CN102658187A - Method for preparing vermicular mesoporous tungsten carbide/charcoal composite material - Google Patents
Method for preparing vermicular mesoporous tungsten carbide/charcoal composite material Download PDFInfo
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Abstract
The invention discloses a method for preparing a vermicular mesoporous tungsten carbide/charcoal composite material. The method comprises the following steps: (1) dissolving a surfactant in a mixed solution of ethanol and water, sequentially adding a carbon source and a tungsten source, and violently stirring for 15 to 60 minutes to form water-in-oil microemulsion; (2) putting the microemulsion obtained in the step (1) in an open utensil, evaporating at the temperature of between 30 and 60 DEG C to remove a mixed solvent, and curing at the temperature of between 100 and 150DEG C for 6 to 48 hours to obtain a solid product; and (3) in reducing atmosphere, calcining the solid product obtained in the step (2) at the temperature of between 700 and 1,600DEG C for 1 to 7 hours, and cooling and grinding to obtain the vermicular mesoporous tungsten carbide/charcoal composite material. The method has simple steps, quick and time-saving; and the prepared vermicular mesoporous tungsten carbide/charcoal composite material has the characteristics of vermicular pores, uniform distribution of tungsten carbide particles, single phase and the like.
Description
Technical field
The present invention relates to a kind of preparation method of worm meso-porous tungsten carbide/carbon composite, the invention still further relates to the preparation of catalyst in electrochemistry and the organic synthesis or catalyst carrier.
Background technology
Research shows that tungsten carbide has the catalytic activity of similar platinum, physics and stable chemical performance, and cheap.Along with people's is to the attention of clean energy resource, and tungsten carbide is at catalytic field, and for example the application of aspects such as DMFC, catalytic hydrogen evolution, super-capacitor and catalytic desulfurization has caused scientist's extensive concern.In electrochemical field, tungsten carbide is that as the advantage of anode catalyst it not only has catalytic performance and can replace precious metals such as platinum, palladium, and is difficult for being poisoned by carbon monoxide.Thereby tungsten carbide catalyst can partly replace or save precious metals such as platinum, palladium to a certain extent, and it has a extensive future.
The tungsten carbide traditional preparation method is " solid reaction process ", and it gets 1600 ℃ of pyroreactions through tungsten powder and powdered carbon.The tungsten carbide particle that makes in this way is prone to reunite, specific area is little, can only satisfy the metallurgical industry needs, can not effectively bring into play its catalytic action.And in electrochemical applications, the porous charcoal carrier plays an important role to catalytic activity and the stability that improves tungsten carbide.Possesses excellent conducting performance mainly due to the charcoal carrier; The high-specific surface area of charcoal carrier helps the high degree of dispersion of tungsten carbide; The open pore passage structure of charcoal carrier helps " mass transfer " process of catalytic reaction; The chemistry of charcoal carrier, physical stability are good, are applicable to various applied environments.Therefore, the preparation of tungsten carbide/carbon composite has in recent years caused scientific research personnel's concern with application.
Up to now, the preparation method of the tungsten carbide/carbon composite of bibliographical information is confined to " infusion process " basically (Chem. Commun. 2005,31,4408 for H. Meng, etc; Q. Zhu, etc, J. Power Sources, 2009,193,495), " hydro-thermal method " (Y. Wang, etc, J. Mater. Chem., 2009,19,6149), " hard template method " (Small 2009,5 for Z. X. Wu, etc, 2738; Y. H. Zhang, etc, Chem. Commun., 2010,46,862) etc., all there is deficiency in various degree.Therefore, how to adopt simple method to prepare tungsten carbide good dispersion, thing is mutually single, the aperture is adjustable mesoporous tungsten carbide/carbon composite, have important scientific meaning and application prospects.
Summary of the invention
The object of the present invention is to provide a kind of simple " soft template " method to prepare worm meso-porous tungsten carbide/carbon composite.It is simple that this method prepares process, and the mesoporous tungsten carbide/carbon composite of preparation has characteristics such as vermiform duct, tungsten carbide particle are evenly distributed, thing is mutually single.This composite can be widely used in various electrochemical catalysis, sensor and organic synthesis etc., especially can be directly as the catalyst or the carrier of methanol fuel cell, to reach the purpose of practicing thrift platinum catalyst.
The technical problem that the present invention solved adopts following technical scheme to realize:
A kind of preparation method of worm meso-porous tungsten carbide/carbon composite comprises the steps:
(1) surfactant is dissolved in the mixed solution of second alcohol and water, adds carbon source and tungsten source then successively, vigorous stirring 15～60 minutes forms " Water-In-Oil " microemulsion;
(2) step (1) gained microemulsion is placed uncovered vessel, evaporate down at 30～60 ℃ and remove mixed solvent, curing obtained solid product in 6～48 hours under 100～150 ℃ then;
(3) under reducing atmosphere, step (2) gained solid product 700～1600 ℃ of down calcinings 1～7 hour, is cooled off then, grinds and obtain worm meso-porous tungsten carbide/carbon composite.
The mass ratio of water and ethanol is 1 in the described mixed solution: (1～10); The mass ratio of surfactant and mixed solution is 1: (50～200); The mass ratio of tungsten source and carbon source is 1: (1～20); The mass ratio of carbon source and mixed solution is 1: (10～40).
Described surfactant is a kind of among non-ionic surface active agent P123, the F127.
Described carbon source is A rank phenolic aldehyde prepolymer, carbamide prepolymer (M
w<500) a kind of in.Described prepolymer can pass through known technology: prepare like the base catalyzed reactions between phenolic aldehyde and formaldehyde or melamine and the formaldehyde.
Described tungsten source is one or more mixtures in the oxide, wolframic acid, tungstates, metatungstate of tungsten.Described tungsten source is water-soluble, is insoluble to ethanol, or is slightly soluble in ethanol.
Described reducing atmosphere is that throughput is that 20～60mL/min, volume ratio are 1: the hydrogen of (1～6) and the gaseous mixture of nitrogen.
Temperature in the step (3) is preferably 900～1200 ℃.
Time in the step (3) is preferably 3～5 hours.
The present invention compares with existing " infusion process ", " hydro-thermal method ", " hard template method ", and have following advantage: the present invention has mixed " microemulsion " process on the basis of " solvent evaporates is induced self-assembly method ", develop a kind of new synthetic method.It is advantageous that the formation of " Water-In-Oil " microemulsion, help the even distribution of tungsten carbide particle in the charcoal carrier, do not influence again and induce the volatilization self assembling process, can generate the vermiform mesoscopic structure; " original position " generates tungsten carbide particle simultaneously, is difficult for stopping up the duct of raw material of wood-charcoal material; Secondly, carbon source and tungsten source need not be precipitated out from solution in phase-splitting, are convenient to regulate the theoretical molar ratio in carbon source and tungsten source, thereby obtain the mutually single mesoporous tungsten carbide/carbon composite of thing.Step of the present invention is simple, saves time fast, and carbon source and tungsten source presoma range of choice are wide, and the mesoporous tungsten carbide/carbon composite of preparation has characteristics such as vermiform duct, tungsten carbide particle are evenly distributed, thing is mutually single.This composite can be widely used in various electrochemical catalysis, sensor and organic synthesis etc., especially can be used as the catalyst or the carrier of DMFC, to reach the target of practicing thrift platinum catalyst.
Description of drawings
Fig. 1 is the wide-angle x-ray diffraction figure of worm meso-porous tungsten carbide/carbon composite.
Fig. 2 is the transmission electron microscope picture of worm meso-porous tungsten carbide/carbon composite.
Fig. 3 is and the corresponding constituency of Fig. 2 ability spectrogram.
Fig. 4 is the N of worm meso-porous tungsten carbide/carbon composite
2Adsorption-desorption curve and corresponding pore size distribution curve.
The specific embodiment
Below in conjunction with embodiment technical scheme of the present invention is done further to describe, but be not subject to these embodiment.
Embodiment 1
Under 40 ℃; Taking by weighing 10.0g surfactant F127 is dissolved in the mixed solution of 120.0g ethanol and 30.0 g water fully; Add 5.0 g carbamide performed polymers and 2.5 g ammonium metatungstate aqueous solutions (wt.%=33.3) then, vigorous stirring 30min obtains " Water-In-Oil " microemulsion.Above-mentioned microemulsion is placed uncovered vessel, leave standstill 24h under 40 ℃ to obtain colourless dope, place baking oven then, 105 ℃ solidify 12h down and obtain the resin-like material.Grind to form fragment then, place tube furnace, feeding throughput is that 30 mL/min, volume ratio are the nitrogen of 3:1 and the gaseous mixture of hydrogen, is warming up to 900 ℃ gradually, calcines 3 hours, and temperature programming speed is 5 ℃/min.Naturally cooling is ground then, promptly obtains worm meso-porous tungsten carbide/carbon composite.
Under 40 ℃; Taking by weighing 10.0g surfactant F127 is dissolved in the mixed solution of 100.0g ethanol and 50.0 g water fully; Add 5.0 g carbamide performed polymers and 5.0 g ammonium metatungstate aqueous solutions (wt.%=33.3) then, vigorous stirring 30min obtains " Water-In-Oil " microemulsion.Above-mentioned microemulsion is placed uncovered culture dish, leave standstill 24h under 40 ℃ to obtain colourless viscous liquid, place baking oven then, 105 ℃ solidify 48h down and obtain the resin-like material.Grind to form fragment then, place tube furnace, feeding throughput is that 40 mL/min, volume ratio are the nitrogen of 3:1 and the gaseous mixture of hydrogen, is warming up to 1000 ℃ gradually, calcines 3 hours, and temperature programming speed is 5 ℃/min.Naturally cooling is ground then, promptly obtains worm meso-porous tungsten carbide/carbon composite.
Embodiment 3
Under 40 ℃; Taking by weighing 8.0g surfactant P123 is dissolved in the mixed solution of 100.0g ethanol and 20.0 g water fully; Add 5.0 g P-F performed polymers and 2.0 g ammonium metatungstate aqueous solutions (wt.%=33.3) then, vigorous stirring 30min obtains " Water-In-Oil " microemulsion.Above-mentioned microemulsion is placed uncovered culture dish, leave standstill 24h under 40 ℃ to obtain colourless viscous liquid, place baking oven then, 105 ℃ solidify 24h down and obtain the resin-like material.Grind to form fragment then, place tube furnace, feeding throughput is that 30 mL/min, volume ratio are the nitrogen of 3:1 and the gaseous mixture of hydrogen, is warming up to 900 ℃ gradually, calcines 3 hours, and temperature programming speed is 5 ℃/min.Naturally cooling is ground then, promptly obtains worm meso-porous tungsten carbide/carbon composite.
Embodiment 4
Under 40 ℃; Taking by weighing 8.0g surfactant P123 is dissolved in the mixed solution of 100.0g ethanol and 50.0 g water fully; Add 5.0 g P-F performed polymer performed polymers and 5.0 g ammonium metatungstate aqueous solutions (wt.%=33.3) then, vigorous stirring 30min obtains " Water-In-Oil " microemulsion.Above-mentioned microemulsion is placed uncovered culture dish, leave standstill 24h under 40 ℃ to obtain colourless viscous liquid, place baking oven then, 105 ℃ solidify 24h down and obtain the resin-like material.Grind to form fragment then, place tube furnace, feeding throughput is that 40 mL/min, volume ratio are the nitrogen of 3:1 and the gaseous mixture of hydrogen, is warming up to 1000 ℃ gradually, calcines 3 hours, and temperature programming speed is 5 ℃/min.Naturally cooling is ground then, promptly obtains worm meso-porous tungsten carbide/carbon composite.
More than show and described basic principle of the present invention, 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; That describes in the foregoing description and the specification just explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and equivalent thereof.
Claims (8)
1. the preparation method of a worm meso-porous tungsten carbide/carbon composite is characterized in that, comprises the steps:
(1) surfactant is dissolved in the mixed solution of second alcohol and water, adds carbon source and tungsten source then successively, vigorous stirring 15～60 minutes forms " Water-In-Oil " microemulsion;
(2) step (1) gained microemulsion is placed uncovered vessel, evaporate down at 30～60 ℃ and remove mixed solvent, curing obtained solid product in 6～48 hours under 100～150 ℃ then;
(3) under reducing atmosphere, step (2) gained solid product 700～1600 ℃ of down calcinings 1～7 hour, is cooled off then, grinds and obtain worm meso-porous tungsten carbide/carbon composite.
2. the preparation method of a kind of worm meso-porous tungsten carbide/carbon composite according to claim 1 is characterized in that, the mass ratio of water and ethanol is 1 in the described mixed solution: (1～10); The mass ratio of surfactant and mixed solution is 1: (50～200); The mass ratio of tungsten source and carbon source is 1: (1～20); The mass ratio of carbon source and mixed solution is 1: (10～40).
3. the preparation method of a kind of worm meso-porous tungsten carbide/carbon composite according to claim 1 and 2 is characterized in that, described surfactant is a kind of among non-ionic surface active agent P123, the F127.
4. the preparation method of a kind of worm meso-porous tungsten carbide/carbon composite according to claim 1 and 2 is characterized in that, described carbon source is a kind of in A rank phenolic aldehyde prepolymer, the carbamide prepolymer.
5. the preparation method of a kind of worm meso-porous tungsten carbide/carbon composite according to claim 1 and 2 is characterized in that, described tungsten source is one or more mixtures in the oxide, wolframic acid, tungstates, metatungstate of tungsten.
6. the preparation method of a kind of worm meso-porous tungsten carbide/carbon composite according to claim 1 is characterized in that, described reducing atmosphere is that throughput is that 20～60mL/min, volume ratio are 1: the hydrogen of (1～6) and the gaseous mixture of nitrogen.
7. the preparation method of a kind of worm meso-porous tungsten carbide/carbon composite according to claim 1 is characterized in that, the temperature in the step (3) is 900～1200 ℃.
8. the preparation method of a kind of worm meso-porous tungsten carbide/carbon composite according to claim 1 is characterized in that, the time in the step (3) is 3～5 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103381368A (en) * | 2013-05-16 | 2013-11-06 | 中南林业科技大学 | Hierarchical porous tungsten carbide/charcoal composite material and its preparation method |
| CN105858663A (en) * | 2016-06-08 | 2016-08-17 | 太原理工大学 | Preparation method of bowl-shaped carbon-molybdenum carbide composite material |
| CN106430209A (en) * | 2016-09-19 | 2017-02-22 | 中冶东方工程技术有限公司 | Preparing method of mesoporous nano tungsten carbide and product |
| CN108899559A (en) * | 2018-06-19 | 2018-11-27 | 华东师范大学 | A kind of anode of fuel cell hydrogen oxidation catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101869853A (en) * | 2010-05-28 | 2010-10-27 | 中山大学 | Ordered mesoporous carbon/tungsten carbide composite material and supported catalyst thereof and preparation method thereof |
| US20110189504A1 (en) * | 2010-02-01 | 2011-08-04 | Los Alamos National Security, Llc | Preparation of metal carbide films |
-
2012
- 2012-05-10 CN CN2012101434456A patent/CN102658187A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110189504A1 (en) * | 2010-02-01 | 2011-08-04 | Los Alamos National Security, Llc | Preparation of metal carbide films |
| CN101869853A (en) * | 2010-05-28 | 2010-10-27 | 中山大学 | Ordered mesoporous carbon/tungsten carbide composite material and supported catalyst thereof and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《中南林业科技大学学报》 20120131 XIA Liao-yuan et al "Synthesis and characterization of mesoporous tungsten carbide/carbon nanocomposites" 摘要，第1.1，1.2节 1-8 第32卷, 第1期 * |
| XIA LIAO-YUAN ET AL: ""Synthesis and characterization of mesoporous tungsten carbide/carbon nanocomposites"", 《中南林业科技大学学报》, vol. 32, no. 1, 31 January 2012 (2012-01-31) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103381368A (en) * | 2013-05-16 | 2013-11-06 | 中南林业科技大学 | Hierarchical porous tungsten carbide/charcoal composite material and its preparation method |
| CN103381368B (en) * | 2013-05-16 | 2016-01-20 | 中南林业科技大学 | A kind of level hole tungsten carbide/carbon composite and preparation method thereof |
| CN105858663A (en) * | 2016-06-08 | 2016-08-17 | 太原理工大学 | Preparation method of bowl-shaped carbon-molybdenum carbide composite material |
| CN105858663B (en) * | 2016-06-08 | 2017-11-28 | 太原理工大学 | A kind of preparation method of bowl-shape carbon and carbonization molybdenum composite material |
| CN106430209A (en) * | 2016-09-19 | 2017-02-22 | 中冶东方工程技术有限公司 | Preparing method of mesoporous nano tungsten carbide and product |
| CN108899559A (en) * | 2018-06-19 | 2018-11-27 | 华东师范大学 | A kind of anode of fuel cell hydrogen oxidation catalyst and preparation method thereof |
| CN108899559B (en) * | 2018-06-19 | 2021-10-12 | 华东师范大学 | Fuel cell anode hydrogen oxidation catalyst and preparation method thereof |
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Application publication date: 20120912 |