CN101492159A - Graphitized stephanoporate material with carbon element and method of producing the same - Google Patents
Graphitized stephanoporate material with carbon element and method of producing the same Download PDFInfo
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- CN101492159A CN101492159A CNA2009100797554A CN200910079755A CN101492159A CN 101492159 A CN101492159 A CN 101492159A CN A2009100797554 A CNA2009100797554 A CN A2009100797554A CN 200910079755 A CN200910079755 A CN 200910079755A CN 101492159 A CN101492159 A CN 101492159A
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Abstract
The invention relates to a method for preparing graphitized porous carbon materials, which comprises that: hydrous metal oxide nano-particles dispersed in an aqueous solution are taken as templates to form metal oxide-organic polymer composite structures through condensation polymerization of a phenolic aldehyde precursor around a template phase; and in the subsequent high-temperature carbonization process, the composition structures form graphitized structures under the catalysis action of metal, and the graphitized porous carbon materials are obtained after the metal is dissolved by acid, wherein partial materials have magnetism. The materials can be applied in the fields of battery, adsorption, catalysis, water pollution removal, and the like.
Description
Technical field
The invention belongs to raw material of wood-charcoal material preparing technical field, particularly belong to the preparation method of graphitized stephanoporate material with carbon element.
Background technology
The chemical stability of graphite material and conduction and heat conductivility are all relatively good, but natural graphite material does not possess vesicular structure, and specific surface area is no more than 20m usually
2/ g has limited its application in some fields.The synthesizing porous carbon of template is one of research and development focus in recent years, is divided into hard template method and soft template method usually.Hard template is commonly referred to as some inorganic porous materials, and as silicon oxide colloid crystal, molecular sieve, clay etc., template exists with solid-state form in building-up process.Soft template refers to the supramolecular structure of organic surface active agent or the formation of polymkeric substance in water or organic solvent.The building-up process of hard template method and soft template method is more complicated all often, and synthetic cost is higher.And generally, the synthetic porous carbon is mainly amorphous structure, and graphited degree is very low.In order to obtain degree of graphitization than higher porous carbon, need be at higher Temperature Treatment (＞2000 ℃), but can cause the havoc of pore structure.In addition, the higher porous carbon of degree of graphitization can be synthetic by the method for chemical vapour deposition, but carbon-source cpd acetonitrile commonly used has very strong toxicity.On the basis of the synthetic amorphous porous charcoal of template,, can under lower temperature, be converted into graphited structure, and maintain certain pore texture, but synthesis step is more by impregnated catalyst.
Summary of the invention
The invention provides the preparation method of the higher graphitized stephanoporate material with carbon element of a kind of specific surface area.
Core of the present invention is to use the hydrated metal oxide colloidal particle of stable dispersion in the aqueous solution as template, and template also plays the effect of catalyzed graphitization in carbonization process.Method combines the advantage of soft template method and hard template method, but has any different in general soft, hard template method: template and carbon source presoma form mixture by the sol-gel process in the liquid phase, and this is similar to soft template method; But, use inorganic particulate as template, this is similar to hard template method.
Preparation process is as follows:
Phenol is dissolved in the colloidal solution of hydrated metal oxide, add formaldehyde, 20-150 ℃ of reaction 0.2-144 hour, after solid product separation and drying, in inert atmosphere 500-2400 ℃ charing 0.2-5 hour, the product that obtains is immersed in the acid, removes metallic element as much as possible, separate obtaining graphitized stephanoporate material with carbon element.
Described hydrated metal oxide nanoparticle refers to the nanoparticle (preparation method is with reference to Chinese patent ZL 200510012045.1) that weak acid dissolution of metals oxyhydroxide obtains, or the nanoparticle that obtains of regulator solution acidic moiety hydrolysis metal-salt, stable being dispersed in forms colloidal solution in the water.
Metallic element in the described hydrated metal oxide nanometer colloid particle template is iron, cobalt, manganese, copper or manganese.
Described phenol is phenol, pyrocatechol, Resorcinol, Resorcinol, oxyhydroquinone or Phloroglucinol.
The mol ratio of described phenol and formaldehyde is 1: 1-1: 5.
The described acid that is used to remove metallic element is hydrochloric acid, sulfuric acid or nitric acid.
Present method preparation technology is simple, and is with low cost, and product has higher degree of graphitization, and electrical and thermal conductivity performance is good, has bigger reference area (200-600m
2/ g), have application promise in clinical practice in fields such as fuel cell, absorption, energy storage, catalysis.And, because the part metals element by the complete coating of graphite-structure, can not be removed by acid soak, in final product, contain to a certain degree elemental metals or metal oxide.The product that contains metallic iron or cobalt metal has magnetic, can be separated by magnetic, may be applied in water pollution control or other field.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of the graphitized stephanoporate material with carbon element of the embodiment of the invention 1 preparation
Fig. 2 is the Raman spectrogram of the embodiment of the invention 2 preparation graphitized stephanoporate material with carbon element
Embodiment
Embodiment 1
2.3 gram Resorcinols are dissolved in 45 restrain (aqua oxidation cobalt sol particles is obtained by acetate and cobaltous hydroxide reaction) in the water and cobalt oxide colloidal solution that contains 0.04 mole of cobalt element, adding 5 gram concentration are 37% formaldehyde, after stirring, 50 ℃ were reacted 0.5 hour, after solid product is filtered, 100 ℃ of dryings, 900 ℃ of charings are 2 hours in nitrogen, and product soaked 24 hours in 20% hydrochloric acid, filter, drying obtains the greying porous carbon, the about 250m of reference area
2/ g has magnetic.The X-ray diffraction spectrogram of material as shown in Figure 1.
Embodiment 2
2 gram phenol are dissolved in 35 restrain (the hydrated ferric oxide sol particle is obtained by acetate and ironic hydroxide reaction) in the water and colloid of iron oxide solution that contains 0.04 moles iron element, adding 5 gram concentration are 37% formaldehyde, after stirring, 80 ℃ were reacted 4 hours, after solid product is filtered, 100 ℃ of dryings, 800 ℃ of charings are 2 hours in nitrogen, and product soaked 2 hours in 10% hydrochloric acid, filter, drying obtains the greying porous carbon, the about 470m of reference area
2/ g has magnetic, and the Raman spectrogram of material as shown in Figure 2.
Embodiment 3
2.4 gram Phloroglucinols are dissolved in 35 to be restrained in the water and colloid of iron oxide solution that contains 0.02 moles iron element (the hydrated ferric oxide sol particle is obtained by hydro-oxidation sodium partial hydrolysis iron nitrate), adding 4.2 gram concentration are 37% formaldehyde, after stirring, 50 ℃ were reacted 1 hour, after solid product is filtered, 100 ℃ of dryings, 900 ℃ of charings are 2 hours in nitrogen, and product soaked 2 hours in 10% hydrochloric acid, filter, drying obtains the greying porous carbon, the about 330m of reference area
2/ g has magnetic.
Embodiment 4
2.4 gram Resorcinols are dissolved in 35 to be restrained in the water and colloid of iron oxide solution that contains 0.04 moles iron element (the hydrated ferric oxide sol particle is obtained by hydro-oxidation sodium partial hydrolysis iron nitrate), adding 5 gram concentration are 37% formaldehyde, after stirring, 50 ℃ were reacted 1 hour, after solid product is filtered, 100 ℃ of dryings, 700 ℃ of charings are 2 hours in nitrogen, and product soaked 2 hours in 10% hydrochloric acid, filter, drying obtains the greying porous carbon, the about 570m of reference area
2/ g has magnetic.
Embodiment 5
2.3 gram Resorcinols are dissolved in 35 restrain (the manganese oxide hydrate sol particles is obtained by acetate and manganous hydroxide reaction) in the water and manganese oxide colloidal solution that contains 0.04 mole of manganese element, adding 5 gram concentration are 37% formaldehyde, after stirring, 50 ℃ were reacted 2 hours, after solid product is filtered, 100 ℃ of dryings, 900 ℃ of charings are 2 hours in nitrogen, and product soaked 24 hours in 20% hydrochloric acid, filter, drying obtains the greying porous carbon, the about 430m of reference area
2/ g.
Claims (5)
1. the synthetic method of a greying porous carbon, it is characterized in that with hydrated metal oxide nanometer colloid particle as template, the preparation method is as follows: add phenol in the colloidal solution of hydrated metal oxide nanoparticle, treat to add formaldehyde again after the phenol dissolving, phenol and formaldehyde generation polycondensation, around template, be cross-linked to form novolac polymer, with solid product elevated temperature charing and greying in inert atmosphere, after the cooling, in acid solution, soak, after separation, the drying, obtain graphitized stephanoporate material with carbon element.
2. the synthetic method of a kind of greying porous carbon as claimed in claim 1, it is characterized in that, hydrated metal oxide nanoparticle as template refers to the nanoparticle that weak acid dissolution of metals oxyhydroxide obtains, or the nanoparticle that obtains of adjustment of acidity partial hydrolysis metal-salt, take place before the phenolic aldehyde polycondensation, stable being dispersed in forms colloidal solution in the water.
3. the synthetic method of a kind of greying porous carbon as claimed in claim 2 is characterized in that the metallic element in the hydrated metal oxide nanoparticle template is iron, cobalt, copper or manganese.
4. the synthetic method of a kind of greying porous carbon as claimed in claim 1 is characterized in that described phenol is phenol, pyrocatechol, Resorcinol, Resorcinol, oxyhydroquinone or Phloroglucinol.
5. the synthetic method of a kind of greying porous carbon as claimed in claim 1 is characterized in that described acid is hydrochloric acid, sulfuric acid or nitric acid.
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| WO2012131628A1 (en) * | 2011-03-31 | 2012-10-04 | Basf Se | Particulate porous carbon material and use thereof in lithium cells |
| CN103569995A (en) * | 2012-07-30 | 2014-02-12 | 中国科学院兰州化学物理研究所 | Preparation method of porous carbon microsphere |
| CN103738935A (en) * | 2013-12-13 | 2014-04-23 | 天津大学 | Method for preparing porous carbon material by using porous copper as template |
| CN103950915A (en) * | 2014-04-16 | 2014-07-30 | 奇瑞汽车股份有限公司 | Carbon nanoribbon with large specific surface area and preparation method thereof |
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| US9892835B2 (en) | 2010-09-16 | 2018-02-13 | South Dakota Board Of Regents | Composite materials with magnetically aligned carbon nanoparticles and methods of preparation |
| CN107799771A (en) * | 2017-11-16 | 2018-03-13 | 湖州创亚动力电池材料有限公司 | A kind of carbon negative pole material for lithium ion battery and preparation method thereof |
| CN108840698A (en) * | 2018-07-19 | 2018-11-20 | 航天特种材料及工艺技术研究所 | A kind of porous C/C composite and preparation method |
| CN112017868A (en) * | 2020-08-28 | 2020-12-01 | 陕西科技大学 | Mesoporous hollow carbon micron cage material and preparation method and application thereof |
| CN115626643A (en) * | 2022-10-28 | 2023-01-20 | 西安交通大学 | Three-dimensional porous graphite sieve and preparation method thereof |
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| US9892835B2 (en) | 2010-09-16 | 2018-02-13 | South Dakota Board Of Regents | Composite materials with magnetically aligned carbon nanoparticles and methods of preparation |
| CN102107868A (en) * | 2011-03-01 | 2011-06-29 | 哈尔滨工程大学 | Method for preparing porous graphene material |
| WO2012131628A1 (en) * | 2011-03-31 | 2012-10-04 | Basf Se | Particulate porous carbon material and use thereof in lithium cells |
| CN103459312A (en) * | 2011-03-31 | 2013-12-18 | 巴斯夫欧洲公司 | Particulate porous carbon material and use thereof in lithium cells |
| CN103569995A (en) * | 2012-07-30 | 2014-02-12 | 中国科学院兰州化学物理研究所 | Preparation method of porous carbon microsphere |
| CN103738935A (en) * | 2013-12-13 | 2014-04-23 | 天津大学 | Method for preparing porous carbon material by using porous copper as template |
| US9312046B2 (en) | 2014-02-12 | 2016-04-12 | South Dakota Board Of Regents | Composite materials with magnetically aligned carbon nanoparticles having enhanced electrical properties and methods of preparation |
| CN103950915A (en) * | 2014-04-16 | 2014-07-30 | 奇瑞汽车股份有限公司 | Carbon nanoribbon with large specific surface area and preparation method thereof |
| CN103950915B (en) * | 2014-04-16 | 2016-08-24 | 奇瑞汽车股份有限公司 | A kind of carbon nanobelts of high-specific surface area and preparation method thereof |
| US9666861B2 (en) | 2014-04-25 | 2017-05-30 | South Dakota Board Of Regents | High capacity electrodes |
| US10950847B2 (en) | 2014-04-25 | 2021-03-16 | South Dakota Board Of Regents | High capacity electrodes |
| US11626584B2 (en) | 2014-04-25 | 2023-04-11 | South Dakota Board Of Regents | High capacity electrodes |
| CN107799771A (en) * | 2017-11-16 | 2018-03-13 | 湖州创亚动力电池材料有限公司 | A kind of carbon negative pole material for lithium ion battery and preparation method thereof |
| US11824189B2 (en) | 2018-01-09 | 2023-11-21 | South Dakota Board Of Regents | Layered high capacity electrodes |
| CN108840698A (en) * | 2018-07-19 | 2018-11-20 | 航天特种材料及工艺技术研究所 | A kind of porous C/C composite and preparation method |
| CN112017868A (en) * | 2020-08-28 | 2020-12-01 | 陕西科技大学 | Mesoporous hollow carbon micron cage material and preparation method and application thereof |
| CN115626643A (en) * | 2022-10-28 | 2023-01-20 | 西安交通大学 | Three-dimensional porous graphite sieve and preparation method thereof |
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