CN103381368B - A kind of level hole tungsten carbide/carbon composite and preparation method thereof - Google Patents

A kind of level hole tungsten carbide/carbon composite and preparation method thereof Download PDF

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CN103381368B
CN103381368B CN201310180077.7A CN201310180077A CN103381368B CN 103381368 B CN103381368 B CN 103381368B CN 201310180077 A CN201310180077 A CN 201310180077A CN 103381368 B CN103381368 B CN 103381368B
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tungsten carbide
carbon composite
level hole
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carbon
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CN103381368A (en
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夏燎原
田梁材
胡云楚
吴义强
邓凌峰
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Central South University of Forestry and Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The preparation method of a kind of level hole tungsten carbide/carbon composite, comprise the steps: that (1) presoma is prepared: at 40 DEG C, appropriate template is dissolved in the mixed solution of second alcohol and water, then carbon source and tungsten source is added successively, abundant stirring obtains homogeneous transparent solution, obtains precursor solution; (2) vacuum impregnation: step (1) gained precursor solution is transferred in wood powder, then volatilization removing mixed solvent, the drying at 30 ~ 60 DEG C of negative pressure of vacuum dipping, solidifies and obtains prepolymer product; (3) carbonizing reduction: under reducing atmosphere, is placed in reacting furnace by step (2) gained prepolymer product, roasting a few hours at 700 ~ 1400 DEG C, then cools, grinds and obtain level hole tungsten carbide/carbon composite.Step of the present invention simply, fast saves time, production cost is low, can improve the biomass material such as added value and efficiency utilization timber of tungsten carbide, have a extensive future.

Description

A kind of level hole tungsten carbide/carbon composite and preparation method thereof
Technical field
The present invention relates to field of material technology, the invention still further relates to the preparation of catalyst or catalyst carrier in electrochemistry and organic synthesis, be specially a kind of level hole tungsten carbide/carbon composite and its preparation method and application.
Background technology
Research shows, tungsten carbide has the catalytic activity of similar platinum, and process based prediction model is stablized, and cheap.Along with people are to the attention of clean energy resource, tungsten carbide is at catalytic field, and the application of the aspects such as such as DMFC, catalytic hydrogen evolution, super-capacitor and catalytic desulfurization causes the extensive concern of scientist; In electrochemical field, as the advantage of anode catalyst, tungsten carbide is that it not only has catalytic performance and can replace the precious metal such as platinum, palladium, and not easily poisoned by carbon monoxide.Thus, tungsten carbide partly can replace as catalyst or save the precious metal such as platinum, palladium to a certain extent, and it has a extensive future.
The traditional preparation method of tungsten carbide is " solid reaction process ", it is obtained 1600 DEG C of pyroreactions by tungsten powder and powdered carbon, make that the tungsten carbide particle obtained in this way is easily reunited, specific area is little, but metallurgical industry needs can only be met, can not effectively play its catalytic action.And in electrochemical applications, porous charcoal carrier plays an important role to the catalytic activity and stability that improve tungsten carbide, this possesses good electric conductivity mainly due to high-area carbon; The high-specific surface area of high-area carbon, is conducive to the high degree of dispersion of tungsten carbide; The pore passage structure that high-area carbon opens contributes to " mass transfer " process of catalytic reaction; Chemistry, the physical stability of high-area carbon are good, are applicable to various applied environment.Therefore, the preparation and application of level hole tungsten carbide/carbon composite cause the concern of scientific research personnel in recent years.Up to now, the preparation method of the tungsten carbide/carbon composite of bibliographical information is confined to " infusion process " (H.Meng, etc, Chem.Commun.2005,31,4408 substantially; Q.Zhu, etc, J.PowerSources, 2009,193,495), " hydro-thermal method " (Y.Wang, etc, J.Mater.Chem., 2009,19,6149), " hard template method " (Z.X.Wu, etc, Small2009,5,2738; Y.H.Zhang, etc, Chem.Commun., 2010,46,862) etc., all there is deficiency in various degree.
Timber has the test-tube baby structure (pore structure) of unidirectional array, the test-tube baby tissue of its fibr tissue from the cell envelope structure of nanometer scale to micron dimension, arrive the annual ring of millimeter magnitude again, define the biological structure features such as unique multi-level, test-tube baby structure, threadiness and anisotropy; The principal component of timber is lignin, cellulose and hemicellulose, and in main component, carbon accounts for 44%.Thus, timber not only can make the stay in place form of biomimesis synthesis, and can as carbon source and the stay in place form preparing carbide composite material.In addition, compared with the material coming from industrial chemicals with other, the outstanding advantage of timber is its " renewable " property and " environmental protection " to meet the strategic idea of human social.Undoubtedly, there is in the composite that the anisotropy graded porous structure that wood template is natural has a special microstructure grading-hole in preparation the advantageous advantage that other stay in place form can not be compared.Obviously, this is that the functional material of pore structure by different level having unique micropore, mesopore and macropore in conjunction with in situ synthesis preparation by biological template method provides new approaches.
Summary of the invention
Technical problem solved by the invention is to provide a kind of level hole tungsten carbide/carbon composite and preparation method thereof, to solve the shortcoming in above-mentioned background technology.
Technical problem solved by the invention realizes by the following technical solutions:
A kind of level hole tungsten carbide/carbon composite and preparation method thereof, utilize bionics and molecular self-assembling principle, take timber as mimicry template, surfactant is " soft " template, tungsten source, carbon source are presoma, prepare the tungsten carbide/carbon composite with unique hierarchical pore structure by means of solvent evaporation induced self-assembly process and polynary coupling.The method preparation process is simple, production cost is low, can improve the biomass material such as added value and efficiency utilization timber of tungsten carbide, the level hole tungsten carbide/carbon composite of preparation has the features such as high-specific surface area and unique micropore, mesopore and macropore hierarchical pore structure, tungsten carbide thing be mutually single.Tungsten carbide/carbon composite can be widely used in various electrochemical catalysis, sensor and organic synthesis etc., especially can directly as catalyst or the carrier of methanol fuel cell, to reach the object of saving platinum, palladium precious metal catalyst.
A preparation method for level hole tungsten carbide/carbon composite, comprises the steps:
(1) precursor solution preparation: at 40 DEG C, be dissolved in by appropriate template in a certain amount of ethanol and water mixed solution, then add carbon source and tungsten source successively, fully stirs and obtains homogeneous transparent solution, obtain precursor solution;
(2) vacuum impregnation: the precursor solution that step (1) is prepared is transferred in a certain amount of wood powder, negative pressure of vacuum dipping 30 ~ 90 minutes, then volatilization removing mixed solvent, drying at 30 ~ 60 DEG C, then at 100 ~ 150 DEG C, namely solidification obtains prepolymer product in 12 ~ 48 hours;
(3) carbonizing reduction: under reducing atmosphere, to be placed at high temperature reaction stove 700 ~ 1400 DEG C roasting 1 ~ 7 hour, then to cool, grinds by step (2) gained prepolymer product, level hole tungsten carbide/carbon composite.
In the present invention, in the mixed solution described in step (1), the mass ratio of water and ethanol is 1:(1 ~ 20); The mass ratio of template and mixed solution is 1:(20 ~ 100); The mass ratio of tungsten source and carbon source is 1:(1 ~ 15); The mass ratio of carbon source and mixed solution is 1:(6 ~ 40).
In the present invention, the template described in step (1) is three surfactant (EO such as block or diblock copolymer such as PEO-PPOX, oxirane-polybutylene oxide npO meO n, EO nbO meO n, EO nbO m, EO npO m) in one or more mixture, be EO as preferred surfactant 20pO 70eO 20(P123), EO 106pO 70eO 106(F127) one or more mixture in.
In the present invention, the carbon source described in step (1) is one in A rank phenolic aldehyde prepolymer, carbamide prepolymer (Mw<500) or two kinds of mixing; Described prepolymer can pass through known technology: as phenolic aldehyde and formaldehyde or the preparation of the base catalyzed reactions between melamine and formaldehyde.
In the present invention, the tungsten source described in step (1) is one or more mixtures in the oxide of tungsten, wolframic acid, tungstates, metatungstate; Described tungsten source is water-soluble or be dissolved in the mixed liquor of ethanol and water or be slightly soluble in ethanol.
In the present invention, the wood powder described in step (2) is arbitrary timber elaboration products; Wherein, the mass ratio of wood powder and precursor solution is 1:(1 ~ 8).
In the present invention, the reducing atmosphere described in step (3) is throughput is 20 ~ 80mL/min, volume ratio is 1:(1 ~ 6) hydrogen and the gaseous mixture of nitrogen.
In the present invention, the temperature in step (3) is preferably 900 ~ 1200 DEG C.
In the present invention, the time in step (3) is preferably 3 ~ 6 hours.
beneficial effect
The present invention is compared with existing " infusion process ", " hydro-thermal method ", " hard template method ", and tool has the following advantages:
(1) in method, " knowledge nature ", adopt biomimesis synthetic method, take timber as mimicry template, surfactant is " soft " template, tungsten source, carbon source are presoma, are introduced by vacuum impregnation, prepare the tungsten carbide/carbon composite of the hierarchical pore structure with micropore, mesopore and macropore by means of solvent evaporation induced self-assembly process and the polynary coupling of thermal field;
(2) in resource, the tungsten ore resource of low quality wood, wood machining residues and China's abundant is effectively utilized, the level hole tungsten carbide/Pd/carbon catalyst of innovative development high added value;
(3) carbon composite is widely used in various electrochemical catalysis, sensor and organic synthesis etc., especially can be used as catalyst or the carrier of DMFC, to reach the target of saving platinum catalyst, promote the industrialization of the related green energy such as fuel cell.
Accompanying drawing explanation
Fig. 1 is the little angle x-ray diffraction pattern of level hole tungsten carbide/carbon composite prepared by embodiment 3.
Fig. 2 is the wide-angle x-ray diffraction figure of level hole tungsten carbide/carbon composite prepared by embodiment 3.
Fig. 3 is composite macropore cross section (a) structure chart in the level hole tungsten carbide/carbon composite scanning electron microscopic picture of embodiment 3 preparation.
Fig. 4 is composite macropore section (b) structure chart in the level hole tungsten carbide/carbon composite scanning electron microscopic picture of embodiment 3 preparation.
Fig. 5 is the N of level hole tungsten carbide/carbon composite prepared by embodiment 3 2adsorption-desorption curve and corresponding pore size distribution curve.
Fig. 6 is the methanol oxidation cyclic voltammetry curve of level hole tungsten carbide/carbon composite load 7.5%Pt prepared by embodiment 3.
Detailed description of the invention
The technological means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with concrete diagram, setting forth the present invention further.
Embodiment 1
(1) get 20% (wt.) low order phenolic resins 5.0g, add ethanol 20g and 10g water, at 40 DEG C, stir about 20 minutes, then adds 2.0gF127, continues to stir until dissolve completely; Then add the AMT solution 1.0g of 33.3wt%, fully dispersion obtains homogeneous transparent solution, continues to stir 1h, obtains precursor solution;
(2) above-mentioned precursor solution is transferred in 10g wood powder, negative pressure of vacuum dipping 30min, then volatilize mixed solvent at 40 DEG C, until bone dry, be then placed in 105 DEG C oven for curing 24 hours, obtain prepolymer product;
(3) above-mentioned prepolymer product is ground into fragment, is placed in tubular react furnace, pass into that throughput is 60mL/min, volume ratio is the nitrogen of 3:1 and the gaseous mixture of hydrogen, is warming up to 900 DEG C gradually, calcining at constant temperature 3 hours, programmed rate is 5 DEG C/min; Then naturally cool, grinding, obtains level hole tungsten carbide/carbon composite.
Embodiment 2
(1) take 20% (wt.) low order phenolic resins 5.0g, add ethanol 20g and 14g water, at 40 DEG C, stir about 20 minutes, then adds 2.0gF127, continues to stir until dissolve completely; Then add the AMT solution 2.0g of 33.3wt%, fully dispersion obtains homogeneous transparent solution, continues to stir 1h, obtains precursor solution;
(2) above-mentioned precursor solution is transferred in 8g wood powder, negative pressure of vacuum dipping 30min, then volatilize mixed solvent at 40 DEG C, until bone dry, be then placed in 105 DEG C oven for curing 24 hours, obtain prepolymer product;
(3) above-mentioned prepolymer product is ground into fragment, is placed in tubular react furnace, pass into that throughput is 30mL/min, volume ratio is the nitrogen of 3:1 and the gaseous mixture of hydrogen, is warming up to 1200 DEG C gradually, calcine 3 hours, programmed rate is 5 DEG C/min; Then naturally cool, grinding, obtains level hole tungsten carbide/carbon composite.
Embodiment 3
(1) take 20% (wt.) low order phenolic resins 5.0g, add ethanol 20g and 16g water, at 40 DEG C, stir about 20 minutes, then adds 2.5gF127, continues to stir until dissolve completely; Then add the AMT solution 3.0g of 33.3wt%, fully dispersion obtains homogeneous transparent solution, continues to stir 1h, obtains precursor solution;
(2) above-mentioned precursor solution is transferred in 10g wood powder, negative pressure of vacuum dipping 60min, then volatilize mixed solvent at 40 DEG C, until bone dry, be then placed in 105 DEG C oven for curing 24 hours, obtain prepolymer product;
(3) above-mentioned prepolymer product is ground into fragment, is placed in tubular react furnace, pass into that throughput is 40mL/min, volume ratio is the nitrogen of 4:1 and the gaseous mixture of hydrogen, is warming up to 1000 DEG C gradually, calcine 4 hours, programmed rate is 5 DEG C/min.Then naturally cool, grinding, obtains level hole tungsten carbide/carbon composite.
See the little angle x-ray diffraction pattern that Fig. 1 is level hole tungsten carbide/carbon composite prepared by embodiment 3, diagram display, this composite has obvious mesoscopic structure characteristic diffraction peak.
See the wide-angle x-ray diffraction figure that Fig. 2 is level hole tungsten carbide/carbon composite prepared by embodiment 3, according to standard card (PDF#51-0939), in three diffraction maximums that 2 θ are 31.361,35.660 and 48.319 places, (001), (100) and (101) these three crystal faces of corresponding WC, show that level hole tungsten carbide/carbon composite prepared by this embodiment is single WC thing phase respectively.
It is composite macropore cross section (a) structure chart in the level hole tungsten carbide/carbon composite scanning electron microscopic picture of embodiment 3 preparation see Fig. 3.
It is composite macropore section (b) structure chart in the level hole tungsten carbide/carbon composite scanning electron microscopic picture of embodiment 3 preparation see Fig. 4.
See the N that Fig. 5 is level hole tungsten carbide/carbon composite prepared by embodiment 3 2adsorption-desorption curve and corresponding pore size distribution curve, in the present embodiment, adopt the specific area of the ASAP2010 nitrogen adsorption instrument of Micromeritics company of the U.S. and the mercury injection apparatus test layer secondary aperture tungsten carbide/carbon composite of PoreMaster, pore volume and pore-size distribution, result shows, the specific area of this material is 891.7m 2/ g, pore volume is up to 3.92cm 3/ g.
The level hole tungsten carbide/carbon composite adopting preparation in embodiment 3 is carrier, adds appropriate H 2ptCl 6solution (2mmol/L) ultrasonic disperse, wherein the mass percentage of Pt is 7.5%, and adjust ph is 8; Then excessive 1MNaBH is added 4solution, mixes, fully reacts; Then repeatedly rinse precipitation 3 times to remove sodium ion with freezing distilled water, neutralization reaction mixture, namely obtains the level hole tungsten carbide/carbon electric catalyst of load 7.5%Pt.Corresponding catalytic reaction electrode is according to document (WangY., SongS.Q., ShenP.K., etal.Nanochain-structuredmesoporoustungstencarbideandits superiorelec-trocatalysis [J] .J.Mater.Chem., 2009,19:6149 – 6153.) method preparation.
See the methanol oxidation cyclic voltammetry curve that Fig. 6 is level hole tungsten carbide/carbon composite load 7.5%Pt prepared by embodiment 3, can find out, repeatedly there is forward current peak at sweep interval all respectively in catalyst, illustrate that the oxidation performance of this catalyst to methyl alcohol goes out good catalytic effect near forward scan reverse scan.
Embodiment 4
(1) take 20% (wt.) low order phenolic resins 5.0g, add ethanol 20g and 18g water, at 40 DEG C, stir about 20 minutes, then adds 2.0gF127, continues to stir until dissolve completely; Then add the AMT solution 4.0g of 33.3wt%, fully dispersion obtains homogeneous transparent solution, continues to stir 1h, obtains precursor solution;
(2) above-mentioned precursor solution is transferred in 10g wood powder, negative pressure of vacuum dipping 30min, then volatilize mixed solvent at 40 DEG C, until bone dry, be then placed in 105 DEG C oven for curing 48 hours, obtain prepolymer product;
(3) above-mentioned prepolymer product is ground into fragment, is placed in tubular react furnace, pass into that throughput is 40mL/min, volume ratio is the nitrogen of 3:1 and the gaseous mixture of hydrogen, is warming up to 1400 DEG C gradually, calcine 3 hours, programmed rate is 5 DEG C/min.Then naturally cool, grinding, obtains level hole tungsten carbide/carbon composite.
Embodiment 5
(1) take ethanol 20g and 16g water, then add 2.0gF127, be stirred at 40 DEG C and dissolve completely; Then add the AMT solution 3.0g of 33.3wt%, fully dispersion obtains homogeneous transparent solution, continues to stir 1h, obtains precursor solution;
(2) above-mentioned precursor solution is transferred in 10g wood powder, negative pressure of vacuum dipping 60min, then volatilize mixed solvent at 40 DEG C, until bone dry, be then placed in 105 DEG C oven for curing 12 hours, obtain prepolymer product;
(3) above-mentioned prepolymer product is ground into fragment, is placed in tubular react furnace, pass into that throughput is 80mL/min, volume ratio is the nitrogen of 4:1 and the gaseous mixture of hydrogen, is warming up to 1000 DEG C gradually, calcine 3 hours, programmed rate is 5 DEG C/min; Then naturally cool, grinding, obtains level hole tungsten carbide/carbon composite.
Embodiment 6
(1) get 20% (wt.) low order phenolic resins 5.0g, add ethanol 20g and 14g water, at 40 DEG C, stir about 20 minutes, then adds 2.0gP123, continues to stir until dissolve completely; Then add the AMT solution 2.0g of 33.3wt%, fully dispersion obtains homogeneous transparent solution, continues to stir 1h, obtains precursor solution;
(2) above-mentioned precursor solution is transferred in 10g wood powder, negative pressure of vacuum dipping 60min, then volatilize mixed solvent at 40 DEG C, until bone dry, be then placed in 105 DEG C oven for curing 24 hours, obtain prepolymer product;
(3) above-mentioned prepolymer product is ground into fragment, is placed in tubular react furnace, pass into that throughput is 60mL/min, volume ratio is the nitrogen of 4:1 and the gaseous mixture of hydrogen, is warming up to 1000 DEG C gradually, calcining at constant temperature 4 hours, programmed rate is 3 DEG C/min; Then naturally cool, grinding, obtains level hole tungsten carbide/carbon composite.
More than show and describe general principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and description just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.

Claims (7)

1. the preparation method of level hole tungsten carbide/carbon composite, it is characterized in that, comprise the steps: that (1) precursor solution is prepared: at 40 DEG C, appropriate template is dissolved in a certain amount of ethanol and water mixed solution, template is one or both mixing in non-ionic surface active agent P123, F127, then carbon source and tungsten source is added successively, carbon source is the one in A rank phenolic aldehyde prepolymer, carbamide prepolymer, abundant stirring obtains homogeneous transparent solution, obtains precursor solution; (2) vacuum impregnation: the precursor solution that step (1) is prepared is transferred in a certain amount of wood powder, negative pressure of vacuum dipping 30 ~ 90 minutes, then volatilization removing mixed solvent, drying at 30 ~ 60 DEG C, then at 100 ~ 150 DEG C, namely solidification obtains prepolymer product in 12 ~ 48 hours; (3) carbonizing reduction: under reducing atmosphere, to be placed at high temperature reaction stove 700 ~ 1400 DEG C roasting 1 ~ 7 hour, then to cool, grinds by step (2) gained prepolymer product, level hole tungsten carbide/carbon composite.
2. the preparation method of a kind of level hole according to claim 1 tungsten carbide/carbon composite, it is characterized in that, in the mixed solution described in step (1), the mass ratio of water and ethanol is 1:(1 ~ 20); The mass ratio of template and mixed solution is 1:(20 ~ 100); The mass ratio of tungsten source and carbon source is 1:(1 ~ 15); The mass ratio of carbon source and mixed solution is 1:(6 ~ 40).
3. the preparation method of a kind of level hole according to claim 1 and 2 tungsten carbide/carbon composite, is characterized in that, the tungsten source described in step (1) is one or more mixtures in wolframic acid, tungstates, metatungstate.
4. the preparation method of a kind of level hole according to claim 1 and 2 tungsten carbide/carbon composite, is characterized in that, the wood powder described in step (2) is arbitrary timber elaboration products; Wherein, the mass ratio of wood powder and precursor solution is 1:(1 ~ 8).
5. the preparation method of a kind of level hole according to claim 1 tungsten carbide/carbon composite, is characterized in that, the reducing atmosphere described in step (3) is throughput is 20 ~ 80mL/min, volume ratio is 1:(1 ~ 6) hydrogen and the gaseous mixture of nitrogen.
6. the preparation method of a kind of level hole according to claim 1 tungsten carbide/carbon composite, it is characterized in that, the temperature in step (3) is 900 ~ 1200 DEG C.
7. the preparation method of a kind of level hole according to claim 1 tungsten carbide/carbon composite, it is characterized in that, the time in step (3) is 3 ~ 6 hours.
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