CN103506144B - The tungsten carbide of core shell structure/platinum composite and its preparation and application - Google Patents
The tungsten carbide of core shell structure/platinum composite and its preparation and application Download PDFInfo
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- CN103506144B CN103506144B CN201210216737.8A CN201210216737A CN103506144B CN 103506144 B CN103506144 B CN 103506144B CN 201210216737 A CN201210216737 A CN 201210216737A CN 103506144 B CN103506144 B CN 103506144B
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 219
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000011258 core-shell material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 11
- 230000009467 reduction Effects 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000000446 fuel Substances 0.000 claims abstract description 7
- 238000001694 spray drying Methods 0.000 claims abstract description 5
- 238000006073 displacement reaction Methods 0.000 claims abstract description 4
- 238000005253 cladding Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 17
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000006722 reduction reaction Methods 0.000 description 8
- 238000012876 topography Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005255 carburizing Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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 tungsten carbide of core shell structure/platinum composite and its preparation and application, the particle of the tungsten carbide of the core shell structure/platinum composite is using tungsten carbide as core, platinum cladding is grown on tungsten carbide surface, and the particle diameter of tungsten carbide/platinum composite of the core shell structure is in 50 ~ 150nm.The preparation method is that first passing through tungsten carbide/carbon/carbon-copper composite material that core shell structure is made in spray drying reduction and carbonization, then obtained Cu is reduced in carbonisation by Pt displacements, so as to obtain tungsten carbide/platinum composite of core shell structure, overall preparation process is simple, cost is low.The invention provides the tungsten carbide of the core shell structure/application of the platinum composite as elctro-catalyst in methanol fuel cell, as a result show, it can significantly improve catalytic conversion efficiency and catalyst service life.
Description
（One）Technical field
The present invention relates to a kind of tungsten carbide of core shell structure/platinum composite（Pt@WC）And its prepare and apply, especially
It is used as application of the elctro-catalyst in methanol fuel cell.
（Two）Background technology
Composite, is by two or more material of different nature, by method physically or chemically, in macroscopic view
Upper material of the composition with new capability.Various materials make up for each other's deficiencies and learn from each other in performance, produce cooperative effect, make composite
Combination property is better than former composition material and meets a variety of requirements.Tungsten carbide（WC）It is a kind of metallic compound, document report
Road（Referring to document：Science,1973,181:547）Point out, WC surface electronics layer is similar with Pt, has in some reactions
Class Pt catalytic activity.WC, which not only possesses, substitutes the characteristics of noble metal catalyst such as Pt and good anti-poisoning capability, but also
There are very strong acid resistance and preferable electro catalytic activity.However, due to WC prepare in high-temperature step, reduce its particle size and
Reunion seems more difficult between suppressing particle.Platinum（Pt）It is used as numerous key areas（Organic synthesis, fuel cell, Organic Electricity are closed
Into etc.）In wide variety of catalyst, all receive much concern all the time.Pt catalyst nanos are turned to a main research side
To being furtherd investigate in the past over 20 years.But, nanosizing similar with other catalyst（Grain diameter is down to Nano grade）
The later particle problems such as have reunion, stability not good.Further improve performance, the utilization ratio of Pt catalyst
It is the key issue of catalyst series development with service life.
The concept of bonded composite, the compound of WC and Pt materials is expected to so that both can make up mutually, and then enter one
Step increase performance embodies.The complex form of nucleocapsid structure is even more to have the advantages that to suppress reunion etc., because its unique structure is special
Property, the property of inside and outside two kinds of materials, and the respective deficiency that complements each other are incorporated, is the weight that pattern determines property in recent years
Want research direction.Its core shell structure has higher researching value：By constructing shell, platinum surface modification etc. can be changed well
Performance；Core shell structure is expected to that the physical and chemical performance of integral material can be improved.In catalysis, photocatalysis, battery, gas storage and separation
Aspect has a wide range of applications.Therefore, WC and Pt core shell structures are quite favored by investigation of materials personnel, especially nanometer material
Expect researcher.However, in existing report, rarely seen using Pt as shell, even WC is the preparation of the composite of core.It is existing
Pt/WC catalyst be mainly support type, complete the preparation of composite by loading Binary particle to matrix, and by
Cause blapharoplast larger in WC reunion and be difficult to reach nanosizing.And Pt loads are more with vapour phase reduction, chemical reduction method
To complete, process is relative complex, causes control to cost, the difficulty of process standardization control so that it is extensive prepare compared with
For difficulty.Therefore, preparation condition is controllable, Pt covering properties are good and WC blapharoplasts reach that the composite catalyst of Nano grade is aobvious
Write the key for improving composite Nano catalytic activity and important channel.Further, if can synchronously prepare constituent part, reduce
Preparation process, can more be greatly lowered production time, energy consumption and the production cost produced by this.
So far, from having not seen that relevant Synchronos method prepares the report of the Pt WC composites of spherical core shell structure.
（Three）The content of the invention
First goal of the invention of the present invention is to provide a kind of tungsten carbide/platinum composite of core shell structure（Pt@WC）, should
Stable, catalytic activity height is combined between composite each component, it is thermally-stabilised good.
Second goal of the invention of the present invention is to provide a kind of tungsten carbide/platinum composite of core shell structure（Pt@WC）'s
In preparation method, the preparation method, Pt is coated on WC surfaces, and Pt is obtained by replacing to reduce in carbonisation
Cu is obtained, and overall preparation process is simple, cost is low.
3rd goal of the invention of the invention is to provide a kind of tungsten carbide/platinum composite of core shell structure（Pt@WC）As
Application of the elctro-catalyst in methanol fuel cell.
Technical scheme is illustrated below.
The invention provides a kind of tungsten carbide of core shell structure/platinum composite（Pt@WC）, the carbonization of the core shell structure
The particle of tungsten/platinum composite is that, using tungsten carbide as core, platinum cladding is grown on tungsten carbide surface, the carbonization of the core shell structure
The particle diameter of tungsten/platinum composite is in 50 ~ 150nm.
Further, platinum content is 5 ~ 30wt% in the tungsten carbide of the core shell structure/platinum composite.
Present invention also offers the tungsten carbide of described core shell structure/platinum composite（Pt@WC）Preparation method, it is described
Preparation method comprises the following steps：
（1）Ammonium metatungstate and copper nitrate mixed solution are granulated using the method for spray drying；By obtained particle in richness
Reduction and carbonization is carried out using temperature programming-gas-solid reaction method under nitrogen atmosphere, cooling obtains tungsten carbide/composite copper material after the completion of carbonization
Material（WC-Cu）；
（2）By tungsten carbide/carbon/carbon-copper composite material（WC-Cu）Enter line replacement reaction in input compound containing platinum solution, obtain core
The tungsten carbide of shell structure/platinum composite（Pt@WC）.
In the present invention, described ammonium metatungstate and copper nitrate mixed solution can be prepared as follows：By inclined tungsten
Sour ammonium and copper nitrate in mass ratio 1：0.1 ~ 1 mixing, plus deionized water are configured to 1 ~ 30wt% solution；It is preferred that ammonium metatungstate with
The mixing quality ratio of copper nitrate is 1：0.5~0.8；It is preferred that ammonium metatungstate and copper nitrate in ammonium metatungstate and copper nitrate mixed solution
Total mass fraction be 8 ~ 22wt%.The present invention will preferably prepare obtained ammonium metatungstate and copper nitrate mixed solution passes through ultrasound
It is spray-dried again after processing progress is fully dispersed, so that its blending ingredients after spray drying in particle is evenly distributed；
Proper extension sonication treatment time helps to obtain scattered mixed solution evenly, it is preferred that sonication treatment time is 1 ~ 3 point
Clock.
In the present invention, the method granulation that ammonium metatungstate and copper nitrate mixed solution are dried using double air-stream sprayings, spraying is dry
The inlet temperature of dry device may be provided at 180 ~ 220 DEG C, and preferred inlet temperatures are 190 ~ 210 DEG C.
In the present invention, particle is carbonized using temperature programming-gas-solid reaction method to prepare the carbon of core shell structure
Change tungsten/carbon/carbon-copper composite material（WC-Cu）.Described carburising step is carried out in high-temperature tubular reacting furnace under hydrogen-rich atmosphere, described
Hydrogen-rich atmosphere refer to H2Mixed atmosphere of the proportion more than 50%, in certain Temperature Programmed Processes under hydrogen-rich atmosphere
In progressively remove volatilizable composition in reaction particles so that the probability for reducing intergranular collision, reuniting, obtains scattered
WC materials.Preferably hydrogen-rich atmosphere of the invention is：Volume ratio is 1：1.1 ~ 2.5 CO and H2Mixed atmosphere.Described temperature programming-
Gas-solid reaction method is preferably：700 ~ 950 DEG C are warming up to 1 ~ 10 DEG C/min hierarchical process to be kept for 1 ~ 8 hour；More preferably：
780 ~ 850 DEG C are warming up to 3 ~ 7 DEG C/min hierarchical process heating rate to be kept for 3 ~ 6 hours.
In the present invention, tungsten carbide/platinum composite of core shell structure（Pt@WC）The powder particle after reduction and carbonization can be passed through
Platinum displacement, which is realized, in the solution carries platinum, carries high-temperature gas reduction, reducing agent reduction that platinum needs etc. without carrying out routine, saves
About raw material and energy consumption.Preferred described compound containing platinum solution of the invention is the platinum acid chloride solution that concentration is 2 ~ 10mmol/L；
The compound containing platinum solution is tungsten carbide/platinum composite quality of prepared core shell structure according to the quality containing Pt
5% ~ 30% feeds intake；Specifically, described platinum displacement is to put tungsten carbide/carbon/carbon-copper composite material under the temperature conditionss of room temperature ~ 100 DEG C
Kept in compound containing platinum solution 1 ~ 24 hour, it is room temperature ~ 50 DEG C preferably to replace temperature, preferably time swap is 5 ~ 12 small
When.
The invention provides the tungsten carbide of described core shell structure/platinum composite（Pt@WC）As elctro-catalyst in first
Application in alcohol fuel battery.As a result show, tungsten carbide/platinum composite of described core shell structure（Pt@WC）Can substantially it carry
High catalytic conversion efficiency and catalyst service life.
Compared with existing Pt nanocrystals catalysis material, the present invention has the advantages that following prominent：
1. the tungsten carbide of core shell structure/platinum composite（Pt@WC）Not only catalytic activity is high, good thermal stability, and by
Stabilization is combined between conventional load, each component in not using.
2. the tungsten carbide of core shell structure/platinum composite（Pt@WC）The stability of catalyst is added containing WC, resists it
Poisoning capability is strengthened.
3. the tungsten carbide of core shell structure/platinum composite（Pt@WC）In Pt for be coated on WC spheroids grow, with reference to steady
It is fixed.
4. the tungsten carbide of core shell structure/platinum composite（Pt@WC）Middle Pt particles are obtained by replacing Cu particles, are eliminated all
The consumption of the raw materials such as many conventional steps and reducing agent carried in Pt methods, step is simple, and cost obtains effective reduction.
5. the tungsten carbide of core shell structure/platinum composite（Pt@WC）The Cu contents in precursor aqueous solution and later stage can be passed through
The regulation and control of platinum acid chloride solution addition carry Pt amounts.
6. the tungsten carbide of core shell structure/platinum composite（Pt@WC）Fuel cell is can be widely applied to as elctro-catalyst
Deng key areas, catalytic performance is significantly improved.
（Four）Brief description of the drawings
Fig. 1 is tungsten carbide/platinum composite of the core shell structure prepared in the embodiment of the present invention 1（Pt@WC）Scanning electricity
Mirror（SEM）Figure.
Fig. 2 is tungsten carbide/platinum composite of the core shell structure prepared in the embodiment of the present invention 1（Pt@WC）Transmission electricity
Mirror（TEM）Figure.
Fig. 3 is tungsten carbide/platinum composite of the core shell structure prepared in the embodiment of the present invention 1（Pt@WC）Partial heat
Weight（DTG）Test chart.
Fig. 4 is tungsten carbide/platinum composite of the core shell structure prepared in the embodiment of the present invention 1（Pt@WC）To methanol
Catalytic activity phenogram.In Fig. 4, abscissa is working electrode potential/V（SCE, using saturated calomel electrode as reference electrode）,
Curve is respectively Pt@WC and 10wt%Pt/C catalyst.Solution during measurement is methanol（2M）And sulfuric acid（1M）Mixing it is water-soluble
Liquid, it is 50mV/s to sweep speed.The 10wt%Pt/C catalyst is routine Pt/C catalyst, passes through impregnation Pt presomas（Chlorine
Platinic acid）Prepared in being reduced after C Surface, filtration drying under 400 DEG C of hydrogen atmospheres.
Fig. 5 is the catalytic activity phenogram of the Pt@WC materials that prepare to methanol in the embodiment of the present invention 1.In Figure 5, it is horizontal
Coordinate is the time (S).Curve is respectively Pt@WC and 10wt%Pt/C catalyst（Preparation method is ibid）.Solution during measurement is first
Alcohol（2M）And sulfuric acid（1M）Mixed aqueous solution, sweep speed be 50mV/s.
Fig. 6 is tungsten carbide/platinum composite of the core shell structure prepared in the embodiment of the present invention 2（Pt@WC）Scanning electricity
Mirror（SEM）Figure.
（Five）Embodiment：
Embodiments given below will the present invention is further illustrated with reference to accompanying drawing, but protection scope of the present invention is not
It is limited to this：
Embodiment 1：
By ammonium metatungstate and copper nitrate in mass ratio 1：0.6 mixing, plus deionized water are configured to 22wt% solution.This
It is fully dispersed laggard by progress in ultrasonically treated 3 minutes that invention will preferably prepare obtained ammonium metatungstate and copper nitrate mixed solution
Row spray drying, is dried using double air-stream sprayings and processing is dried（210 DEG C of inlet temperature）, obtained solid particle is carried out
Reduction and carbonization, carburizing atmosphere is：Volume ratio is 1：2 CO and H2Mixed atmosphere, is with 6 using temperature programming-gas-solid reaction method
DEG C/min hierarchical process heating rate is warming up to 800 DEG C and kept for 4 hours.Particle will be obtained, will be soaked under 50 DEG C of temperature conditionss
In 5mmol/L platinum acid chloride solution, platinum acid chloride solution is thrown according to the quality of Pt in solution for the 10% of prepared Pt@WC mass
Material, after being kept for 6 hours, drying obtains the Pt@WC samples with clad structure after filtering is washed.
Fig. 1 schemes for the SEM of prepared Pt@WC catalyst, and spherical shape is presented in particle as seen from Figure 1, and particle diameter distribution is non-
Often uniform, grain diameter is in 80nm or so.Fig. 2 for sample particle TEM scheme, as can be seen from the figure in sample component point
Cloth, platinum is evenly coated at the outer layer of WC cores, uniformly exists as shell.DTG under air conditionses（Fig. 3）, show sample
Product have good heat endurance in air atmosphere in 500 DEG C of high temperature.Sample is subjected to electrocatalysis characteristic test, sample table
Reveal outstanding methanol electrocatalysis characteristic and stability, as shown in Figure 4,5, its methanol oxidate current is higher than with platinum carrying capacity
Pt/C samples.
Embodiment 2：
It is similar with the process of embodiment 1, but ammonium metatungstate and copper nitrate in mass ratio 1：0.5 mixing, remaining step is identical,
Obtain Pt@WC samples.Fig. 6 schemes for the SEM of prepared Pt@WC materials.Sample particle is nano particle as can be seen from Figure 6.
Embodiment 3：
Similar with the process of embodiment 1, its ultrasonic disperse time is 1 minute, and remaining step is identical, obtains Pt@WC samples,
Sample topography figure is similar to Example 1.
Embodiment 4：
Similar with the process of embodiment 1, its carburizing atmosphere is that volume ratio is 1：1 CO and H2Mixed atmosphere, temperature programming
For 3 DEG C/min, it is warming up to 780 DEG C and is kept for 3 hours, remaining step is identical, obtains Pt@WC samples, sample topography figure and embodiment 1
It is similar.
Embodiment 5：
It is similar with the process of embodiment 1, but ammonium metatungstate and copper nitrate in mass ratio 1：0.8 mixing, remaining step is identical,
Pt nano particle@WC samples are obtained, sample topography figure is similar to Example 1.
Embodiment 6：
It is similar with the process of embodiment 1, but presoma ammonium metatungstate and copper nitrate solution concentration are 8wt%, remaining process phase
Together.Pt@WC samples are obtained, sample topography figure is similar to Example 1.
Embodiment 7：
It is similar with the process of embodiment 1, but it is 190 DEG C that inlet temperature is dried in mixed solution spraying, and other steps are identical.
To Pt@WC samples, sample topography figure is similar to Example 1.
Embodiment 8：
It is similar with the process of embodiment 1, but 20mmol/L platinum acid chloride solutions are added, carry platinum amount according to theory（That is in Pt@WC
Pt contents）5wt% feeds intake, and remaining step is identical, obtains Pt@WC samples, and sample topography figure is similar to Example 1.
Embodiment 9：
It is similar with the process of embodiment 2, but sample in platinum acid chloride solution when only at room temperature (20 DEG C) standing, during processing
Between be 2 hours, remaining step is identical, obtains Pt@WC samples, and sample topography figure is similar to Example 2.
Embodiment 10：
It is similar with the process of embodiment 1, but 1mmol/L platinum acid chloride solutions are added, carry platinum amount according to theory feeds intake for 30%,
Remaining step is identical, obtains Pt@WC samples, and sample topography figure is similar to Example 1.
Claims (7)
1. a kind of tungsten carbide of core shell structure/platinum composite, it is characterised in that the tungsten carbide of the core shell structure/platinum composite wood
The particle of material is that, using tungsten carbide as core, platinum cladding is grown on tungsten carbide surface, tungsten carbide/platinum composite of the core shell structure
Particle diameter in 50~150nm.
2. the tungsten carbide of core shell structure as claimed in claim 1/platinum composite, it is characterised in that：The core shell structure
Platinum content is 5~30wt% in tungsten carbide/platinum composite.
3. a kind of preparation method of the tungsten carbide of core shell structure as claimed in claim 1/platinum composite, it is characterised in that institute
Preparation method is stated to comprise the following steps：
(1) ammonium metatungstate and copper nitrate mixed solution are granulated using the method for spray drying；By obtained particle in hydrogen rich gas
Reduction and carbonization is carried out using temperature programming-gas-solid reaction method under atmosphere, described temperature programming-gas-solid reaction method is：With 1~10
DEG C/min hierarchical process be warming up to 700~950 DEG C keep 1~8 hour, the hydrogen-rich atmosphere is that volume ratio is 1：1.1~2.5
CO and H2Mixed atmosphere, cooling obtains tungsten carbide/carbon/carbon-copper composite material after the completion of carbonization；
(2) tungsten carbide/carbon/carbon-copper composite material is put into compound containing platinum solution and enters line replacement reaction, described displacement is in room temperature
Tungsten carbide/carbon/carbon-copper composite material is placed in compound containing platinum solution under~100 DEG C of temperature conditionss and kept for 1~24 hour, is obtained
The tungsten carbide of core shell structure/platinum composite.
4. the preparation method of the tungsten carbide of core shell structure as claimed in claim 3/platinum composite, it is characterised in that described
Ammonium metatungstate and copper nitrate mixed solution are prepared as follows：By ammonium metatungstate and copper nitrate in mass ratio 1：0.1
~1 mixing, plus deionized water are configured to 1~30wt% solution.
5. the preparation method of the tungsten carbide of core shell structure as claimed in claim 4/platinum composite, it is characterised in that：It will match somebody with somebody
The ammonium metatungstate and copper nitrate mixed solution being made first pass through it is ultrasonically treated carry out it is fully dispersed after be spray-dried again.
6. the preparation method of the tungsten carbide of the core shell structure as described in one of claim 3~5/platinum composite, its feature exists
In：Described compound containing platinum solution is the platinum acid chloride solution that concentration is 2~10mmol/L；The compound containing platinum is according to causing
Quality containing Pt feeds intake for the 5%~30% of tungsten carbide/platinum composite quality of prepared core shell structure.
7. the tungsten carbide of core shell structure as claimed in claim 1/platinum composite is as elctro-catalyst in methanol fuel cell
In application.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210216737.8A CN103506144B (en) | 2012-06-27 | 2012-06-27 | The tungsten carbide of core shell structure/platinum composite and its preparation and application |
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| CN201210216737.8A CN103506144B (en) | 2012-06-27 | 2012-06-27 | The tungsten carbide of core shell structure/platinum composite and its preparation and application |
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| CN103506144A CN103506144A (en) | 2014-01-15 |
| CN103506144B true CN103506144B (en) | 2017-07-28 |
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| CN104307546A (en) * | 2014-11-03 | 2015-01-28 | 太仓派欧技术咨询服务有限公司 | Transition metal catalyst with Pt-group metal dotted active points |
| CN105251487B (en) * | 2015-11-06 | 2018-01-26 | 上海电力学院 | A kind of preparation method of fuel cell W@Pt/C catalyst with core-casing structure |
| CN109952670B (en) * | 2016-04-07 | 2022-09-13 | 存点有限公司 | Lithium ion battery and anode thereof |
| CN106011925B (en) * | 2016-06-28 | 2018-04-13 | 北方工业大学 | Preparation method of sponge structure type Ni-W-Fe alloy based WC @ Pt core-shell structure particle electrode material |
| CN108666583B (en) * | 2017-03-31 | 2020-08-21 | 浙江工业大学 | Preparation method and application of high-bonding-degree nanometer WC-based binary composite material |
| CN109621999B (en) * | 2018-12-30 | 2021-12-07 | 浙江工业大学 | Tungsten carbide-nickel-palladium composite material, preparation thereof and application thereof in fuel cell |
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Application publication date: 20140115 Assignee: ZHEJIANG DONGYU ELECTRIC CO.,LTD. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980045621 Denomination of invention: Tungsten carbide/platinum composite material with core-shell structure and its preparation and application Granted publication date: 20170728 License type: Common License Record date: 20231103 Application publication date: 20140115 Assignee: ZHEJIANG CHANGTONG TECHNOLOGY Co.,Ltd. Assignor: JIANG University OF TECHNOLOGY Contract record no.: X2023980045616 Denomination of invention: Tungsten carbide/platinum composite material with core-shell structure and its preparation and application Granted publication date: 20170728 License type: Common License Record date: 20231103 |