nanotubes [J] .Accounts Chem.Res., 1999,32 (5): 435～445.).The high temperature injection method is in the pyrosol system of tensio-active agent, to inject cold precursor, through the quick dissemination under the high temperature, and moment reaction nucleation; Growth under the protection of tensio-active agent, (typical document comprises: Peng X, Manna L finally to obtain the colloidal nano particle; Yang W, et al., Shape control of CdSe nanocrystals [J] .Nature; 2000,404 (6773): 59～61.).The hydro-thermal solvent method is in the seal-off pressure container, with water as solvent, at high temperature (＞100 ℃); ((typical document comprises a kind of method of preparation material high pressure: Li Y D under＞908MPa) the condition; Duan X F, Qian Y T, et al.Solvothermal Co-reduction Route to the Nanocrystalline III-V Semiconductor InAs [J] .J.Am.Chem.Soc.; 1997,119 (33): 7869～7870.).Template is carbon to be injected template remove template then (typical document comprises: Ryoo R, Joo S H, Jun S. [J] .Journal of Physics., 1999,103 (37): 7743～7746..), and the material of three-dimensional ordered macroporous carbon report not.
Summary of the invention
The object of the invention is exactly the problems referred to above that exist in the prior art in order to solve, and a kind of preparation method of three-dimensional ordered macroporous porous carbon is provided.
The object of the invention is realized through following technical scheme:
The preparation method of three-dimensional ordered macroporous porous carbon is characterized in that may further comprise the steps:
1. step is the silicon source with positive tetraethyl orthosilicate, the preparing spherical SiO 2 carbon particles of 250 nanometers through method for hydrolysis anamorphic zone fluorescence;
2. step is made into the preparing spherical SiO 2 carbon particles aqueous solution with the preparing spherical SiO 2 carbon particles that makes;
3. step adds the aqueous solution that makes in the silicone oil, the powerful stirring;
Step 4., the turbid liquid that 3. step is made leaves standstill, and evaporate to dryness water;
Step 5., with step 4. in prepared product separate through washing with normal hexane, obtain the silicon-dioxide photonic crystal;
6. step is template with the silicon-dioxide photonic crystal, cooperates carbon source, through getting three-dimensional ordered macroporous porous carbon behind the hot setting.
The preparation method of above-mentioned three-dimensional ordered macroporous porous carbon, wherein: the massfraction of the 2. said silicon-dioxide carbon particles of the step aqueous solution is 20w%-30w%.
Further, the preparation method of above-mentioned three-dimensional ordered macroporous porous carbon, wherein: the 4. described evaporate to dryness temperature of step is 70 ℃.
Further, the preparation method of above-mentioned three-dimensional ordered macroporous porous carbon, wherein: the 6. described template construct method of step is that at first adopting glucose is carbon sourceization, and glucose is configured to solution, adds small amount of sulfur acid catalyst and silicon-dioxide photonic crystal; Then, solution is inserted in the electronics baking oven, under 160 ℃ of temperature, dried 24 hours; Afterwards, the black solid that obtains adds and contains in the small amount of sulfur aqueous acid, at 160 ℃ of following evaporates to dryness; At last, product obtains three-dimensional ordered macroporous carbon material 900 ℃ of following vacuum calcinations.
Again further, the preparation method of above-mentioned three-dimensional ordered macroporous porous carbon, wherein: described carbon source comprises glucose, sucrose and starch and compsn thereof.
The advantage of technical scheme of the present invention is mainly reflected in: whole process of preparation is simple to operation, and the carbon gauge ball is homogeneous then, the duct three-dimensional order.And the big I in carbon ball hole is worthy to be popularized through the particle size adjustment of silicon dioxide granule.
Description of drawings
The object of the invention, advantage and characteristics will illustrate through the non-limitative illustration of following preferred embodiment and explain.These embodiment only are the prominent examples of using technical scheme of the present invention, and all technical schemes of taking to be equal to replacement or equivalent transformation and forming all drop within the scope of requirement protection of the present invention.In the middle of these accompanying drawings,
Fig. 1 a, 1b, 1c, 1d adopt the prepared silicon-dioxide photonic crystal of the present invention Electronic Speculum figure;
Fig. 2 a, 2b, 2c, 2d adopt the prepared three-dimensional ordered macroporous carbon Electronic Speculum figure of the present invention;
Fig. 3 a is the TEM figure that adopts the prepared three-dimensional ordered macroporous carbon of the present invention;
Fig. 3 b adopts the prepared three-dimensional ordered macroporous carbon of the present invention to carry Pt catalyzer figure;
Fig. 4 adopts the prepared three-dimensional ordered macroporous carbon of the present invention to carry the cyclic voltammogram of Pt catalyzer in sulphuric acid soln;
Fig. 5 adopts the prepared three-dimensional ordered macroporous carbon of the present invention to carry Pt catalyst oxidation methanol loop voltammogram.
Embodiment
The preparation method of three-dimensional ordered macroporous porous carbon, its unusual part is to adopt following steps: at first, be the silicon source with positive tetraethyl orthosilicate, through the preparing spherical SiO 2 carbon particles of method for hydrolysis Synthetic 2 50 nanometers.
Afterwards, the preparing spherical SiO 2 carbon particles that makes is made into the preparing spherical SiO 2 carbon particles aqueous solution.Realize that thus it fully disperses.Certainly, consider the effect of preparation, with regard to the present invention's one preferred implementation, the massfraction of the silicon-dioxide carbon particles aqueous solution is 20w%-30w%.
Then, the aqueous solution that makes being added in the silicone oil, is in order to guarantee that it fully disperses, can also to adopt powerful the stirring equally.
Subsequently, the turbid liquid that makes is left standstill, and evaporate to dryness water.Concrete rice says that in order to improve the effect of evaporate to dryness, the evaporate to dryness temperature that the present invention adopted is 70 ℃.
Then, the prepared product of institute separates through washing with normal hexane before, obtains the silicon-dioxide photonic crystal;
At last, be template with the silicon-dioxide photonic crystal, cooperate carbon source, through getting three-dimensional ordered macroporous porous carbon behind the hot setting.Further combine the present invention's one preferred implementation again, the template construct method of employing does, step 1., getting glucose is carbon sourceization.Glucose is configured to solution, adds small amount of sulfur acid catalyst and silicon-dioxide photonic crystal.2. step is inserted solution in the electronics baking oven, under 160 ℃ of temperature, dries 24 hours.3. step with the black solid that had before obtained, adds and contains in the small amount of sulfur aqueous acid, at 160 ℃ of following evaporates to dryness.4. step 900 ℃ of following vacuum calcinations, obtains three-dimensional ordered macroporous carbon material with product.
Simultaneously, the production of collective entity makes and is used for seeing, the described carbon source that the present invention adopts can also adopt sucrose and starch except using glucose, can certainly adopt its compsn.And, be not limited to these compounds.
With the silicon-dioxide photonic crystal is template, then with the synthetic three-dimensional ordered macroporous carbon material of template.Utilize glucose carbonization at high temperature to obtain porous carbon structure and be example.(, be ordinary method like no specified otherwise; Said reagent and material like no specified otherwise, all can obtain from commercial sources.)
The preparing spherical SiO 2 particles of 250 nanometers that make is made into the solution that massfraction is 20w%-30w% (glucose is CP, and used solvent is a deionized water).With adding 10g glucose and 0.1ml sulfuric acid catalyst, 70 ℃ of oven dry in the above-mentioned silicon dioxde solution.Add the gained black powder afterwards and contain oven dry once more in 10g glucose and the 0.1ml sulphuric acid soln.Above the black powder that obtains 900 ℃ of following calcinations of vacuum 6 hours.Remove silica template with HF then, promptly obtain three-dimensional ordered macroporous carbon material.
And,, made SEM, TEM, electrochemistry figure respectively for the pattern that characterizes product, composition, as the character of support of the catalyst.Electromicroscopic photograph such as Fig. 1 are the SEM figure of silicon-dioxide photonic crystal, and master map is SEM, TEM.Fig. 2 is the SEM of three-dimensional ordered macroporous carbon.And the TEM of product such as Fig. 3 a, Fig. 3 b are the TEM of its platinum catalyst.Fig. 4 carries platinum as the cyclic voltammogram of catalyzer in sulfuric acid.Fig. 5 is the electrochemistry figure of its methanol catalytic oxidation.Above-mentioned figure spectral representation has showed good catalytic performance as support of the catalyst because the orderly character of its three-dimensional macropore, catalyzer is fully contacted with reactant and reduced reactant in its duct the resistance during circulation.
Can find out that through above-mentioned character express behind employing the present invention, simple to operation, the carbon gauge ball is homogeneous then, the duct three-dimensional order.And the big I in carbon ball hole is worthy to be popularized through the particle size adjustment of silicon dioxide granule.
Claims (5)
1. the preparation method of three-dimensional ordered macroporous porous carbon is characterized in that may further comprise the steps:
1. step is the silicon source with positive tetraethyl orthosilicate, through the preparing spherical SiO 2 carbon particles of method for hydrolysis Synthetic 2 50 nanometers;
2. step is made into the preparing spherical SiO 2 carbon particles aqueous solution with the preparing spherical SiO 2 carbon particles that makes;
3. step adds the aqueous solution that makes in the silicone oil, the powerful stirring;
Step 4., the turbid liquid that 3. step is made leaves standstill, and evaporate to dryness water;
Step 5., with step 4. in prepared product separate through washing with normal hexane, obtain the silicon-dioxide photonic crystal;
6. step is template with the silicon-dioxide photonic crystal, cooperates carbon source, through getting three-dimensional ordered macroporous porous carbon behind the hot setting.
2. the preparation method of three-dimensional ordered macroporous porous carbon according to claim 1, it is characterized in that: the massfraction of the 2. said silicon-dioxide carbon particles of the step aqueous solution is 20w%-30w%.
3. the preparation method of three-dimensional ordered macroporous porous carbon according to claim 1, it is characterized in that: the 4. described evaporate to dryness temperature of step is 70 ℃.
4. the preparation method of three-dimensional ordered macroporous porous carbon according to claim 1; It is characterized in that: the 6. described template construct method of step does; At first adopting glucose is carbon sourceization, and glucose is configured to solution, adds small amount of sulfur acid catalyst and silicon-dioxide photonic crystal; Then, solution is inserted in the electronics baking oven, under 160 ℃ of temperature, dried 24 hours; Afterwards, the black solid that obtains adds and contains in the small amount of sulfur aqueous acid, at 160 ℃ of following evaporates to dryness; At last, product obtains three-dimensional ordered macroporous carbon material 900 ℃ of following vacuum calcinations.
5. the preparation method of three-dimensional ordered macroporous porous carbon according to claim 1, it is characterized in that: described carbon source comprises glucose, sucrose and starch and compsn thereof.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104800851A (en) * | 2015-04-09 | 2015-07-29 | 辽宁医学院 | Preparation method and application of biodegradable three-dimensionally ordered macroporous material |
| CN106129425A (en) * | 2016-09-21 | 2016-11-16 | 许昌学院 | A kind of porous carbon electrode material and its preparation method and application |
| US9982078B2 (en) | 2016-03-30 | 2018-05-29 | National Taipei University Of Technology | Copolymer containing residues of vinylbenzyl halide and vinylbenzyl alcohol and synthesis thereof, porous structure comprising the copolymer and production thereof, and porous carbon sphere |
| CN110407192A (en) * | 2019-08-19 | 2019-11-05 | 上海交通大学 | Three-dimensional order graded porous carbon photonic crystal method is prepared using metal organic frame |
| CN110518247A (en) * | 2019-08-19 | 2019-11-29 | 上海交通大学 | Lithium-sulfur cell and preparation method thereof based on carbon photonic crystal metal coating structure |
| CN113908836A (en) * | 2021-09-30 | 2022-01-11 | 广州市佳境水处理技术工程有限公司 | Neutral advanced oxidation catalyst and preparation method thereof |
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| US20040024074A1 (en) * | 2000-08-09 | 2004-02-05 | Tennison Stephen Robert | Porous carbons |
| CN1730392A (en) * | 2005-06-16 | 2006-02-08 | 复旦大学 | Large aperture capacity silicon oxide vesicle, foamed material and process for preparing the same |
| CN101099929A (en) * | 2007-06-18 | 2008-01-09 | 浙江理工大学 | Method for preparing interface optical catalyst |
| CN101985358A (en) * | 2010-11-09 | 2011-03-16 | 同济大学 | Method for quickly preparing carbon-silicon dioxide composite aerogel |
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2011
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20040024074A1 (en) * | 2000-08-09 | 2004-02-05 | Tennison Stephen Robert | Porous carbons |
| CN1730392A (en) * | 2005-06-16 | 2006-02-08 | 复旦大学 | Large aperture capacity silicon oxide vesicle, foamed material and process for preparing the same |
| CN101099929A (en) * | 2007-06-18 | 2008-01-09 | 浙江理工大学 | Method for preparing interface optical catalyst |
| CN101985358A (en) * | 2010-11-09 | 2011-03-16 | 同济大学 | Method for quickly preparing carbon-silicon dioxide composite aerogel |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104800851A (en) * | 2015-04-09 | 2015-07-29 | 辽宁医学院 | Preparation method and application of biodegradable three-dimensionally ordered macroporous material |
| CN104800851B (en) * | 2015-04-09 | 2017-08-04 | 辽宁医学院 | A kind of preparation method of biodegradable There-dimensional ordered macroporous materials and application |
| US9982078B2 (en) | 2016-03-30 | 2018-05-29 | National Taipei University Of Technology | Copolymer containing residues of vinylbenzyl halide and vinylbenzyl alcohol and synthesis thereof, porous structure comprising the copolymer and production thereof, and porous carbon sphere |
| CN106129425A (en) * | 2016-09-21 | 2016-11-16 | 许昌学院 | A kind of porous carbon electrode material and its preparation method and application |
| CN110407192A (en) * | 2019-08-19 | 2019-11-05 | 上海交通大学 | Three-dimensional order graded porous carbon photonic crystal method is prepared using metal organic frame |
| CN110518247A (en) * | 2019-08-19 | 2019-11-29 | 上海交通大学 | Lithium-sulfur cell and preparation method thereof based on carbon photonic crystal metal coating structure |
| CN113908836A (en) * | 2021-09-30 | 2022-01-11 | 广州市佳境水处理技术工程有限公司 | Neutral advanced oxidation catalyst and preparation method thereof |
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Application publication date: 20121010 |