CN101774571A - Method for preparing oxide-doped amorphous carbon material - Google Patents
Method for preparing oxide-doped amorphous carbon material Download PDFInfo
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Abstract
The invention relates to a method for preparing an amorphous carbon material. The method is characterized by using dicyclopentadienyl iron and chloralkane as the raw materials, using heteropolyacid as the catalyst, or using the heteropolyacid as the catalyst and using quaternary ammonium salt as a phase transfer agent to make the heteropolyacid dissolved in a water phase transferred into an organic phase so that the heteropolyacid is uniformly dispersed in a mixed liquor of the organic phase and the reactant, then arranging the mixed liquor in a sealed container to carry out heating reaction, and finally washing the obtained product by water and ethanol and drying the product. The method provided by the invention has the characteristics of mild reactive conditions and simple process. And as the heteropolyacid, such as phosphomolybdic acid, phosphotungstic acid and the like are added, the obtained carbon material is doped with molybdenum oxide and tungstic oxide, has large specific surface area, is expected to be the catalyst carrier, the electrochemical material and the like.
Description
Technical field
The present invention relates to a kind of preparation method of amorphous carbon material, particularly relate to a kind of method for preparing oxide-doped amorphous carbon material.
Background technology
Since Ijima in 1991 finds multi-walled carbon nano-tubes and found Single Walled Carbon Nanotube in 1993, because of its excellent electricity, mechanics and chemical property have wide application prospect in fields such as Materials science and physical chemistry.On this basis, the research of various carbon materials is also risen thereupon, and the carbon material of existing report has Nano carbon balls, horn-like, onion shape carbon structure, carbon fiber, Graphene or the like.By doped metal ion, carbon material has been endowed a lot of new performances, such as by adding precious metal or transition metal, makes it have potential application at catalytic field; Make it be expected to be used for contrast medium by adding magnetic particles such as iron content, cobalt, nickel.
Up to now, owing to be subjected to the promotion that carbon nanotube is used, the researchist has been developed multiple synthetic method, and mature methods has: arc discharge method, catalytic pyrolysis method, laser evaporation method.Yet the research of other carbon material synthetic method then relatively lags behind than carbon nanotube, often occurs as the by product in the carbon nanotube building-up process.At present, Chang Yong method mainly contains: use metal-doped graphite rod arc discharge method; The carbonaceous mixture pyrolysis method, catalysis auxiliary chemical vapor deposition method or the like.For example, people's reported first such as Rao the use ferrocene as raw material, the pyrolytic chemical Vapor deposition process prepares carbon nanotube (Rao, C.N.R. under argon gas atmosphere; Sen, R.; Satishkumar, B.C.; Govindaraj, A.Chem.Commun.1998,1525-1526.).Liu Baiyang etc. are raw material with ferrocene and ammonium chloride, after ball milling mixes, at high temperature are decomposed to form amorphous carbon nanotube (Chinese patent application number: 200610009787.3).The operation steps of similar synthetic method is more complicated all generally, and aspect the kind of doping metals and the content considerable restraint are being arranged.Another kind of method is that the different types of organometallic compound of pyrolysis comes synthesizing carbon nanotubes (Iyer, V.S. under the high pressure by spontaneous generation in reactor; Vollhardt, K.P.C.; Wilhelm, R.Angew.Chem.2003,115,4515-4519.), carbon nanometer cable (Zhi, L.J.; Gorelik, T.; Friedlein, R.; Wu, J.S.; Kolb, U.; Salaneck, W.R.; M ü llen, K.Small 2005,1,798-801.), carbon onion ball (Dosa, P.I.; Erben, C.; Iyer, V.S.; Vollhardt, K.P.C.; Wasser, I.M.J.Am.Chem.Soc.1999,121,10430-10431.) and carbon micro-spheres (Nyamori, V.O.; Coville, N.J.Organometallics 2007,26,4083-4085.) etc.
Than the crystalline state carbon material, amorphous carbon material helps the carrying out of catalyzed reaction and electrochemical reaction because of its significant specific surface area and surface imperfection, thereby obtains extensive concern and application.
Recently, people such as Zhu person of outstanding talent use wet chemistry method to prepare amorphous carbon nanotube with the principle of ferrocene as the thermal synthesis of raw material water draw, and method is simple for this, and suitable large-scale production (Shen, J.M.; Xu, L.; Liu, Y.G.; Lu, C.L.; Hou, W.H.; Zhu, J.J.Chem Mater 2008,20,3034-3041.; Chinese patent application number: 200710021019.4).Yet the finished product that obtain with this method are many with a bunch shape pattern appearance, can't obtain a large amount of single tubulose products.
In the report of many synthetic carbon materials, its grammar is based on the decomposition deposition of selected carbon source more.In this process, catalyzer plays very important influence.Heteropolyacid is the important new catalyst of a class, is widely used in the organic catalysis field, and it has strongly-acid and strong oxidizing property simultaneously, thereby the carbon source that is expected effectively to improve under the hydrothermal condition is decomposed effect.Yet, the low-solubility of heteropolyacid in organic phase will have a strong impact on its catalytic performance, in order to improve catalytic efficiency, the heteropolyacid " transfer " that can select for use suitable consisting of phase-transferring agent to make usually to be dissolved in water can effectively be evenly dispersed in organic phase solvent and the reactant mixed solution it to organic phase.Consisting of phase-transferring agent commonly used mainly contains quaternary ammonium salt, as tri-n-octyl methyl ammonium chloride and dimethyl diallyl ammonium chloride, the ionic liquid that positively charged ion in the consisting of phase-transferring agent and heteropolyacid anions form can effectively be scattered in most organic phases, thereby form design of the present invention.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of method of simple and easy to do synthesis oxide doped amorphous carbon material is provided.
Technical scheme of the present invention is summarized as follows:
A kind of method for preparing amorphous carbon material, it is characterized in that with ferrocene and chloroparaffin be raw material, be catalyzer with the heteropolyacid or be catalyzer with the heteropolyacid and be consisting of phase-transferring agent with the quaternary ammonium salt, be dispersed in reactant mixed solution and the organic phase solvent, make mixing solutions and then mixed solution is placed the sealed vessel reacting by heating, last water and ethanol clean and oven dry.
It is characterized in that adopting in following three kinds of methods any:
Method A
1) earlier ferrocene and chloroparaffin are mixed, stir, add heteropolyacid again, mixing and stirring becomes mixing solutions;
2) mixed solution that step 1 is made is put into encloses container, and sealed vessel is put into the heater heats reaction, and temperature of reaction is 120-180 ℃;
3) cooling was naturally opened container and is cleaned collecting reaction product respectively with ethanol and water after reaction was finished, and 60-80 ℃ of drying;
Method B
1) earlier ferrocene and chloroparaffin are mixed, stirs, add heteropolyacid and consisting of phase-transferring agent again, be stirred into mixed solution;
2) mixed solution that step 1 is made is put into encloses container, and sealed vessel is put into the heater heats reaction, and temperature of reaction is 120-180 ℃;
3) cooling was naturally opened container and is cleaned collecting reaction product respectively with ethanol and water after reaction was finished, and 60-80 ℃ of drying;
Method C
1) earlier ferrocene and chloroparaffin are mixed; Then heteropolyacid is dissolved in deionized water, consisting of phase-transferring agent is dispersed in the chloroparaffin, and both are mixed stirring, the heteropolyacid that is soluble in the aqueous phase is transferred in the organic phase, after separated and collected organic phase, drying treatment are removed remaining moisture content, dropwise join in the mixed solution of ferrocene and chloroparaffin again;
2) mixed solution that step 1 is made is put into encloses container, and sealed vessel is put into the heater heats reaction, and temperature of reaction is 120-180 ℃;
3) cooling was naturally opened container and is cleaned collecting reaction product respectively with ethanol and water after reaction was finished, and 60-80 ℃ of drying;
Described heteropolyacid is phospho-molybdic acid or phospho-wolframic acid;
Described consisting of phase-transferring agent is tri-n-octyl methyl ammonium chloride or dimethyl diallyl ammonium chloride;
Described chloroparaffin is the mixture of any or they in monochloro methane, methylene dichloride, trichloromethane and the tetracol phenixin.
Wherein, be characterised in that:
A) concentration range of ferrocene is 0.01-0.2mol/L in the solution of method A, method B or method C;
B) in the step 2 of method A, B or C, be 1 by the volume and the encloses container volume proportional range of the mixing solutions of step 1 preparation: 3-4: 5;
C) concentration of heteropolyacid in deionized water is 0.0001-0.1mol/L in method C step 1;
D) in the step 1 of method B or C the concentration of consisting of phase-transferring agent in chloroparaffin less than 100g/L greater than 0;
E) mass ratio of the unit volume of consisting of phase-transferring agent and heteropolyacid is less than 5 in the step 1 of method B or method C, and the concentration of heteropolyacid in mixed solution is less than 0.1mol/L among the method A.
Be further characterized in that:
A) concentration of ferrocene is 0.1mol/L in method A, method B and the described reaction soln of method C;
B) in the step 2 of method A, method B or method C, it is 4: 5 by the volume and the encloses container volumetric ratio of the mixing solutions of step 1 preparation;
C) concentration of heteropolyacid in deionized water is 0.005mol/L in the method C step 1;
D) in the step 1 of method B or C the concentration of consisting of phase-transferring agent in chloroparaffin less than 50g/L;
E) in method B or the method C step 1 mass ratio of the unit volume of consisting of phase-transferring agent and heteropolyacid less than 1.25.
According to the prepared amorphous carbon material pattern that goes out of aforesaid method the present invention is tubulose, sheet and flower-shaped.Wherein,
(i) its thickness of pipe of tubulose amorphous carbon material is 20nm～200nm, and its length is 3 μ m～120 μ m, and there is the tube-in-tube pattern in the tubulose carbon material;
(ii) its sheet thickness of sheet amorphous carbon material is 20nm～200nm;
(iii) flower-shaped its lamellar spacing of amorphous carbon material is 20nm～200nm, and its cluster size is 1 μ m～10 μ m;
Be doped with Tungsten oxide 99.999 or molybdenum oxide in the (iv) prepared amorphous carbon material.
Method of the present invention has mild condition, the technology characteristic of simple, and simultaneously owing to added heteropolyacids such as phospho-molybdic acid or phospho-wolframic acid, resulting carbon material mixed molybdenum oxide and Tungsten oxide 99.999, and specific surface area is big, is expected to as support of the catalyst, electrochemical material etc.
Description of drawings
Fig. 1 is the TEM figure of the tubulose carbon material of method preparation of the present invention.
Fig. 2 is the TEM figure of the tubulose carbon material of method preparation of the present invention.
Fig. 3 is the SEM figure of the flower-shaped carbon material of method preparation of the present invention.
Fig. 4 is the SEM figure of the sheet carbon material of method preparation of the present invention.
Fig. 5 is the TEM figure of the tubulose carbon material of method preparation of the present invention.
Fig. 6 is the SEM figure of the flower-shaped carbon material of method preparation of the present invention.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
The 0.2295g ferrocene is dissolved in the 12mL methylene dichloride, fully stirs.1.1524g (0.4mmol) phospho-wolframic acid is dissolved in the 8ml deionized water, the 0.5g tri-n-octyl methyl ammonium chloride is dispersed in the 10ml trichloromethane, both are mixed stirring, the separated and collected organic phase is removed remaining moisture content with anhydrous sodium sulfate drying agent drying treatment.Get the above-mentioned phospho-wolframic acid-tri-n-octyl methyl ammonium chloride that makes through phase transition behavior of 2mL-chloroform soln, dropwise join in ferrocene-methylene dichloride mixed solution, be transferred to after stirring in the 15mL hydrothermal reaction kettle, in 180 ℃ of following hydro-thermal reaction 30h, naturally cool to room temperature, the repeatedly back 60 ℃ of oven dry of water and washing with alcohol are spent the night.The caliber of resulting tubulose carbon material is 20nm～200nm, and length is 3 μ m～120 μ m.Products therefrom is shown in attached Fig. 1 and 2.
Embodiment 2
The 0.1148g ferrocene is dissolved in the 7mL methylene dichloride, fully stirs.1.1524g (0.4mmol) phospho-wolframic acid is dissolved in the 10ml deionized water, the 1g dimethyl diallyl ammonium chloride is dispersed in the 10ml methylene dichloride, both are mixed stirring, the separated and collected organic phase uses anhydrous sodium sulfate drying agent drying treatment to remove remaining moisture content.Get the above-mentioned phospho-wolframic acid-dimethyl diallyl ammonium chloride that makes through phase transition behavior of 2mL-dichloromethane solution, dropwise add in ferrocene-methylene dichloride mixed solution, be transferred to after stirring in the 15mL hydrothermal reaction kettle, in 180 ℃ of following hydro-thermal reaction 20h, naturally cool to room temperature, the repeatedly back 60 ℃ of oven dry of water and washing with alcohol are spent the night.Resulting its lamellar spacing of flower-shaped carbon material is 20nm～200nm, and the cluster size is 1 μ m～10 μ m.Products therefrom as shown in Figure 3.
Embodiment 3
The 0.2295g ferrocene is dissolved in the 12mL methylene dichloride, fully stir, add 2.3042g (0.8mmol) phospho-wolframic acid and 0.2g tri-n-octyl methyl ammonium chloride, be transferred to after stirring in the 15mL hydrothermal reaction kettle, in 180 ℃ of following hydro-thermal reaction 15h, naturally cool to room temperature, the repeatedly back 60 ℃ of oven dry of water and washing with alcohol are spent the night.Its sheet thickness of sheet carbon material is 20nm～200nm.Products therefrom as shown in Figure 4.
Embodiment 4
The 0.1148g ferrocene is dissolved in the 12mL monochloro methane, fully stirs.0.73g (0.4mmol) phospho-molybdic acid is dissolved in the 8ml deionized water, the 0.5g tri-n-octyl methyl ammonium chloride is dispersed in the 10ml tetracol phenixin, both are mixed stirring, separated and collected organic phase, drying treatment are removed remaining moisture content.Get phospho-molybdic acid-tri-n-octyl methyl ammonium chloride-carbon tetrachloride solution that the above-mentioned phase transition behavior of 2mL makes, dropwise add in ferrocene-monochloro methane mixed solution, be transferred to after stirring in the 15mL hydrothermal reaction kettle, in 180 ℃ of following hydro-thermal reaction 10h, naturally cool to room temperature, the repeatedly back 60 ℃ of oven dry of water and washing with alcohol are spent the night.The caliber of resulting tubulose carbon material is 20nm～200nm, and length is 3 μ m～120 μ m.Products therefrom as shown in Figure 5.
Embodiment 5
The 0.1148g ferrocene is dissolved in the 7mL methylene dichloride, fully stirs.0.73g (0.4mmol) phospho-molybdic acid is dissolved in the 8ml deionized water, the 0.5g tri-n-octyl methyl ammonium chloride is dispersed in the 10ml tetracol phenixin, both are mixed stirring, the separated and collected organic phase uses anhydrous sodium sulfate drying agent drying treatment to remove remaining moisture content.Get phospho-molybdic acid-tri-n-octyl methyl ammonium chloride-carbon tetrachloride solution that the above-mentioned phase transition behavior of 4mL makes, dropwise add in ferrocene-monochloro methane mixed solution, be transferred to after stirring in the 15mL hydrothermal reaction kettle, in 180 ℃ of following hydro-thermal reaction 15h, naturally cool to room temperature, the repeatedly back 60 ℃ of oven dry of water and washing with alcohol are spent the night.Resulting its lamellar spacing of flower-shaped carbon material is 20nm～200nm, and the cluster size is 1 μ m～10 μ m.As shown in Figure 6.
Embodiment 6
The 0.1148g ferrocene is dissolved in the 12ml monochloro methane, fully stirs.0.73g (0.4mmol) phospho-molybdic acid is added in ferrocene-monochloro methane mixed solution, be transferred to after stirring in the 15ml hydrothermal reaction kettle, in 180 ℃ of following hydro-thermal reaction 30h, naturally cool to room temperature, the repeatedly back 60 ℃ of oven dry of water and washing with alcohol are spent the night.The caliber of resulting tubulose carbon material is 20-200nm, and length is 3-120 μ m.
Claims (9)
1. method for preparing amorphous carbon material, it is characterized in that with ferrocene and chloroparaffin be raw material, be catalyzer with the heteropolyacid or be catalyzer with the heteropolyacid and be consisting of phase-transferring agent with the quaternary ammonium salt, be dispersed in reactant mixed solution and the organic phase solvent, make mixing solutions and then mixed solution is placed the sealed vessel reacting by heating, last water and ethanol clean and oven dry.
2. by the described method for preparing amorphous carbon material of claim 1, it is characterized in that adopting in following three kinds of methods any:
Method A
A) earlier ferrocene and chloroparaffin are mixed, stir, add heteropolyacid again, mixing and stirring becomes mixing solutions;
B) mixed solution that step a) is made is put into encloses container, and sealed vessel is put into the heater heats reaction, and temperature of reaction is 120-180 ℃;
C) cooling was naturally opened container and is cleaned collecting reaction product respectively with ethanol and water after reaction was finished, and 60-80 ℃ of drying;
Method B
A) earlier ferrocene and chloroparaffin are mixed, stir, add heteropolyacid and consisting of phase-transferring agent again, be stirred into mixed solution;
B) mixed solution that step a) is made is put into encloses container, and sealed vessel is put into the heater heats reaction, and temperature of reaction is 120-180 ℃;
C) cooling was naturally opened container and is cleaned collecting reaction product respectively with ethanol and water after reaction was finished, and 60-80 ℃ of drying;
Method C
A) earlier ferrocene and chloroparaffin are mixed; Then heteropolyacid is dissolved in deionized water, consisting of phase-transferring agent is dispersed in the chloroparaffin, and both are mixed stirring, the heteropolyacid that is soluble in the aqueous phase is transferred in the organic phase, after separated and collected organic phase, drying treatment are removed remaining moisture content, dropwise join in the mixed solution of ferrocene and chloroparaffin again;
B) mixed solution that step a) is made is put into encloses container, and sealed vessel is put into the heater heats reaction, and temperature of reaction is 120-180 ℃;
C) cooling was naturally opened container and is cleaned collecting reaction product respectively with ethanol and water after reaction was finished, and 60-80 ℃ of drying;
Described heteropolyacid is phospho-molybdic acid or phospho-wolframic acid;
Described consisting of phase-transferring agent is tri-n-octyl methyl ammonium chloride or dimethyl diallyl ammonium chloride;
Described chloroparaffin is the mixture of any or they in monochloro methane, methylene dichloride, trichloromethane and the tetracol phenixin.
3. by claim 1 or the 2 described methods that prepare amorphous carbon material, it is characterized in that:
A) concentration range of ferrocene is 0.01-0.2mol/L in the solution of method A, method B or method C;
B) in the step b of method A, B or C, be 1 by the volume and the encloses container volume proportional range of the mixing solutions of step a preparation: 3-4: 5;
C) concentration of heteropolyacid in deionized water is 0.0001-0.1mol/L in method C step a;
D) among the step a of method B or C the concentration of consisting of phase-transferring agent in chloroparaffin less than 100g/L greater than 0;
E) mass ratio of the unit volume of consisting of phase-transferring agent and heteropolyacid is less than 5 among the step a of method B or method C, and the concentration of heteropolyacid in mixed solution is less than 0.1mol/L among the method A.
4. by the described method for preparing amorphous carbon material of claim 3, it is characterized in that:
A) concentration of ferrocene is 0.1mol/L in method A, method B and the described reaction soln of method C;
B) in the step b of method A, method B or method C, it is 4: 5 by the volume and the encloses container volumetric ratio of the mixing solutions of step a preparation;
C) concentration of heteropolyacid in deionized water is 0.005mol/L among the method C step a;
D) among the step a of method B or C the concentration of consisting of phase-transferring agent in chloroparaffin less than 50g/L;
E) among method B or the method C step a mass ratio of the unit volume of consisting of phase-transferring agent and heteropolyacid less than 1.25.
5. by the described method for preparing amorphous carbon material of claim 2, it is characterized in that the temperature of step 1 stirring should be lower than the boiling point of employed chloroparaffin.
6. by claim 1 or the 2 described methods that prepare amorphous carbon material, it is characterized in that the amorphous carbon material pattern for preparing is tubulose, sheet or flower-shaped.
7. by the described method for preparing amorphous carbon material of claim 6, it is characterized in that:
A) thickness of pipe of tubulose amorphous carbon material is 20-200nm, and length is 3-120 μ m;
B) sheet thickness of sheet amorphous carbon material is 20-200nm;
C) lamellar spacing of flower-shaped amorphous carbon material is 20-200nm; The cluster size is 1-10 μ m.
8. by claim 6 or the 7 described methods that prepare amorphous carbon material, it is characterized in that the tubulose amorphous carbon material has the tube-in-tube pattern.
9. by claim 6 or the 7 described methods that prepare amorphous carbon material, it is characterized in that described amorphous carbon material is doped with Tungsten oxide 99.999 or molybdenum oxide.
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| CN101941695A (en) * | 2010-09-09 | 2011-01-12 | 北京化工大学 | Method for synthesizing graphene |
| CN102698713A (en) * | 2012-05-24 | 2012-10-03 | 山东中烟工业有限责任公司 | Porous carbon piece, preparation method of porous carbon piece, and application of porous carbon piece in cigarette filter |
| CN102814152A (en) * | 2012-08-20 | 2012-12-12 | 漳州师范学院 | Process for preparing carbon-doped titanium dioxide hollow microsphere |
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2010
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101941695A (en) * | 2010-09-09 | 2011-01-12 | 北京化工大学 | Method for synthesizing graphene |
| CN101941695B (en) * | 2010-09-09 | 2012-07-04 | 北京化工大学 | Method for synthesizing graphene |
| CN102698713A (en) * | 2012-05-24 | 2012-10-03 | 山东中烟工业有限责任公司 | Porous carbon piece, preparation method of porous carbon piece, and application of porous carbon piece in cigarette filter |
| CN102698713B (en) * | 2012-05-24 | 2014-05-21 | 山东中烟工业有限责任公司 | Porous carbon piece, preparation method of porous carbon piece, and application of porous carbon piece in cigarette filter |
| CN102814152A (en) * | 2012-08-20 | 2012-12-12 | 漳州师范学院 | Process for preparing carbon-doped titanium dioxide hollow microsphere |
| CN103400632A (en) * | 2013-07-17 | 2013-11-20 | 常州二维碳素科技有限公司 | Graphene doping material, and preparation method and application of graphene doping material |
| CN103400632B (en) * | 2013-07-17 | 2016-05-11 | 常州二维碳素科技股份有限公司 | A kind of Graphene dopant material and application thereof |
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Open date: 20100714 |