CN101613100A - The biomass-based graphitized carbon and the microwave preparation of carbon-carbon composite - Google Patents
The biomass-based graphitized carbon and the microwave preparation of carbon-carbon composite 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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Abstract
The present invention relates to graphite carbon, specifically a kind of is the carbonization precursor with the biomass combined thing of PPy/, flash carbonization and greying under microwave action, the non-hard template method of the graphite composite material of preparation bigger serface.Concrete preparation method is: at first, the employing iron trichloride is a catalyzer, adopts the vapor phase polymerization technique to prepare the biomass combined thing of Fe/PPy/; Secondly, the biomass combined thing of Fe/PPy/ with preparation carries out the microwave carbonizing treatment; At last, sample is removed the iron carbide of generation through peracid treatment, obtains the graphitized carbon material of high-specific surface area.Adopt similar method, the applicant has also successfully prepared metallic carbide/graphitized carbon matrix 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)
1. the microwave preparation of a biomass-based graphitized carbon material, it is characterized in that: it is the carbonization precursor with the biomass combined thing of PPy/, flash carbonization and greying under microwave action, the graphite composite material of preparation bigger serface; Be specially, selecting the biomass polymer of rich cellulose is the carbonization precursor, at first, adopts FeCl
3Be catalyzer, the biomass combined thing of Fe/PPy/ is prepared in the vapor phase polymerization; Secondly, the biomass combined thing of Fe/PPy/ is carried out the microwave carbonizing treatment; At last, sample is removed the FeC of generation through peracid treatment
3, obtain the graphitized carbon material of high-specific surface area.
2. preparation method according to claim 1 is characterized in that: the biomass polymer of rich cellulose is placed FeCl
3Flood in the solution, take out the back in drying at room temperature; Exsiccant is impregnated with FeCl
3Biomass suspension be hung on a bottom and fill in pyrroles's the encloses container, 20-110 ℃ of temperature condition vapor phase polyreaction 0.5-14 days, obtain the mixture of Fe/PPy/ biomass=mass ratio 2～15/2～15/100; The biomass combined thing of Fe/PPy/ is transferred in the microwave reactor microwave treatment 1-600 second, the power control 700-3000W of microwave; The biomass combined thing of Fe/PPy/ continues to keep red-hot state in reaction process, after reaction finished, the resultant cool to room temperature after peracid treatment, was removed the iron of generation, obtains the graphitized carbon nano structured material of high-specific surface area.
3. preparation method according to claim 2 is characterized in that: the solvent of dissolving PPy polymerizing catalyst iron trichloride is methyl alcohol, ethanol, tetrahydrofuran (THF) or water; The concentration of iron trichloride is 0.1-1.0mol/L, floods 0.5-3 hour.
4. the microwave preparation of a carbon-carbon composite is characterized in that: with the biomass combined thing of PPy/ that flooded molybdenum or tungsten salt is the carbonization precursor, flash carbonization and greying under microwave action, preparation carbide/graphitized carbon nano matrix material; Be specially, the biomass combined thing of Fe/PPy/ impregnated in ammonium molybdate or the ammonium metatungstate solution drying at room temperature; Then resultant is packed in the crystal reaction tube, transfer in the microwave oven, with 700～3000W microwave treatment 2～5 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 or wolfram varbide/graphite nanometer composite material.
5. preparation method according to claim 4 is characterized in that: the biomass polymer of rich cellulose is placed FeCl
3Flood in the solution, take out the back in drying at room temperature; Exsiccant is impregnated with FeCl
3Biomass suspension be hung on a bottom and fill in pyrroles's the encloses container, 20-110 ℃ of temperature condition vapor phase polyreaction 0.5-14 days, obtain the mixture of Fe/PPy/ biomass=mass ratio 2～15/2～15/100.
Place the ammonium molybdate of 0.01～0.1 gram/ml or ammonium metatungstate solution to flood drying at room temperature 2～5 hours the biomass combined thing of Fe/PPy/ that generates; Resultant is transferred in the microwave reactor, microwave treatment 1-5 minute, the power control 700-3000W of microwave; After reaction finishes, the resultant cool to room temperature, after peracid treatment, remove iron carbide after, obtain molybdenum carbide or wolfram varbide/graphitized carbon nano structured material, the loading of metal is 0.1-20.0wt%.
6. according to claim 1 or 4 described preparation methods, it is characterized in that: the biomass polymer of described rich cellulose is the biomass of natural cellulose and phyteral.
7. preparation method according to claim 6 is characterized in that: described natural cellulose is paper or cotton; The biomass of described phyteral are crop stalk or timber; The material of employed microwave reactor is quartzy.
8. according to claim 2 or 5 described preparation methods, it is characterized in that: describedly remove the employed acid of de-iron and be: hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid; Its concentration is 0.1-10.0mol/L; Treatment time is 0.1-10.0 hour.
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| CN108521754A (en) * | 2018-04-11 | 2018-09-11 | 南京航空航天大学 | Porous carbon-based electromagnetic wave absorption agent of one kind and preparation method thereof |
| CN108521754B (en) * | 2018-04-11 | 2019-11-29 | 南京航空航天大学 | Porous carbon-based electromagnetic wave absorption agent of one kind and preparation method thereof |
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