CN101613100A - Microwave preparation method of biomass-based graphitized carbon and carbon-carbon composite materials - Google Patents
Microwave preparation method of biomass-based graphitized carbon and carbon-carbon composite materials Download PDFInfo
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- CN101613100A CN101613100A CN200810011997A CN200810011997A CN101613100A CN 101613100 A CN101613100 A CN 101613100A CN 200810011997 A CN200810011997 A CN 200810011997A CN 200810011997 A CN200810011997 A CN 200810011997A CN 101613100 A CN101613100 A CN 101613100A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 41
- 239000002028 Biomass Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 title claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 17
- 239000010439 graphite Substances 0.000 claims abstract description 17
- 238000003763 carbonization Methods 0.000 claims abstract description 15
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- 229910001567 cementite Inorganic materials 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000010306 acid treatment Methods 0.000 claims description 10
- 229920000742 Cotton Polymers 0.000 claims description 9
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 8
- 229910039444 MoC Inorganic materials 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012808 vapor phase Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 239000002717 carbon nanostructure Substances 0.000 claims description 3
- 239000002114 nanocomposite Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 4
- 150000001875 compounds Chemical class 0.000 claims 2
- 238000005470 impregnation Methods 0.000 claims 2
- 229920002521 macromolecule Polymers 0.000 claims 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 150000001247 metal acetylides Chemical class 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 239000002685 polymerization catalyst Substances 0.000 claims 1
- 239000010902 straw Substances 0.000 claims 1
- 150000003657 tungsten Chemical class 0.000 claims 1
- 238000005087 graphitization Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229920000128 polypyrrole Polymers 0.000 description 19
- 239000002086 nanomaterial Substances 0.000 description 14
- 230000005540 biological transmission Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000007770 graphite material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 150000003233 pyrroles Chemical class 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920001940 conductive polymer Polymers 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002322 conducting polymer Substances 0.000 description 3
- 239000002127 nanobelt Substances 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
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- 239000011159 matrix material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012725 vapour phase polymerization Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000007903 penetration ability Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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Abstract
本发明涉及石墨碳，具体地说是一种以PPy/生物质复合物为碳化前驱物，在微波作用下快速碳化并石墨化，制备大比表面积的石墨复合材料的非硬模板方法。具体制备方法是：首先，采用三氯化铁为催化剂，采用蒸汽相聚合技术制备出Fe/PPy/生物质复合物；其次，将制备的Fe/PPy/生物质复合物进行微波碳化处理；最后，样品经过酸处理，除去生成的碳化铁，得到高比表面积的石墨化碳材料。采用类似的方法，申请人还成功地制备出了金属碳化物/石墨化碳复合材料。The invention relates to graphite carbon, specifically a non-hard template method for preparing graphite composite materials with large specific surface area by using PPy/biomass composites as carbonization precursors, rapid carbonization and graphitization under the action of microwaves. The specific preparation method is as follows: firstly, Fe/PPy/biomass composite is prepared by steam phase polymerization technology using ferric chloride as catalyst; secondly, the prepared Fe/PPy/biomass composite is subjected to microwave carbonization treatment; finally , the sample was treated with acid to remove the generated iron carbide and obtain a graphitized carbon material with a high specific surface area. Using a similar method, the applicant also successfully prepared a metal carbide/graphitized carbon composite material.
Description
Technical field
The present invention relates to graphite carbon, specifically the microwave fast preparation method of a kind of graphitized carbon of high-specific surface area and metallic carbide/graphitized carbon matrix material.
Background technology
Compare with decolorizing carbon, graphite carbon has high degree of crystallinity, high thermostability, high specific conductivity and very strong antioxidant property.In recent years, owing to the potential application of graphite material in fields such as electrocatalysis, fuel cell and lithium ion batteries, increasing scientific research personnel begins to pay close attention to the preparation of the graphite material with bigger serface.The general method for preparing graphite all comprises the step of pyroprocessing, usually will be above 2000 ℃.Yet this treatment process causes the specific surface area of carbon material and pore volume very little usually through regular meeting.In order to overcome this shortcoming, the method that nearest people have been developed a kind of template prepares the graphite material of bigger serface.With silicon ball or mesopore silicon oxide is template, and filling soft carbon material is the carbonization precursor, through high temperature cabonization, removes steps such as template, obtains the graphited carbon material of part.Though the graphitized carbon material degree of order of this method preparation is better, but, this method need be used expensive mesopore silicon oxide template, and numerous and diverse operating performance such as follow-up many template removals, and can only obtain the graphited meso-porous carbon material of part.Therefore, press for a kind of simple and easy to do preparation method of invention,, be its application developing wide prospect in actual production to reduce the preparation cost of bigger serface greying porous carbon.
The carbonization of rich carbon polymer is a kind of important method of preparation carbon material, and polymkeric substance has programmable rich functional groups, can form covalent linkage or coordinate bond with metal, therefore can a step prepare carbon and metal-carbon composite easily.Biomass carbonization prepares porous carbon and process of active carbon has been used many centuries, with the raw material of other preparation carbon material as hydro carbons and polymer phase ratio, biomass have many original advantages: as: source and widely distributed, low price, environmental protection and renewable etc.Advantages such as microwave heating has rapidly and efficiently, energy consumption is low, pollution-free and easy to control, at present, the microwave carbonization has become a kind of very promising preparation carbon and carbon composite method.
Summary of the invention
The object of the present invention is to provide the fast preparation method of a kind of graphite carbon simple and easy to do, that have high-specific surface area and carbon-metal carbide matrix material, and carbon prepared by this method and carbon-metal carbide nanometer structured material.
The invention provides a kind of wave absorbtion matter of conductive polymers PPy (polypyrrole) and little/mesoscopic structure feature of biopolymer utilized cleverly, provide energy with microwave, as the adulterated conducting polymer of catalyst iron/biomass combined thing rapid greying at short notice, form bigger serface, rich and varied graphited carbon nano-structured method with iron.
Biological material has special microcosmic and is situated between sees the multiple dimensioned structure that combines, and through dipping and vapor phase polymerization, and even in the process of microwave carbonization, this structure has all obtained maintenance.The existence of this structure has improved the assimilated efficiency of material to microwave just, guaranteed material greying process continue carry out.
Biomass are decomposed the gas that generation contains hydro carbons and hydrogen in a large number under microwave action, they and decolorizing carbon are in the presence of catalyst Fe, in the graphited while of biological material, generated the multiple nanostructure that comprises carbon nanotube, carbon nanobelts, graphite flake etc. in microwave processing process; The material of crossing through peracid treatment had not only had macropore but also had had mesoporously, additionally added under the situation of any hard mould agent not having simultaneously, and material also has very high specific surface area and pore volume.
Utilize the energy presentation mode of the adulterated conducting polymer of iron/biomass combined thing uniqueness under the microwave field effect, a kind of quick method for preparing carbide/carbon nano-composite material has been proposed, utilize the method for microwave heating, success prepared metallic carbide/carbon nano-structured.
The present invention is the carbonization precursor with the adulterated conducting polymer of iron of vapor phase polymerization preparation and the mixture of biomass formation, adopt microwave for giving the energy mode, prepared graphitic carbon nano structured material easily and fast with high-specific surface area, what generate carbon nano-structuredly has a very high degree of graphitization, comprising carbon nanotube, carbon nanobelts, graphite flake etc.; The material of crossing through peracid treatment had not only had macropore but also had had mesoporously, additionally added under the situation of any hard mould agent not having simultaneously, and material also has very high specific surface area and pore volume, and the pore volume of this material is 0.2-0.6cm
3/ g, specific surface area is 250-500m
2/ g.
After the biomass combined thing microwave treatment of the Fe/PPy/ of ammonium molybdate or ammonium metawolframate load, supersound process is to remove the FeC of generation in concentrated hydrochloric acid
3, obtaining molybdenum carbide (or wolfram varbide)/graphite nanometer composite material, metal is scattered in the Nano graphite structure with the carbide nanometer crystalline form, and the metal content of this material is 0.1-20.0wt%.
The graphitic carbon nano structured material of high-specific surface area of the present invention and the preparation method of carbide/graphite nanometer composite material are as follows:
(1) at first with pyrroles polymerizing catalyst-FeCl
3Be dissolved in the solvent, obtain certain density settled solution;
(2) biomass of rich cellulose be impregnated in the above-mentioned solution take out drying at room temperature after for some time;
(3) resultant is exposed in pyrroles's the steam, temperature 20-110 ℃ following vapour phase polymerization 0.5-14.0 days, obtain the biomass combined thing of Fe/PPy/;
(4) with the biomass combined thing of the Fe/PPy/ of gained microwave treatment 10-600 second (microwave power is 700-3000W) in quartz reactor, after reaction finishes, the resultant cool to room temperature, through after the certain density acid treatment, remove the iron carbide of generation, obtain the graphitized carbon nano structured material of high-specific surface area;
(5) the biomass combined thing of Fe/PPy/ that obtains in the step (3) be impregnated in certain density ammonium molybdate or the ammonium metatungstate solution take out after for some time, after the drying at room temperature, microwave treatment 10-600 second (microwave power is 700-3000W) in quartz reactor, after reaction finishes, the resultant cool to room temperature, through after the certain density acid treatment, remove the iron carbide of generation, obtain carbide/graphite nanometer composite material.
Among the present invention, the paper that the employed biomass precursor of graphitic carbon nano structured material of preparation high-specific surface area is a rich cellulose, timber and cotton etc., it exists extensively at nature.
Among the present invention, can be used for dissolving pyrroles's polymeric catalyzer-FeCl
3Solvent comprise: methyl alcohol, ethanol, tetrahydrofuran (THF) or water etc.
The biomass combined thing of Fe/PPy/ adopts the preparation of vapor phase polymerization process among the present invention, and its vapour phase polymerization condition is: temperature 20-110 ℃; Time 0.5-8.0 days.
The graphitic carbon nano structured material of high-specific surface area adopts the microwave heating method preparation among the present invention, and the condition of its microwave treatment is: treatment time 10-600 second; Microwave power 700-3000W.
The material of the microwave reactor that uses is taked among the present invention is not only to have had high microwave penetration ability but also the quartz material with resistance to elevated temperatures.
Removing the employed acid of iron carbide that generates in the dereaction among the present invention is mineral acid, as: hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid; Its concentration is 0.1-10.0mol/L; Treatment time is 0.5-10.0 hour.
The present invention has following advantage:
The microwave heating technique that the present invention is used, the carbon material degree of graphitization height that obtains, technology is simple, quick, easy to operate, need not specific installation, and process is amplified easily, realizes mass preparation easily.
The present invention is a presoma with various common biomass, and the raw material selectable range is wide, the source is easy to get, and preparation cost is low.
The present invention serves as wave absorbing agent with polypyrrole in microwave heating process, thereby reaction system is reached a high temperature rapidly, does not inhale ripple and surrounding environment comprises container, thereby its efficiency of energy utilization height, and energy consumption is low, and operational safety is reliable.
Description of drawings
Fig. 1 is to be the typical scan electromicroscopic photograph of graphite carbon material of the high-specific surface area of precursor preparation with timber (a) filter paper (b) and cotton (c).
Fig. 2 be carbon material before acid treatment and acid treatment after the exemplary x-ray diffraction spectrogram.
Fig. 3 is to be the typical Raman spectrogram of graphite carbon material of the high-specific surface area of precursor preparation with timber (a) filter paper (b) and cotton (c).
The typical transmission electron microscope photo (a) and the high-resolution-ration transmission electric-lens photo (b) of the iron carbide nanoparticle that remaining graphite coats after Fig. 4 acid treatment.
Fig. 5 is to be the typical nitrogen adsorption isotherm figure of graphite carbon material of the high-specific surface area of precursor preparation with timber (a) filter paper (b) and cotton (c).
Fig. 6 is to be the typical transmission electron microscope photo and the high-resolution-ration transmission electric-lens photo (d) of the graphite carbon material of precursor preparation with filter paper (a) timber (b) and cotton (c).
Fig. 7 is the graphitic carbon nano structure that generates: spongy nanostructure (a); Nano flake (b); Nanotube (c) and nano belt (d).
Fig. 8 is the exemplary x-ray diffraction spectrogram of molybdenum carbide/carbon composite nano structured material (a) and tungsten carbide carbon composite nanostructure material (b).
Fig. 9 is that (a is b) with tungsten carbide carbon composite nanostructure material (c, feature transmission electron microscope photo d) for molybdenum carbide/carbon composite nano structured material; Wherein (a) and (c) be light field mutually, (b) with (d) for details in a play not acted out on stage, but told through dialogues mutually.
Embodiment
The present invention is further described below by example, but the present invention is not limited in following embodiment.
Restrain filter paper in the FeCl of 0.1 gram/ml with 0.324
3Dipping is 0.5 hour in the solution (15mL), and taking-up is dried.Air dried is impregnated with FeCl
3Filter paper hang on one and fill in pyrroles's the encloses container, 30 ℃ of temperature condition vapor phase polyreactions 7 days, obtain Fe/PPy/ filter paper mixture (mass ratio 2.5/2.5/100).Fe/PPy/ filter paper mixture is transferred in the microwave reactor microwave treatment 5 minutes, the power control 1000W of microwave.Fe/PPy/ filter paper mixture continues to keep red-hot state in reaction process, after reaction finishes, and the resultant cool to room temperature, after being the acid treatment of 2mol/L through over-richness, remove the iron carbide of generation, filter, drying obtains the graphitized carbon nano structured material of high-specific surface area, and its pore volume is 0.33cm
3/ g, specific surface area is 293.2m
2/ g.Scanning electron microscope result shows that the both macro and micro pattern of biomass has obtained maintenance (Fig. 1) after carbonization.X-ray diffraction (Fig. 2) and Raman spectrum (Fig. 3) result show that material has higher degree of graphitization, and in the microwave carbonization process, generated iron carbide, after peracid treatment, most iron carbide can be removed, and the iron carbide that a small amount of graphite carbon coats still is present in (Fig. 4) in the sample.Transmission electron microscope results shows, sample have the spumescence vesicular structure (Fig. 6 a, d), in addition, also found some other carbon nano-structured (Fig. 7).
Embodiment 2
With 0.5 the gram timber in the FeCl of 0.1 gram/ml
3Dipping is 3 hours in the solution (15mL), and taking-up is dried.Air dried is impregnated with FeCl
3Timber hang on one and fill in pyrroles's the encloses container, 50 ℃ of temperature condition vapor phase polyreactions 14 days, obtain Fe/PPy/ wood composites (mass ratio 14.5/14.5/100).The Fe/PPy/ wood composites is transferred in the microwave reactor microwave treatment 5 minutes, the power control 1000W of microwave.The Fe/PPy/ wood composites continues to keep red-hot state in reaction process, after reaction finishes, and the resultant cool to room temperature, after being the acid treatment of 4mol/L through over-richness, remove the iron carbide of generation, filter, drying obtains the graphitized carbon nano structured material of high-specific surface area, and its pore volume is 0.24cm
3/ g, specific surface area is 350.9m
2/ g.
With 0.5 the gram cotton in the FeCl of 0.1 gram/ml
3Dipping is 1.5 hours in the solution (15mL), and taking-up is dried.Air dried is impregnated with FeCl
3Cotton hang on one and fill in pyrroles's the encloses container, 30 ℃ of temperature condition vapor phase polyreactions 9 days, obtain Fe/PPy/ cotton mixture (mass ratio 9.5/9.5/100).Fe/PPy/ cotton mixture is transferred in the microwave reactor microwave treatment 5 minutes, the power control 700W of microwave.Fe/PPy/ filter paper mixture continues to keep red-hot state in reaction process, after reaction finishes, and the resultant cool to room temperature, after being the acid treatment of 2mol/L through over-richness, remove the iron carbide of generation, filter, drying obtains the graphitized carbon nano structured material of high-specific surface area, and its pore volume is 0.26cm
3/ g, specific surface area is 431.3m
2/ g.
Embodiment 4
The biomass combined thing of Fe/PPy/ of 0.5 gram be impregnated in the ammonium molybdate solution that concentration is 0.1 gram/ml 3 hours, drying at room temperature.Then resultant is packed in the crystal reaction tube, transfer in the microwave oven, with the microwave treatment of 1000W 5 minutes.Behind the sample cool to room temperature, supersound process is to remove the FeC of generation in concentrated hydrochloric acid
3, obtain molybdenum carbide/graphite nanometer composite material.(Fig. 8 a) show sample has the diffraction peak of typical molybdenum carbide to the X-ray diffraction result of sample, and (Fig. 9 a b) shows that molybdenum carbide particles exists with nanocrystalline formation to transmission electron microscope results, and its size is less than 10 nanometers.
Embodiment 5
The biomass combined thing of Fe/PPy/ of 0.5 gram be impregnated in the ammonium metatungstate solution that concentration is 0.1 gram/ml 3 hours, drying at room temperature.Then resultant is packed in the crystal reaction tube, transfer in the microwave oven, with the microwave treatment of 1000W 5 minutes.Behind the sample cool to room temperature, supersound process is to remove the FeC of generation in concentrated hydrochloric acid
3, obtain wolfram varbide/graphite nanometer composite material.The X-ray diffraction result of sample (Fig. 8 b) show sample has the diffraction peak of typical wolfram varbide, and (Fig. 9 c d) shows that tungsten carbide particle exists with nanocrystalline formation to transmission electron microscope results, and its size is less than 10 nanometers.
Claims (8)
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102451727A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | A kind of M/N-C catalyst and its preparation and application |
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| US6723299B1 (en) * | 2001-05-17 | 2004-04-20 | Zyvex Corporation | System and method for manipulating nanotubes |
| CN1294076C (en) * | 2001-12-28 | 2007-01-10 | 南京师范大学 | Carbon atom wire and process for preparing carbon nanotube and carbon atom wire by pyrolyzing solid-state carbon source |
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