CN106920975B - A kind of preparation method of three-dimensional network shape tungsten carbide-carbon nano tube compound material - Google Patents

A kind of preparation method of three-dimensional network shape tungsten carbide-carbon nano tube compound material Download PDF

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CN106920975B
CN106920975B CN201710233351.0A CN201710233351A CN106920975B CN 106920975 B CN106920975 B CN 106920975B CN 201710233351 A CN201710233351 A CN 201710233351A CN 106920975 B CN106920975 B CN 106920975B
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tungsten
carbon
microwave
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acetylene
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CN106920975A (en
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施梅勤
黄丽珍
陈赵扬
江叶坤
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Zhejiang University of Technology ZJUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a kind of preparation methods of three-dimensional network shape tungsten carbide-carbon nano tube compound material: tungsten source being dissolved in solvent in microwave tube, after mixing evenly, microwave tube is placed in microwave synthesizer, 40~60min is reacted at 160~180 DEG C, obtains the W with oxygen defect18O49；By the W18O49It is placed in tube furnace, under carbon source atmosphere, is carbonized at 700~900 DEG C, is then cooled to room temperature under nitrogen protection atmosphere, obtains WC-CNTs particle.Operation of the present invention is simple and easy, using the tungsten oxide with oxygen defect as presoma, promotes atom diffusion, be conducive to carburizing process, the in-situ growing carbon nano tube on tungsten base simultaneously, it forms using WC little particle as fulcrum, carbon pipe is the complex three-dimensional network structure of skeleton, can effectively be dispersed WC particle, it ensure that WC and Pt possess more contact surfaces, the whole electric conductivity for promoting composite material, preferably performance three's collective effect, improve electro-catalysis effect.

Description

A kind of preparation method of three-dimensional network shape tungsten carbide-carbon nano tube compound material
(1) technical field:
The present invention relates to a kind of preparation methods of three-dimensional network shape tungsten carbide-carbon nano tube compound material.
(2) background technique:
Direct methanol fuel cell (DMFC) battery structure is simple, specific energy density with higher, and fuel methanol Abundance is easy to transport and store.This makes direct methanol fuel cell be highly suitable for vehicle-mounted and portable device electricity Source becomes the hot spot studied instantly.Catalyst used in fuel cell is based on Pt and Pt system noble metal catalyst, but Pt system Precious Metals Resources are rare, expensive, and Methanol Anode oxidation product CO easily makes its poisoning.Above-mentioned these problems make methanol Fuel cell can not carry out large-scale commercial applications and promote, and seriously constrain the application and development of fuel cell.Therefore, Non-precious metal catalyst is developed, the catalytic performance of fuel-cell catalyst is improved, catalyst cost is reduced and is of great significance.
Early in 1970s, just there is scientist to find that tungsten carbide (WC) has and electronic shell knot as Pt race metal phase Structure, then some researches show that catalytic activity of the tungsten carbide with eka-platinium in many reactions, while having the characteristic of CO tolerance catalysts, The stability with higher in acid, alkaline system, good catalytic activity.Though tungsten carbide have eka-platinium catalytic performance and compared with Strong CO tolerance catalysts ability, but its dispersibility is poor, and specific surface area is smaller, easily reunites, and electric conductivity is poor, and catalysis is lived Property is also undesirable, and there are still biggish gaps compared with the noble metal catalysts such as platinum.
Catalyst carrier is also an important factor for influencing catalyst activity.Carbon nanotube (CNTs) is at present in DMFC In the carrier material that is commonly used.Carbon nanotubes is due to possessing superior Electronic Performance, nanoscale tubular structure, big specific surface The features such as long-pending, class graphite multi-layer wall, the dispersibility of supported active component, while strengthening material can be improved well as carrier The electric conductivity of material.It is to improve tungsten carbide to urge that WC-CNTs composite material will be prepared on tungsten carbide nano-particles reinforcement to carbon nanotube Change one of active effective ways.Studies have shown that WC-CNTs composite material is significantly stronger than pure carbonization to the electrocatalysis characteristic of methanol Tungsten.
The method of most common synthesis WC-CNTs composite material has: load method and in-situ synthesis.Load method is first Synthesizing carbon nanotubes, then tungsten carbide is loaded on it.Because carbon nano tube surface micropore is less, lack active sites, Pt noble metal Particle is difficult uniformly to deposit attachment on its surface, and noble metal granule is caused to be reunited.If obtaining preferable dispersibility, usually It needs carbon nanotube in strong oxidizing property acid solution (such as dense HNO3/H2SO4) processing, increase the distal opening of its pipe by contact surface Product, while its surface can also be made to generate more active sites (being formed on its surface oxygen-containing functional group) to enhance and metal The effect of grain.Although the mode for carrying out surface oxidation with strong oxidizing property acid solution is fairly simple, its controlling is poor, is difficult Uniform and enough oxygen-containing functional group is generated in the whole surface of CNTs.So that WC is difficult to load on CNTs, even if load Success, load capacity is also seldom and uneven, and easy-sintering during reduction and carbonization.In-situ synthesis is added in tungsten source Catalyst Fe, the catalyst such as Co, Ni, in surface of metal particles situ catalytic synthesizing carbon nanotubes.In-situ synthesis step is simple, CNTs can be directly grown on granular precursor surface, make WC that there is good dispersibility.But the introducing that can be difficult to avoid that Other catalyst impurities.Lee et al. uses W (CO)6It is catalyst, C2H2Carbon is generated by vapour deposition process (CVD) for carbon source to receive Mitron shows that tungsten sill has certain catalytic activity to the synthesis of carbon nanotube.But this method target product is received for carbon Mitron, rather than three-dimensional network shape tungsten carbide-carbon nanotube.And the W (CO) selected in the preparation method6It is expensive, CVD method behaviour Make complexity, there need to be professional equipment.
(3) summary of the invention:
To solve WC material problem easy to reunite in the preparation, not high to methanol oxidation activity, the present invention provides one kind Tungsten carbide-carbon nano tube compound material preparation method.Using the tungsten oxide with oxygen defect as presoma, promote atom Diffusion is formed using WC little particle as fulcrum, and carbon pipe is the complex three-dimensional network structure of skeleton.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of tungsten carbide-carbon nano tube compound material preparation method with three-dimensional net structure of the invention, it is described Method carries out as follows:
(1) tungsten source is dissolved in solvent in microwave tube, after mixing evenly, microwave tube is placed in microwave synthesizer, 160~ 40~60min, after reaction, the post-treated W for obtaining that there is oxygen defect of reaction product are reacted at 180 DEG C18O49；The tungsten Source is WCl6；
(2) by W obtained by step (1)18O49It is placed in tube furnace, under carbon source atmosphere, is carbonized at 700~900 DEG C, so It is cooled to room temperature under nitrogen protection atmosphere afterwards, obtains tungsten carbide-carbon nanotube particulate.
Further, in the step (1), the solvent is dehydrated alcohol.
Further, in the step (1), the volumetric usage of solvent is calculated as 50~200mL/g with tungsten source quality.
Further, in the step (1), 13~15bar of pressure of microwave reaction.
Further, the post-processing approach of the step (1) are as follows: to after reaction, with deionized water and dehydrated alcohol After centrifuge washing, it is put into 50~60 DEG C of vacuum drying ovens dry 6~8h and obtains the W with oxygen defect18O49。
Further, in the step (2), the carbon source is carbon monoxide or acetylene.
Further, in the step (2), carburizing temperature is 900 DEG C, and carbonization time is 180 minutes.
Further, the gas flow of carbon source described in the step (2) is 100mL/min.
Further, when carbon source described in the step (2) is acetylene, the carbon source is using acetylene and hydrogen, argon gas The form of gaseous mixture provide, the acetylene and hydrogen, argon gas volume ratio be 3:3:4.
Further, method of the present invention specifically carries out as follows:
Tungsten source is dissolved in solvent in microwave tube by a, after mixing evenly, microwave tube is placed in microwave synthesizer, at 160 DEG C Reaction product is cooled to room temperature by reaction 60min after reaction, after deionized water and dehydrated alcohol centrifuge washing, is put into Dry 6h obtains the W with oxygen defect in 50 DEG C of vacuum drying ovens18O49；The tungsten source is WCl6, the solvent is dehydrated alcohol, institute It states solvent volume dosage and 100mL/g, the pressure 15bar of the microwave reaction is calculated as with tungsten source quality；
B is by W obtained by step a18O49It is placed in tube furnace, under carbon source atmosphere, in 900 DEG C of carbonization 180min, then in nitrogen It is cooled to room temperature under gas shielded atmosphere, obtains tungsten carbide-carbon nanotube particulate；When the carbon source is acetylene, using acetylene and hydrogen The gaseous mixture of gas, argon gas, the acetylene: hydrogen: argon gas volume ratio=30:30:40；The flow of the gaseous mixture is 100mL/ min。
Compared with prior art, the beneficial effects of the present invention are:
(1) W is prepared using microwave-assisted thermal reduction substitution conventional hydrothermal method18O49Presoma reduces the reaction time；
(2) using there is the tungsten oxide of oxygen defect as presoma, promote atom diffusion, be conducive to carburizing process, together When on tungsten base in-situ growing carbon nano tube, tungsten carbide-carbon nano-tube material of the polymolecularity of morphology controllable is prepared.
(3) particularity of composite material of the invention is, carbon nanotube is not only grow on material surface, while in material Fissure hole in also have the growth of carbon nanotube on the active metal face that exposes, sample is strutted, is formd with WC little particle For fulcrum, carbon pipe is the complex three-dimensional network structure of skeleton.This three-dimensional net structure can effectively be divided WC particle It dissipates, ensure that WC and Pt possess more contact surfaces.Such structure can also make carbon nanotube while touch WC and Pt, whole Body promotes the electric conductivity of composite material, preferably performance three's collective effect, improves electro-catalysis effect.
(4) Detailed description of the invention
Fig. 1 is the XRD diagram of different carburizing temperature WC-CNTs in embodiment 1,2,3.
Fig. 2 is the SEM figure that difference carburizing temperature WC-CNTs amplifies 50000 times in embodiment 1,2,3.
Fig. 3 is the TEM figure of different carburizing temperature WC-CNTs in embodiment 1,2,3.
Fig. 4 is the chemical property figure of different carburizing temperature Pt/WC-CNTs in embodiment 1,2,3.
Fig. 5 is the chemical property figure of the Pt/WC-CNTs of different tungsten source quality in embodiment 3,4,5.
Fig. 6 is the chemical property figure of the Pt/WC-CNTs of different carbon source in embodiment 3,6.
(5) specific embodiment
Below with reference to specific example, invention is further described in detail:
Embodiment 1
1. weighing 0.2g WCl in glove box6, it is dissolved in 20mL dehydrated alcohol, is put into after mixing evenly in Initiator In EXP microwave synthesizer, the reaction pressure of microwave reaction is 15bar, reacts 1h at 160 DEG C.To after reaction, be cooled to Room temperature is put into 50 DEG C of vacuum drying ovens 6 hours dry after deionized water and dehydrated alcohol centrifuge washing 3 times.
2. the sample after above-mentioned drying is put into tube furnace, calcined 3 hours for 700 DEG C under 100mL/min CO atmosphere, Then it is cooled to room temperature under nitrogen protection atmosphere, obtains WC-CNTs particle, be labeled as WC-CNTs-700.
It it can be concluded that, is 31.5 ° in 2 θ diffraction Angle Positions by the XRD diagram of WC-CNTs-700 shown in figure 1A, 35.6 °, 48.3 °, 64.0 °, 73.1 °, 75.5 ° of diffraction maximum is respectively belonging to (001) of WC, (100), (101), (110), (111), (200) crystal face (01-072-0097).Show that the material is made of pure phase WC, crystallinity is good.
W as shown in Figure 218O49(a), the SEM figure of WC-CNTs-700 (b) is as can be seen that W18O49There is elongated receive on surface Rice is rodlike, and whole pattern is sea urchin shape structure.WC-CNTs-700 and W18O49Pattern it is almost the same, the nanometer rods on surface are in carbon Short and thick nano bar-shape is remained as after change, overall structure is slightly shunk than presoma.
Embodiment 2
1. weighing 0.2g WCl in glove box6, it is dissolved in 20mL dehydrated alcohol, is put into after mixing evenly in Initiator In EXP microwave synthesizer, the reaction pressure of microwave reaction is 15bar, is reacted 1 hour at 160 DEG C.It is cold to after reaction But it is put into 50 DEG C of vacuum drying ovens 6 hours dry after deionized water and dehydrated alcohol centrifuge washing 3 times to room temperature.
2. the sample after above-mentioned drying is put into tube furnace, calcined 3 hours for 800 DEG C under 100mL/min CO atmosphere, Then it is cooled to room temperature under nitrogen protection atmosphere, obtains the WC-CNTs particle for growing carbon nanotube.Labeled as WC-CNTs- 800。
In the XRD diagram of the WC-CNTs-800 as shown in Figure 1B it can be concluded that, 2 θ diffraction Angle Positions be 31.5 °, 35.6 °, 48.3 °, 64.0 °, 73.1 °, 75.5 ° of diffraction maximum is respectively belonging to (001) of WC, (100), (101), (110), (111), (200) crystal face (01-072-0097).Show that the material is made of pure phase WC, crystallinity is good.Compared with WC-CNTs-700, Peak intensity enhancing.
The SEM of WC-CNTs-800 (c) as shown in Figure 2 schemes as can be seen, observing that a small amount of carbon is received in microsphere surface Mitron generate, but catalyst granules still with W18O49Pattern it is almost the same.
Embodiment 3
1. weighing 0.2g WCl in glove box6, it is dissolved in 20mL dehydrated alcohol, is put into after mixing evenly in Initiator In EXP microwave synthesizer, the reaction pressure of microwave reaction is 15bar, reacts 1h at 160 DEG C.To after reaction, be cooled to Room temperature is put into 50 DEG C of vacuum drying ovens 6 hours dry after deionized water and dehydrated alcohol centrifuge washing 3 times.
2. the sample after above-mentioned drying is put into tube furnace, 900 DEG C calcining 3 hours under 100mL/minCO atmosphere, so It is cooled to room temperature under nitrogen protection atmosphere afterwards, obtains the WC particle for growing carbon nanotube.Labeled as WC-CNTs-900.
In the XRD diagram of the WC-CNTs-900 as shown in Fig. 1 C it can be concluded that, 2 θ diffraction Angle Positions be 31.5 °, 35.6 °, 48.3 °, 64.0 °, 73.1 °, 75.5 ° of diffraction maximum is respectively belonging to (001) of WC, (100), (101), (110), (111), (200) crystal face (01-072-0097).Show that the material is made of pure phase WC, crystallinity is good.
The SEM figure of WC-CNTs-900 (d) as shown in Figure 2 can be seen that carbon pipe is not only grown on the surface of the material, while It is grown on the active metal face exposed in the fissure hole of material, sample is strutted, formed using WC little particle as fulcrum, carbon pipe is The complex three-dimensional network structure of skeleton.
To the WC-CNTs-700 of above-mentioned preparation, WC-CNTs-800, WC-CNTs-900 material load 10wt% platinum.Fig. 3 a It is respectively the TEM figure that Pt/WC-CNTs-700 amplifies 75000 and 295000 times with 3b, Fig. 3 c and 3d are respectively Pt/WC-CNTs- The TEM figure of 800 75000 and 295000 times of amplifications, Fig. 3 e and 3f are respectively that Pt/WC-CNTs-900 amplifies 15000 and 590000 times TEM figure, from Fig. 3 a, 3c, 3e as can be seen that Pt/WC-CNTs-700 there is no the generation of carbon nanotube, Pt/WC-CNTs- 800 microsphere surfaces observe that a small amount of carbon nanotube generates, but there is no spread out catalyst granules.Carbon pipe will Pt/WC-CNTs-900 is strutted, and is formd using WC little particle as fulcrum, and carbon pipe is the complex three-dimensional network structure of skeleton.This with not SEM spectrum result before carrying platinum is consistent.From 3f it can be seen that the lattice fringe of Pt and WC is closely bound up and is formed different Matter interface.The Mapping that Fig. 3 g is Pt/WC-CNTs-900 schemes, it can be seen from the figure that tri- kinds of elements of C, W and Pt are in composite wood It is uniformly distributed in material.
To the Pt/WC-CNTs-700 of above-mentioned preparation, Pt/WC-CNTs-800, its electricity of Pt/WC-CNTs-900 testing of materials Chemical property.Fig. 4 is Pt/WC-CNTs-700, the electrochemistry of Pt/WC-CNTs-800, Pt/WC-CNTs-900 and business Pt/C Performance map.Fig. 4 a is above-mentioned each catalyst in 0.5M H2SO4Cyclic voltammogram in solution, there it can be seen that Pt/WC- CNTs-700, Pt/WC-CNTs-800, Pt/WC-CNTs-900 and business Pt/C show typical hydrogen adsorption desorption peak.Fig. 4 b It is above-mentioned each catalyst in 0.5M H2SO4With 0.5M CH3Cyclic voltammogram in OH, current density are respectively 900mA mg- 1Pt,900mA mg-1Pt,1350mA mg-1Pt,480mA mg-1Pt, the Pt/WC-CNTs catalyst series of this method preparation Current density is above business Pt/C, and Fig. 4 c is each catalyst in 0.5M H2SO4Carbon monoxide De contamination curve in solution, room Under temperature, sweep speed 20mV/s, it can be seen from the figure that each Pt/WC-CNTs catalyst series play spike potential and spike potential It is above business Pt/C.Wherein spike potential (0.53V) of Pt/WC-CNTs-900 catalyst and spike potential (0.64V) are than business Pt/C's plays spike potential (0.57V) and the negative shifting 40mV and 30mV of spike potential (0.67V).
Fig. 4 d is each catalyst in 0.5M H2SO4With 0.5M CH3Chronoa mperometric plot in OH, step potential are 0.65V, temperature are 50 DEG C.It can be seen from the figure that the current density after each catalyst stabilization is also above business Pt/C.
Embodiment 4
1. weighing 0.1g WCl in glove box6, it is dissolved in 20mL dehydrated alcohol, is put into Initiator after mixing evenly In EXP microwave synthesizer, the reaction pressure of microwave reaction is 15bar, reacts 1h at 160 DEG C.To after reaction, be cooled to Room temperature is put into 50 DEG C of vacuum drying ovens 6 hours dry after deionized water and dehydrated alcohol centrifuge washing 3 times.
2. the sample after above-mentioned drying is put into tube furnace, calcined 3 hours for 900 DEG C under 100mL/min CO atmosphere, Then it is cooled to room temperature under nitrogen protection atmosphere, obtains WC particle, be labeled as WC-0.1-900.
Embodiment 5
1. weighing 0.4g WCl in glove box6, it is dissolved in 20mL dehydrated alcohol, is put into Initiator after mixing evenly In EXP microwave synthesizer, the reaction pressure of microwave reaction is 15bar, reacts 1h at 160 DEG C.To after reaction, be cooled to Room temperature is put into 50 DEG C of vacuum drying ovens 6 hours dry after deionized water and dehydrated alcohol centrifuge washing 3 times.
2. the sample after above-mentioned drying is put into tube furnace, 900 DEG C calcining 3 hours under 100mL/minCO atmosphere, so It is cooled to room temperature under nitrogen protection atmosphere afterwards, obtains WC particle, be labeled as WC-0.4-900.
To the WC-0.1-900 of above-mentioned preparation, WC-0.2-900, WC-0.4-900 material load 10wt% platinum is labeled as Pt/WC-0.1-900,Pt/WC-0.2-900,Pt/WC-0.4-900.Fig. 5 is Pt/WC-0.1-900, Pt/WC-0.2-900, The chemical property figure of Pt/WC-0.4-900 and business Pt/C.Fig. 5 a is above-mentioned each catalyst in 0.5M H2SO4Following in solution Ring voltammogram, there it can be seen that Pt/WC-0.1-900, Pt/WC-0.2-900, Pt/WC-0.4-900 are shown typically Hydrogen adsorption desorption peak.Fig. 5 b is above-mentioned each catalyst in 0.5M H2SO4With 0.5M CH3Cyclic voltammogram in OH.Current density point It Wei not 900mA mg-1Pt,1350mA mg-1Pt,600mA mg-1Pt, 480mA mg-1Pt is prepared with the tungsten chloride of different quality The current densities of Pt/WC catalyst series be above business Pt/C.From take-off potential, Pt/WC-0.1-900, Pt/WC- The spike potential that rises of 0.2-900, Pt/WC-0.4-900 are all born than business Pt/C, and methanol is easier to be oxidized.Each catalyst of Fig. 5 c exists 0.5M H2SO4With 0.5M CH3Chronoa mperometric plot in OH, step potential 0.65V, temperature are 50 DEG C.It can from figure Out, due to the quick charge of electric double layer, so that the initial current of catalyst is relatively high, within the incipient several hundred seconds time, Their current density is all rapid decay, and with the progress of reaction, the electric current of catalyst tends towards stability, but Pt/ WC-0.2-900 sample ratio Pt/WC-0.1-900 and Pt/WC-0.4-900 decays slowly, and when being finally at steady state, The current density that Pt/WC-0.2-900 is kept is also than big on Pt/WC-0.1-900, Pt/WC-0.4-900 and commercialization Pt/C.
Fig. 5 d is each catalyst in 0.5M H2SO4Carbon monoxide De contamination curve in solution, at room temperature, sweep speed is 20mV/s, as can be seen from the figure the spike potential of each Pt/WC catalyst series and spike potential are above business Pt/C.Show CO It is easier to be oxidized removing on Pt/WC catalyst series；Meanwhile from peak current as can be seen that Pt/WC-0.2-900 peak current It is higher than the peak current of business Pt/C, it can adsorb and handle more CO, to expose more platinum active surfaces.
Embodiment 6
1. weighing 0.2g WCl in glove box6, it is dissolved in 20mL dehydrated alcohol, is put into Initiator after mixing evenly In EXP microwave synthesizer, the reaction pressure of microwave reaction is 15bar, reacts 1h at 160 DEG C.To after reaction, be cooled to Room temperature is put into 50 DEG C of vacuum drying ovens 6 hours dry after deionized water and dehydrated alcohol centrifuge washing 3 times.
2. the sample after above-mentioned drying is put into tube furnace, in acetylene: hydrogen: (total under argon gas=30:30:40 atmosphere It 100mL/min) calcines 3 hours for 900 DEG C, is then cooled to room temperature under nitrogen protection atmosphere, obtains WC particle, be labeled as WC- 0.2-C2H2。
To the WC-0.2-C of above-mentioned preparation2H210wt% platinum is loaded with WC-0.2-CO prepared by embodiment 3, is labeled as Pt/ WC-0.2-C2H2,Pt/WC-0.2-CO.Fig. 6 is Pt/WC-0.2-C2H2, Pt/WC-0.2-CO, the chemical property of business Pt/C Figure.Fig. 6 a is above-mentioned each catalyst in 0.5M H2SO4Cyclic voltammogram in solution, there it can be seen that WC-0.2-CO is showed The hydrogen adsorption desorption peak of typical Pt out, Pt/WC-0.2-C2H2The less obvious Fig. 6 b in hydrogen adsorption desorption peak is that above-mentioned each catalyst exists 0.5M H2SO4With 0.5M CH3Cyclic voltammogram in OH is from peak current, the sample P t/WC-0.2-CO of CO atmosphere carbonization Peak current density be up to 1300mA/mg, in contrast, Pt/WC-0.2-C2H2Oxidation peak current density it is smaller, in 900mA/ Mg or so is still higher than business Pt/C.From from spike potential, Pt/WC-0.2-C2H2It is similar with Pt/WC-0.2-CO, than commercialization Pt/C is negative.Each catalyst of Fig. 6 c is in 0.5M H2SO4With 0.5M CH3Chronoa mperometric plot in OH, step potential 0.65V, temperature Degree is 50 DEG C.It can be seen from the figure that due to the quick charge of electric double layer, so that the initial current of catalyst is relatively high, In the incipient several hundred seconds time, the current density of their threes is all rapid decay, with the progress of reaction, catalyst Electric current tends towards stability.But Pt/WC-0.2-CO sample ratio Pt/WC-0.2-C2H2Decay slowly, and is being finally at steady state When, the current density that Pt/WC-0.2-CO is kept also compares Pt/WC-0.2-C2H2With it is big on commercial Pt/C.
Fig. 6 d is each catalyst in 0.5M H2SO4Carbon monoxide De contamination curve in solution, at room temperature, sweep speed is 20mV/s, as can be seen from the figure the spike potential of each Pt/WC catalyst series and spike potential are above business Pt/C.Show CO It is easier to be oxidized removing on Pt/WC catalyst series；Meanwhile from peak current as can be seen that Pt/WC-0.2-CO peak current It is higher than the peak current of business Pt/C, it can adsorb and handle more CO, to expose more platinum active surfaces.

Claims (10)

1. a kind of tungsten carbide-carbon nano tube compound material preparation method with three-dimensional net structure, which is characterized in that described Method carries out as follows:
(1) tungsten source is dissolved in solvent in microwave tube, after mixing evenly, microwave tube is placed in microwave synthesizer, 160~180 40~60min, after reaction, the post-treated W for obtaining that there is oxygen defect of reaction product are reacted at DEG C18O49；The tungsten source is WCl6；
(2) by W obtained by step (1)18O49It is placed in tube furnace, under carbon source atmosphere, is carbonized at 700~900 DEG C, then in nitrogen It is cooled to room temperature under gas shielded atmosphere, obtains tungsten carbide-carbon nanotube particulate.
2. the method as described in claim 1, which is characterized in that solvent described in the step (1) is dehydrated alcohol.
3. the method as described in claim 1, which is characterized in that the volumetric usage of step (1) solvent is in terms of the quality of tungsten source For 50~200mL/g.
4. the method as described in claim 1, which is characterized in that 13~15bar of pressure of microwave reaction in the step (1).
5. the method as described in claim 1, which is characterized in that the post-processing approach of the step (1) are as follows: to the end of reacting Afterwards, it obtains lacking with oxygen with after deionized water and dehydrated alcohol centrifuge washing, being put into 50~60 DEG C of vacuum drying ovens dry 6~8h Sunken W18O49。
6. the method as described in claim 1, which is characterized in that carbon source described in the step (2) is carbon monoxide or acetylene.
7. the method as described in claim 1, which is characterized in that carburizing temperature described in the step (2) is 900 DEG C, carbonization Time is 180 minutes.
8. method as claimed in claim 6, which is characterized in that the gas flow of carbon source described in the step (2) is 100mL/min。
9. the method as described in claim 1, which is characterized in that when carbon source described in the step (2) is acetylene, the carbon Source using acetylene and hydrogen, argon gas gaseous mixture in the form of provide, the volume ratio of the acetylene and hydrogen, argon gas is 3:3:4.
10. the method as described in claim 1, which is characterized in that the method carries out as follows:
Tungsten source is dissolved in solvent in microwave tube by a, after mixing evenly, microwave tube is placed in microwave synthesizer, is reacted at 160 DEG C Reaction product is cooled to room temperature by 60min after reaction, after deionized water and dehydrated alcohol centrifuge washing, is put into 50 DEG C Dry 6h obtains the W with oxygen defect in vacuum drying oven18O49；The tungsten source is WCl6, the solvent is dehydrated alcohol, described molten Agent volumetric usage is calculated as 100mL/g, the pressure 15bar of the microwave reaction with tungsten source quality；
B is by W obtained by step a18O49It is placed in tube furnace, under carbon source atmosphere, in 900 DEG C of carbonization 180min, is then protected in nitrogen It is cooled to room temperature under shield atmosphere, obtains tungsten carbide-carbon nanotube particulate；When the carbon source is acetylene, using acetylene and hydrogen, argon The gaseous mixture of gas, the acetylene: hydrogen: argon gas volume ratio=30:30:40；The flow of the gaseous mixture is 100mL/min.
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