CN102001648A - Method for preparing phosphorus-doped spherical graphite - Google Patents
Method for preparing phosphorus-doped spherical graphite Download PDFInfo
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- CN102001648A CN102001648A CN 201010528639 CN201010528639A CN102001648A CN 102001648 A CN102001648 A CN 102001648A CN 201010528639 CN201010528639 CN 201010528639 CN 201010528639 A CN201010528639 A CN 201010528639A CN 102001648 A CN102001648 A CN 102001648A
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Abstract
The invention provides a method for preparing phosphorus-doped spherical graphite. The method comprises the following steps of: putting a clean quartz tube into a tube type furnace, and under the protection of argon which is inert gas, rising the temperature of a high-temperature part of the quartz tube to a reaction temperature; adding toluene into a conical flask, and then adding triphenylphosphorus; after the triphenylphosphorus is completely dissolved, injecting the mixed solution into the quartz tube through a constant flow pump under the protection of argon; after the solution is gasified, bringing the gasified solution to a high-temperature area, decomposing carbon source methylbenzene and the phosphorus source triphenylphosphorus to grow phosphorus-doped spherical graphite on the wall of the quartz tube; after the solution is completely injected, cooling the quartz tube to room temperature under the protection of argon; and taking the sample down from the wall of the quartz tube to obtain prepared phosphorus-doped spherical graphite.
Description
Technical field
The present invention relates to the graphite material field, be specifically related to a kind of preparation method of phosphorus doping globular graphite.
Background technology
Graphite is a kind of important carbon material, and its form that exists has three kinds of compact crystal shape graphite (blocky graphite), crystalline flake graphite and aphanitic graphites (amorphous graphite or amorphous graphite).Because its unique character, corrosive chemical stability as high temperature resistant, favorable conductive thermal conductivity, oilness, plasticity-and energy acid and alkali-resistance and organic solvent, and greatly application is arranged in industry such as metallurgy, electrical equipment and machineries, graphite still is the polishing agent and the rust-preventive agent of glass and papermaking in the light industry in addition, is to make pencil, prepared Chinese ink, pitch-dark, printing ink and man-made diamond, the indispensable raw material of diamond.Along with modern science and technology and industrial expansion, the Application Areas of graphite is also constantly being widened, and has become the important source material of advanced composite material in the high-tech area, has important effect in national economy.
Technology of preparing constantly perfect for preparing material along with graphite, people begin to turn to the research of aspects such as other heteroatoms and application thereof of mixing in graphite.Adulterated nonmetallic heteroatoms has B, N and S etc. in graphite at present, the doping of these non-metallic atoms directly influences the structure and the character of graphite, as in graphite, mixing the N atom, the N atom can form conjugated system by the valence electron of its outermost valence electron and graphite carbon, and change the electric density of graphite carbon, thereby influence the structure and properties of graphite or change graphite; And for example investigate from the angle of fuel-cell catalyst, the hydrogen reduction take-off potential of the adulterated graphite of nitrogen can exceed much than the hydrogen reduction performance of simple graphite carbon, and its stability and anti-methanol permeability are considerably beyond the noble metal catalyst of graphite carbon area load.Although the P atomic radius is big more a lot of than carbon atom, theoretical investigation shows in graphite carbon can mix the P atom fully, because the bond distance of carbon phosphorus key is littler than the carbon-carbon bond than the bond angle of the length of carbon-carbon bond and carbon phosphorus key, so along with mixing of phosphorus atom, certain variation can take place in the pattern of graphite surface, as can form some tangible projections or distortion formation botryoidalis or coralloid unusual form at graphite surface.
Investigators such as Liu Ruili have reported the preparation of nitrogen doped graphite carbon, do not relate to the preparation of phosphorus doping graphite carbon in the literary composition; Prepare nitrogen phosphorus adulterated multi-walled carbon nano-tubes simultaneously though there is investigator such as Terrones to report the employing ferrocene as catalyzer, and investigator such as Jourdain reported synthetic many walls of phosphorus doping carbon pipe on the NiFe catalyzer of the anodised pellumina load of phosphorated, but the report of at present still without phosphorus adulterated globular graphite carbon preparation.
Summary of the invention
The objective of the invention is to overcome the prior art above shortcomings, a kind of preparation method of phosphorus doping globular graphite is provided.The present invention adopts CVD method Doping Phosphorus atom in the globular graphite preparation, prepares the phosphorus doping globular graphite.
Technical purpose of the present invention realizes by following technical proposals: a kind of preparation method of phosphorus doping globular graphite, adopt chemical Vapor deposition process, and it is characterized in that comprising the steps:
4) silica tube that has a quartz boat of cleaning is put into tube furnace, under the protection of argon gas rare gas element, the temperature of silica tube high-temperature part is elevated to temperature of reaction;
5) in container bottle, add toluene, add triphenyl phosphorus again, after treating that triphenyl phosphorus dissolves fully, under argon shield, the mixing solutions that will obtain after will dissolving by constant flow pump injects silica tube, taken to the high-temperature zone by argon gas behind the vaporizer, carbon source toluene and phosphorus source triphenyl phosphorus decompose, and the phosphorus doping globular graphite begins to grow;
6) after solution to be mixed injects fully, under argon shield,, from quartz boat, take out sample, the phosphorus doping globular graphite that obtains preparing with the silica tube cool to room temperature.
The preparation method of above-mentioned phosphorus doping globular graphite need not any catalyzer, and the consumption of triphenyl phosphorus is 2.5～20wt% toluene.
The preparation method of above-mentioned phosphorus doping globular graphite, the triphenyl phosphorus that is adopted is the phosphorus source; Toluene is carbon source; Argon gas is protection gas.
The preparation method of above-mentioned phosphorus doping globular graphite, described temperature of reaction are 1000-1200 ℃.The flow velocity of step 1) argon gas rare gas element is 0.5～0.8L/min.Step 2) flow velocity of constant flow pump is 2～3mL/h.
The flow velocity of step 3) argon gas is 0.1～0.3L/min.
The present invention compared with prior art has following advantage and effect:
(1) to adopt triphenyl phosphorus be the phosphorus source in the present invention, and employing toluene is carbon source, can successfully control the content of phosphorus in the phosphorus doping globular graphite by the content of control triphenyl phosphorus in toluene;
(2) the phosphorus doping globular graphite of the present invention preparation, owing to adopt decomposition reactant under the comparatively high temps, the atom after the decomposition is used for directly generating globular graphite more, so the productive rate of prepared phosphorus doping globular graphite is higher.
(3) compared with prior art, the preparation of phosphorus doping globular graphite of the present invention, method is simple, the output height of phosphorus doping globular graphite, and operation controllability is strong.
Description of drawings
Fig. 1 is the sem photograph of the embodiment of the invention 3 prepared phosphorus doping globular graphite.
Fig. 2 is the Raman spectrogram of the embodiment of the invention 3 prepared phosphorus doping globular graphite.
The XPS spectrum figure of the P of the phosphorus doping globular graphite that Fig. 3 makes for the embodiment of the invention 1.
Embodiment
For better understanding the present invention, below in conjunction with embodiment the present invention is done detailed description further, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
1) silica tube that has a quartz boat of cleaning being put into tube furnace, is under the protection of argon gas rare gas element of 0.5L/min at flow velocity, and the temperature of silica tube high-temperature part is elevated to 1000 ℃;
2) toluene of adding 8mL in container bottle slowly adds triphenyl phosphorus, wherein the consumption 2.5wt% toluene of triphenyl phosphorus again; After treating that triphenyl phosphorus dissolves fully, under argon shield, with the flow velocity of 2mL/h this mixing solutions is injected into silica tube by constant flow pump, taken to the high-temperature zone by argon gas behind the vaporizer, carbon source toluene and phosphorus source triphenyl phosphorus decompose, and beginning is in quartzy tube wall growth phosphorus doping globular graphite;
3) treat that solution injects fully after, stop the heating, be under the argon shield of 0.1L/min at flow velocity, with the silica tube cool to room temperature, from quartz boat, take out sample, the content that obtains the phosphorus doping globular graphite that the EDS analysis revealed obtains is 1.62wt%.
Embodiment 2
1) silica tube that has a quartz boat of cleaning being put into tube furnace, is under the protection of argon gas rare gas element of 0.6L/min at flow velocity, and the temperature of silica tube high-temperature part is elevated to 1100 ℃;
2) toluene of adding 10mL in container bottle slowly adds triphenyl phosphorus again, and wherein the consumption of triphenyl phosphorus is a 5wt% toluene; After treating that triphenyl phosphorus and ferrocene dissolve fully, under argon shield, with the flow velocity of 2.5mL/h this mixing solutions is injected into silica tube by constant flow pump, taken to the high-temperature zone by argon gas behind the vaporizer, carbon source toluene and phosphorus source triphenyl phosphorus decompose, and the phosphorus doping globular graphite begins to grow;
3) treat that solution injects fully after, stop the heating, be under the argon shield of 0.2L/min at flow velocity, with the silica tube cool to room temperature, from quartz boat, take out sample, the content that obtains phosphorus in the phosphorus doping globular graphite that the EDS analysis revealed obtains is 2.81wt%.
Embodiment 3
1) silica tube that has a quartz boat of cleaning being put into tube furnace, is under the protection of argon gas rare gas element of 0.8L/min at flow velocity, and the temperature of silica tube high-temperature part is elevated to 1100 ℃;
2) toluene of adding 12mL in container bottle slowly adds triphenyl phosphorus, wherein the consumption 10wt% toluene of triphenyl phosphorus again; After treating that triphenyl phosphorus dissolves fully, under argon shield, with the flow velocity of 3mL/h this mixing solutions is injected into silica tube by constant flow pump, taken to the high-temperature zone by argon gas behind the vaporizer, carbon source toluene and phosphorus source triphenyl phosphorus decompose, and the phosphorus doping globular graphite begins to grow;
3) treat that solution injects fully after, stop the heating, be under the argon shield of 0.3L/min at flow velocity, with the silica tube cool to room temperature, from quartz boat, take out sample, the content that obtains phosphorus in the phosphorus doping globular graphite that the EDS analysis revealed obtains is 3.70wt%.
Embodiment 4
1) silica tube that has a quartz boat of cleaning being put into tube furnace, is under the protection of argon gas rare gas element of 0.8L/min at flow velocity, and the temperature of silica tube high-temperature part is elevated to 1200 ℃;
2) toluene of adding 12mL in container bottle slowly adds triphenyl phosphorus, wherein the consumption 20wt% toluene of triphenyl phosphorus again; After treating that triphenyl phosphorus dissolves fully, under argon shield, with the flow velocity of 3mL/h this mixing solutions is injected into silica tube by constant flow pump, taken to the high-temperature zone by argon gas behind the vaporizer, carbon source toluene and phosphorus source triphenyl phosphorus decompose, and the phosphorus doping globular graphite begins to grow;
3) treat that solution injects fully after, stop the heating, be under the argon shield of 0.3L/min at flow velocity, with the silica tube cool to room temperature, from quartz boat, take out sample, the content that obtains phosphorus in the phosphorus doping globular graphite that the EDS analysis revealed obtains is 5.85wt%.
As seen from Figure 1, prepared phosphorus doping graphite is made up of many graphite pebbless with respect to simple graphite.
D and G band by Fig. 2 Raman spectrum determine that this preparation phosphorus doping carbon material is the graphite carbon material.
Can find that by the XPS spectrum map analysis of Fig. 3 P phosphorus mixes in the globular graphite.
Claims (5)
1. the preparation method of a phosphorus doping globular graphite adopts chemical Vapor deposition process, it is characterized in that comprising the steps:
1) silica tube that will have a quartz boat is put into tube furnace, under the protection of argon gas rare gas element, the temperature of silica tube high-temperature part is elevated to temperature of reaction;
2) in container bottle, add toluene, add triphenyl phosphorus again, after treating that triphenyl phosphorus dissolves fully, under argon shield, the mixing solutions that will obtain after will dissolving by constant flow pump injects silica tube, taken to the high-temperature zone by argon gas behind the vaporizer, carbon source toluene and phosphorus source triphenyl phosphorus decompose, and the phosphorus doping globular graphite begins to grow;
3) after solution to be mixed injects fully, under argon shield,, from quartz boat, take out sample, the phosphorus doping globular graphite that obtains preparing with the silica tube cool to room temperature.
2. the preparation method of phosphorus doping globular graphite according to claim 1 is characterized in that need not any catalyzer, and the consumption of triphenyl phosphorus is 2.5～20wt% toluene.
3. the preparation method of phosphorus doping globular graphite according to claim 1 is characterized in that the triphenyl phosphorus that is adopted is the phosphorus source; Toluene is carbon source; Argon gas is protection gas.
4. according to the preparation method of each described phosphorus doping globular graphite of claim 1～3, it is characterized in that described temperature of reaction is 1000-1200 ℃.
5. the preparation method of phosphorus doping globular graphite according to claim 4 is characterized in that step
1) flow velocity of argon gas rare gas element is 0.5～0.8L/min; Step 2) flow velocity of constant flow pump is 2～3mL/h; The flow velocity of step 3) argon gas is 0.1～0.3L/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102815871A (en) * | 2012-09-03 | 2012-12-12 | 中国矿业大学 | Preparation method of phosphorus-doped graphite optical lens |
| CN103864057A (en) * | 2012-12-07 | 2014-06-18 | 北京大学 | Phosphor-doped graphene, its preparation method and its application |
| CN112028048A (en) * | 2020-08-31 | 2020-12-04 | 华中科技大学 | Binary phosphorus-carbon compound and synthesis method and application thereof |
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| US20030086859A1 (en) * | 2001-10-04 | 2003-05-08 | Soichiro Kawakami | Method for producing nanocarbon materials |
| CN1460639A (en) * | 2003-05-23 | 2003-12-10 | 北京大学 | Carbon base nano tube, its preparation method and application |
| CN1970439A (en) * | 2005-11-25 | 2007-05-30 | 中国科学院金属研究所 | Preparation method of thermolysis carbon ball |
| CN101289181A (en) * | 2008-05-29 | 2008-10-22 | 中国科学院化学研究所 | Doped graphene and method for preparing same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030086859A1 (en) * | 2001-10-04 | 2003-05-08 | Soichiro Kawakami | Method for producing nanocarbon materials |
| CN1460639A (en) * | 2003-05-23 | 2003-12-10 | 北京大学 | Carbon base nano tube, its preparation method and application |
| CN1970439A (en) * | 2005-11-25 | 2007-05-30 | 中国科学院金属研究所 | Preparation method of thermolysis carbon ball |
| CN101289181A (en) * | 2008-05-29 | 2008-10-22 | 中国科学院化学研究所 | Doped graphene and method for preparing same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102815871A (en) * | 2012-09-03 | 2012-12-12 | 中国矿业大学 | Preparation method of phosphorus-doped graphite optical lens |
| CN102815871B (en) * | 2012-09-03 | 2015-01-21 | 中国矿业大学 | Preparation method of phosphorus-doped graphite optical lens |
| CN103864057A (en) * | 2012-12-07 | 2014-06-18 | 北京大学 | Phosphor-doped graphene, its preparation method and its application |
| CN103864057B (en) * | 2012-12-07 | 2015-12-02 | 北京大学 | Phosphorus doping Graphene and its preparation method and application |
| CN112028048A (en) * | 2020-08-31 | 2020-12-04 | 华中科技大学 | Binary phosphorus-carbon compound and synthesis method and application thereof |
| CN112028048B (en) * | 2020-08-31 | 2022-05-20 | 华中科技大学 | Binary phosphorus-carbon compound and synthesis method and application thereof |
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Application publication date: 20110406 |