CN103112854B - Method for synthesizing carbide/porous graphitized carbon nano compound through one-step method - Google Patents

Method for synthesizing carbide/porous graphitized carbon nano compound through one-step method Download PDF

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CN103112854B
CN103112854B CN201310038679.9A CN201310038679A CN103112854B CN 103112854 B CN103112854 B CN 103112854B CN 201310038679 A CN201310038679 A CN 201310038679A CN 103112854 B CN103112854 B CN 103112854B
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carbide
carbon nano
porous graphite
graphite carbon
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CN103112854A (en
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付宏刚
穆光
王蕾
尹婕
于鹏
田国徽
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Heilongjiang University
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Abstract

The invention provides a method for synthesizing a carbide/porous graphitized carbon nano compound through a one-step method, relates to a method for synthesizing a carbide/porous graphitized carbon nano compound and aims to solve the problems of large size, uneven distribution, high aggregation possibility and small specific surface area of carbide particles in the carbide/porous graphitized carbon nano compound preparation in the prior art. The method comprises the following steps: 1, dissolving a carbon source and transition metal salt in solvent; 2, adding a pore forming agent and a graphitizing catalyst; 3, performing high-temperature carbonization; and 4, performing acid treatment, and then drying. The invention has the advantages that the synthesis method is simple, the synthesized carbide particle are small in size, even in distribution and large in specific surface area, the environmental pollution is less, the cost is low and the required synthesis equipment is simple, so that the invention is easy to realize commercialization. The invention is applicable to the field of energy storage and conversion.

Description

The method of one-step synthesis method carbide/porous graphite carbon nano-complex
Technical field
The present invention relates to the method for a kind of synthesizing carbide/porous graphite carbon nano-complex.
Background technology
At present, fossil fuel energy storage capacity is in minimizing day by day, and it discharges a large amount of obnoxious flavoures when burning, therefore, the exploitation that people start to show great attention to the new energy solves the problem of the energy and environment, in recent years, it is found that direct methanol fuel cell is a kind of potential a kind of new forms of energy replacing fossil oil, but because its negative electrode and anode catalyzer used are noble metal catalyst, present majority is based on Pt base, as everyone knows, precious metals pt expensive, storage capacity is few, so use it for catalyzer, to make it cost higher, to such an extent as to cannot commercialization be realized, it is found that transition metal carbide (tungsten subsequently, molybdenum, vanadium) there is the character of eka-platinium, use it for the consumption that catalystic material can reduce Pt, make the reduction of catalyzer cost, thus direct methanol fuel cell commercialization is become a reality.But, prepare carbide (tungsten at present, molybdenum, vanadium) method that mainly adopts of/porous graphite carbon nano-complex: first by after carbon source and molecular sieve mixed calcining, prepare porous graphite carbon and remove out pore-forming material, and then the presoma in tungsten source (molybdenum source or vanadium source) is adsorbed on the surface of porous graphitic carbon, through microwave, obtained carbide (tungsten after high-temperature roasting, molybdenum, vanadium) with the complex body of porous graphitic carbon, but this preparation method's synthesis technique is complicated, and obtained wolfram varbide (molybdenum, vanadium) skewness on graphite carbon easily reunites, size of particles is larger, specific surface area is little, thus affect its methanol electro-oxidizing performance, be difficult to be applied in business.
Summary of the invention
The present invention will solve the mixture that prior art prepares carbide/porous graphitic carbon nanometer to there is wolfram varbide skewness, and size of particles is comparatively large, the problem that specific surface area is little; And provide the method for one-step synthesis method carbide/porous graphite carbon nano-complex.
The method of one-step synthesis method carbide/porous graphite carbon nano-complex of the present invention, completed by following step: one, by mass ratio be 10: 2 carbon source and transition metal salt be dissolved in solvent, then add pore-forming material, then add graphitization catalyst, drying, obtains presoma; Wherein the mass volume ratio of carbon source and solvent is 1: (5 ~ 30), the mass volume ratio of carbon source and pore-forming material is 1: (1 ~ 10), the mass ratio of carbon source and graphite catalyst is 1: (0.5 ~ 5), and wherein transition metal salt is tungsten source, molybdenum source or vanadium source; Two, under the condition of protection of inert gas, rise to 500 ~ 1100 DEG C by room temperature, heat-up rate is 2 ~ 20 DEG C/min, then heat-treats 0.5 ~ 10h to the presoma of step one, obtains pre-product; Three, pre-product grinding step 2 obtained, carry out acid treatment again, then being washed with distilled water to pH is 6 ~ 8, bake drying 4 ~ 12h under 60 ~ 120 DEG C of conditions again, obtain carbide/porous graphite carbon nano-complex, namely complete the method for one-step synthesis method carbide/porous graphite carbon nano-complex.
Technique of the present invention is simple, and carbide is evenly distributed on graphite carbon, and size of particles is little, and inexpensive due to carbon source wide material sources of the present invention, and reduce production cost, and environmental pollution is little, required equipment is simple, is easy to realize commercialization.Product of the present invention has eka-platinium catalyst property, simultaneously all right resistance to carbon monoxide poisoning, therefore can as the electrode materials of direct methanol fuel cell.
Accompanying drawing explanation
Fig. 1 is the low power transmission electron microscope photo of the pure phase wolfram varbide nanoparticle of the wolfram varbide/porous graphite carbon nano-complex of test preparation;
Fig. 2 is the high power transmission electron microscope photo of the pure phase wolfram varbide nanoparticle of the wolfram varbide/porous graphite carbon nano-complex of test preparation;
Fig. 3 is the cyclic voltammogram of the wolfram varbide/porous graphite carbon nano-complex load 10%Pt and commercially available Pt/C of test preparation; Wherein a and c is the cyclic voltammogram of commercially available graphite carbon supporting Pt, b and d is the cyclic voltammogram of the wolfram varbide/porous graphite carbon nano-complex load 10%Pt of test preparation.
Embodiment
Embodiment one: the method for present embodiment one-step synthesis method carbide/porous graphite carbon nano-complex, completed by following step: one, by mass ratio be 10: 2 carbon source and transition metal salt be dissolved in solvent, then pore-forming material is added, add graphitization catalyst again, drying, obtains presoma; Wherein the mass volume ratio of carbon source and solvent is 1: (5 ~ 30), the mass volume ratio of carbon source and pore-forming material is 1: (1 ~ 10), the mass ratio of carbon source and graphite catalyst is 1: (0.5 ~ 5), and wherein transition metal salt is tungsten source, molybdenum source or vanadium source; Two, under the condition of protection of inert gas, rise to 500 ~ 1100 DEG C by room temperature, heat-up rate is 2 ~ 20 DEG C/min, then heat-treats 0.5 ~ 10h to the presoma of step one, obtains pre-product; Three, pre-product grinding step 2 obtained, carry out acid treatment again, then being washed with distilled water to pH is 6 ~ 8, bake drying 4 ~ 12h under 60 ~ 120 DEG C of conditions again, obtain carbide/porous graphite carbon nano-complex, namely complete the method for one-step synthesis method carbide/porous graphite carbon nano-complex.
The technique of present embodiment is simple, and carbide is evenly distributed on graphite carbon, and size of particles is little, and inexpensive due to the carbon source wide material sources of present embodiment, and reduce production cost, and environmental pollution is little, required equipment is simple, is easy to realize commercialization.The product of present embodiment has eka-platinium catalyst property, simultaneously all right resistance to carbon monoxide poisoning, therefore can as the electrode materials of direct methanol fuel cell.
Embodiment two: present embodiment and embodiment one are the extract of farm crop, high molecular polymer or shells extract unlike: the carbon source in step one, and wherein the extract of farm crop is glucose, sucrose, citric acid, sucrose, fructose, maltose, oxalic acid, tartrate or starch; High molecular polymer is a kind of in polystyrene, polyacrylamide, poly furfuryl alcohol, poly-imines, urethane, poly-glucosamine, acid polyethylene methyl esters and polyaniline or wherein several mixture be mixed by any ratio; Shells extract is chitosan or chitin.Other step and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: the tungsten source in step one is H 2w 6o 19, H 3pW 12o 40, H 3siW 12o 40, H 4w 10o 32, (NH 4) 6w 7o 24, Na 2wO 4, Na 2w 6o 19, WCl 6, Na 3pW 12o 40, Na 3siW 12o 40, Na 4w 10o 32, K 2w 6o 19, K 3pW 12o 40, K 3siW 12o 40or K 4w 10o 32; Molybdenum source is H 2mo 6o 19, H 3pMo 12o 40, H 3siMo 12o 40, H 4mo 10o 32, (NH 4) 6mo 7o 24, Na 2moO 4, Na 2mo 6o 19, Na 3pMo 12o 40, Na 3siMo 12o 40, Na 4mo 10o 32, K 2mo 6o 19, K 3pMo 12o 40, K 3siMo 12o 40or K 4mo 10o 32; Vanadium source is: HVO 3, H 3vO 4, H 4v 2o 7, H 3v 3o 9, NaVO 3, NH 4vO 3, Na 3vO 4or (NH 4) 2v 6o 16.Other step and parameter identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three are a kind of in water, methyl alcohol, ethanol and Virahol or wherein several mixture be mixed by any ratio unlike: the solvent in step one.Other step and parameter identical with one of specific embodiment party one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: the pore-forming material in step one is tetraethoxy, silica gel, SBA-n molecular sieve, CMK-n molecular sieve, MCM-22 molecular sieve, Beta molecular sieve, USY molecular sieve, BEA/MOR cocrystallization molecular sieve, MFI/MOR cocrystallization molecular sieve, PS ball, zeolite, polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer, the addition polymer of polypropylene glycol and oxyethane, polymethylmethacrylate, polyvinylpyrrolidone, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, sodium lauryl sulphate, lime acetate, caoxalate, calcium carbonate, volatile salt or bicarbonate of ammonia.Other step and parameter identical with one of specific embodiment party one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the graphitization catalyst in step one be nickelous chloride, nickelous nitrate, single nickel salt, nickelous acetate, iron(ic) chloride, iron protochloride, iron nitrate, Iron nitrate, ferric sulfate, ferrous sulfate, the Tripotassium iron hexacyanide, yellow prussiate of potash, three oxalic acid close a kind of in potassium ferrite, cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol and cobaltous acetates or wherein several mixture be mixed by any ratio.Other step and parameter identical with one of specific embodiment party one to five.
Embodiment seven: one of present embodiment and embodiment one to six are a kind of in nitrogen, argon gas and helium or wherein several mixture be mixed by any ratio unlike: the rare gas element in step 2.Other step and parameter identical with one of specific embodiment party one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: in step 2, heat-treating atmosphere is nitrogen, argon gas, helium, methane, ethene, carbonic acid gas or carbon monoxide, and gas flow is 10 ~ 200mL/min.Other step and parameter identical with one of specific embodiment party one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: in step 3, acid-treated method is: be process after 4 ~ 48h in the sodium hydroxide solution of 0.5 ~ 5mol/L in concentration, then in concentration is the hydrochloric acid of 11.9mol/L or the salpeter solution of 14mol/L under 70 ~ 140 DEG C of conditions 6 ~ 12h in backflow.Other step and parameter identical with one of specific embodiment party one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: in step 3, acid-treated method is: under 20 ~ 40 DEG C of conditions, mass concentration be in 10 ~ 15% hydrofluoric acid stir 6 ~ 72h.Other step and parameter identical with one of specific embodiment party one to nine.
Embodiment 11: one of present embodiment and embodiment one to ten unlike: the heat-up rate in step 2 is 5 DEG C/min.Other step and parameter identical with one of specific embodiment party one to ten.
Embodiment 12: one of present embodiment and embodiment one to ten one unlike: rise to 1000 DEG C by room temperature in step 2.Other step and parameter identical with one of embodiment one to ten one.
By following verification experimental verification beneficial effect of the present invention:
Test: the method for this test one-step synthesis method carbide/porous graphite carbon nano-complex, completed by following step: one, 2g glucose and 0.4g sodium wolframate are dissolved in 30 water, then add the tetraethoxy of 4mL, then add the nickelous chloride of 2g, drying, obtains presoma; Two, under the condition of protection of inert gas, rise to 1000 DEG C by room temperature, heat-up rate is 5 DEG C/min, then heat-treats 2h to the presoma of step one, obtains pre-product; Three, pre-product grinding step 2 obtained, being added to 120mL mass concentration is again in the acetic acid of 15%, 4h is stirred under 25 DEG C of conditions, the pH being washed with distilled water to washing lotion is 7, then bake drying 8h under 100 DEG C of conditions, obtain wolfram varbide/porous graphite carbon nano-complex, namely complete the method for one-step synthesis method carbide/porous graphite carbon nano-complex.
Wolfram varbide/porous graphite carbon nano-complex transmission electron microscope the photo of this test preparation as depicted in figs. 1 and 2, can significantly find out from figure, wolfram varbide nanoparticle evenly spreads on graphite flake, the particle diameter of wolfram varbide is about 10nm, there is vesicular structure, thus to further demonstrate product be that the mixture of wolfram varbide/porous graphitic carbon makes them in some important chemical reactions of catalysis, such as methanol electro-oxidizing, sensitization solar battery to electrode, hydrolytic hydrogen production, ammonolysis craft, oxidizing reaction and the hydrocarbon conversion and building-up reactions etc., present good catalytic performance.The Pt of wolfram varbide porous graphite carbon nano-complex load 10% prepared by test 1, Fig. 3 be load 10%Pt wolfram varbide porous graphite carbon nano-complex and commercially available Pt/C for the cyclic voltammogram of methanol fuel cell catalyst, as can be seen from figure we, load 10%Pt wolfram varbide/porous graphite carbon nano-complex there is higher peak current, and can effectively inhibit carbon monoxide poisoning phenomenon, illustrate load 10%Pt wolfram varbide/porous graphite carbon nano-complex there is good methanol electro-oxidizing-catalyzing performance.

Claims (9)

1. the method for one-step synthesis method carbide/porous graphite carbon nano-complex, it is characterized in that the method for one-step synthesis method carbide/porous graphite carbon nano-complex is completed by following step: one, be that carbon source and the transition metal salt of 10:2 is dissolved in solvent by mass ratio, then pore-forming material is added, add graphitization catalyst again, drying, obtains presoma; Wherein the mass volume ratio of carbon source and solvent is 1:(5 ~ 30), the mass volume ratio of carbon source and pore-forming material is 1:(1 ~ 10), the mass ratio of carbon source and graphite catalyst is 1:(0.5 ~ 5), wherein transition metal salt is tungsten source, molybdenum source or vanadium source; Two, under the condition of protection of inert gas, rise to 500 ~ 1100 DEG C by room temperature, heat-up rate is 2 ~ 20 DEG C/min, then heat-treats 0.5 ~ 10h to the presoma of step one, obtains pre-product; Three, pre-product grinding step 2 obtained, carry out acid treatment again, then being washed with distilled water to pH is 6 ~ 8, bake drying 4 ~ 12h under 60 ~ 120 DEG C of conditions again, obtain carbide/porous graphite carbon nano-complex, namely complete the method for one-step synthesis method carbide/porous graphite carbon nano-complex;
Wherein, in step one, pore-forming material is tetraethoxy, silica gel, SBA-n molecular sieve, CMK-n molecular sieve, MCM-22 molecular sieve, Beta molecular sieve, USY molecular sieve, BEA/MOR cocrystallization molecular sieve, MFI/MOR cocrystallization molecular sieve, PS ball, zeolite, polyethylene oxide-poly(propylene oxide)-polyethylene oxide triblock copolymer, the addition polymer of polypropylene glycol and oxyethane, polymethylmethacrylate, polyvinylpyrrolidone, cetyl trimethylammonium bromide, palmityl trimethyl ammonium chloride, sodium lauryl sulphate, lime acetate, caoxalate, calcium carbonate, volatile salt or bicarbonate of ammonia.
2. the method for one-step synthesis method carbide/porous graphite carbon nano-complex according to claim 1, the carbon source that it is characterized in that in step one is the extract of farm crop, high molecular polymer or shells extract, and wherein the extract of farm crop is glucose, sucrose, citric acid, fructose, maltose, oxalic acid, tartrate or starch; High molecular polymer is a kind of in polystyrene, polyacrylamide, poly furfuryl alcohol, poly-imines, urethane, poly-glucosamine, acid polyethylene methyl esters and polyaniline or wherein several mixture be mixed by any ratio; Shells extract is chitosan or chitin.
3. the method for one-step synthesis method carbide/porous graphite carbon nano-complex according to claim 1, is characterized in that the tungsten source in step one is H 2w 6o 19, H 3pW 12o 40, H 3siW 12o 40, H 4w 10o 32, (NH 4) 6w 7o 24, Na 2wO 4, Na 2w 6o 19, WCl 6, Na 3pW 12o 40, Na 3siW 12o 40, Na 4w 10o 32, K 2w 6o 19, K 3pW 12o 40, K 3siW 12o 40or K 4w 10o 32; Molybdenum source is H 2mo 6o 19, H 3pMo 12o 40, H 3siMo 12o 40, H 4mo 10o 32, (NH 4) 6mo 7o 24, Na 2moO 4, Na 2mo 6o 19, Na 3pMo 12o 40, Na 3siMo 12o 40, Na 4mo 10o 32, K 2mo 6o 19, K 3pMo 12o 40, K 3siMo 12o 40or K 4mo 10o 32; Vanadium source is: HVO 3, H 3vO 4, H 4v 2o 7, H 3v 3o 9, NaVO 3, NH 4vO 3, Na 3vO 4or (NH 4) 2v 6o 16.
4. the method for one-step synthesis method carbide/porous graphite carbon nano-complex according to claim 1, the solvent that it is characterized in that in step one is a kind of in water, methyl alcohol, ethanol and Virahol or wherein several mixture be mixed by any ratio.
5. the method for one-step synthesis method carbide/porous graphite carbon nano-complex according to claim 1, the graphitization catalyst that it is characterized in that in step one is nickelous chloride, nickelous nitrate, single nickel salt, nickelous acetate, iron(ic) chloride, iron protochloride, iron nitrate, Iron nitrate, ferric sulfate, ferrous sulfate, the Tripotassium iron hexacyanide, yellow prussiate of potash, three oxalic acid close a kind of in potassium ferrite, cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol and cobaltous acetates or wherein several mixture be mixed by any ratio.
6. the method for one-step synthesis method carbide/porous graphite carbon nano-complex according to claim 1, the rare gas element that it is characterized in that in step 2 is a kind of in nitrogen, argon gas and helium or wherein several mixture be mixed by any ratio.
7. the method for one-step synthesis method carbide/porous graphite carbon nano-complex according to claim 1, it is characterized in that in step 2, heat-treating atmosphere is nitrogen, argon gas, helium, carbonic acid gas or carbon monoxide, gas flow is 10 ~ 200mL/min.
8. the method for one-step synthesis method carbide/porous graphite carbon nano-complex according to claim 1, it is characterized in that in step 3, acid-treated method is: be process after 4 ~ 48h in the sodium hydroxide solution of 0.5 ~ 5mol/L in concentration, then in concentration be 11.9mol/L hydrochloric acid or 14mol/L salpeter solution under 70 ~ 140 DEG C of conditions 6 ~ 12h in backflow.
9. the method for one-step synthesis method carbide/porous graphite carbon nano-complex according to claim 1, is characterized in that in step 3, acid-treated method is: under 20 ~ 40 DEG C of conditions, is stir 6 ~ 72h in 10 ~ 15% hydrofluoric acid in mass concentration.
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