CN110518265A - A kind of platinum alloy catalyst, fused salt hot preparation method and Proton Exchange Membrane Fuel Cells - Google Patents
A kind of platinum alloy catalyst, fused salt hot preparation method and Proton Exchange Membrane Fuel Cells Download PDFInfo
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- CN110518265A CN110518265A CN201910639415.6A CN201910639415A CN110518265A CN 110518265 A CN110518265 A CN 110518265A CN 201910639415 A CN201910639415 A CN 201910639415A CN 110518265 A CN110518265 A CN 110518265A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 150000003839 salts Chemical class 0.000 title claims abstract description 38
- 229910001260 Pt alloy Inorganic materials 0.000 title claims abstract description 24
- 239000000446 fuel Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000012528 membrane Substances 0.000 title claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 32
- 229910052723 transition metal Inorganic materials 0.000 claims description 27
- 150000003624 transition metals Chemical class 0.000 claims description 27
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910001507 metal halide Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000005275 alloying Methods 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 5
- -1 nitric acid compound Chemical class 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 238000005201 scrubbing Methods 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 150000002697 manganese compounds Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 239000010970 precious metal Substances 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 abstract 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 abstract 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 11
- 229910002836 PtFe Inorganic materials 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 229910001339 C alloy Inorganic materials 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000008246 gaseous mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910002837 PtCo Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CMHKGULXIWIGBU-UHFFFAOYSA-N [Fe].[Pt] Chemical compound [Fe].[Pt] CMHKGULXIWIGBU-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/88—Processes of manufacture
-
- 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
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of platinum alloy catalyst, fused salt hot preparation method and Proton Exchange Membrane Fuel Cells.By using metal framework compound ZIF-8 as self-template, by the way of step pyrolysis, the group that high activity can be obtained is divided into the non-precious metal catalyst of Fe-N-C, the Fe nanometer particles of material internal are dispersed in nitrogenous porous carbon, with outstanding reactivity, excellent catalytic oxidation-reduction performance is shown in three-electrode system, is had a good application prospect on fuel cell and other new energy devices.
Description
Technical field
The present invention relates to a kind of preparation methods of platinum alloy catalyst applied to fuel cell oxygen reduction catalysis reaction, belong to
In new energy materials and application field.
Background technique
Proton Exchange Membrane Fuel Cells (PEMFC) has become as the significant technology for developing Hydrogen Energy society at present
Art circle and the common research hotspot of industry.In PEMFC technology, what is played a key effect is internal platinum based catalyst,
The important function for converting fuel gas hydrogen and oxygen catalytic reaction to electric energy is not only carry, and due to needing in material
Using the noble metal after specially treated, preparation cost is also to account for as many as one third in entire fuel cell.Therefore, in order to
The substantial breakthrough of proton exchange membrane fuel cell electrode material property is realized as early as possible, wherein a key in the urgent need to address
Problem is exactly that there is still a need for reduce for platinum dosage.Under the premise of guaranteeing that cell output does not decline, the use of platinum is reduced
Amount, it is meant that the catalytic activity needs of combination electrode entirety increase substantially, and a large amount of Research foundation shows that constructing platinum alloy receives
Rice catalyst (PtFe, PtCo, Pt3Ni etc.) it can be promoted brilliant inside platinum by platinum and other non-noble metal alloying actions
Stress between face reduces the spacing of lattice of platinum crystal, and catalytic activity greatly promotes.Therefore, this method of platinum alloyization is system
One effective means of standby low-platinum catalyst.
Summary of the invention
The object of the present invention is to provide a kind of platinum alloy catalysts, and provide preparation method.This catalyst tool
Have the advantages that crystallinity is high, activity is high, while also avoiding nanoparticle caused by conventional method in height in preparation method
Temperature under reunion the problems such as.
Technical solution is:
The first aspect of the invention provides:
A kind of platinum alloy catalyst is obtained after the Alloying Treatment that have passed through transition metal with platinum carbon.
In one embodiment, the transition metal refers to VIIB race, VIII group or IB group 4 transition metal.
In one embodiment, the VIIB group 4 transition metal is preferably manganese；VIII group transition metal be preferably iron,
Cobalt or nickel；IB group 4 transition metal is preferably copper.
In an embodiment, the platinum content in platinum carbon is 10-60%.
The second aspect of the invention provides:
The preparation method of above-mentioned platinum alloy catalyst, includes the following steps:
Transition metal inorganic salts are uniformly mixed by step 1 in deionized water with platinum carbon, and evaporating water is heat-treated；
The product of step 1 is uniformly mixed, evaporating water in deionized water with metal halide salt, then is roasted by step 2
Processing, then the metal halide salt of surface is washed away, obtain platinum alloy catalyst.
In one embodiment, transition metal inorganic salts refer to VIIB race, VIII group or IB race in the step 1
The inorganic salts of transition metal.
In one embodiment, the transition metal inorganic salts be the chloride of transition metal, nitric acid compound or
Carbonated.
In one embodiment, the transition metal inorganic salts are the chlorinations of the metals such as iron, nickel, cobalt, copper or manganese
Object, nitric acid compound or carbonated.
In one embodiment, the heat treatment in the step 1 refers to 120~200 DEG C of calcining 2h, and heat treatment is
It is carried out under reducing atmosphere.
In one embodiment, transition metal inorganic salts and the ratio of platinum carbon are according to transition gold in the step 1
Belong to atomic ratio 1:1~3 with platinum.
In one embodiment, in the step 2, calcination process refers to 500~800 DEG C of roasting 3h, roasting be
It is carried out under reducing atmosphere.
In one embodiment, in the step 2, metal halide salt is selected from the halide of IA race metal, preferably
It is KCl or LiCl.
In one embodiment, reducing atmosphere is in the atmosphere such as hydrogen, hydrogen-argon-mixed or ammonia.
In one embodiment, in the step 2, washing refers to using weak acid scrubbing.
In one embodiment, in the step 2, by the weight ratio 1 of the product of step 1 and metal halide salt:
20~50.
The third aspect of the invention provides:
One proton exchanging film fuel battery, load has above-mentioned platinum alloy catalyst in proton exchange membrane.
The fourth aspect of the invention provides:
Application of the metal halide salt in the performance for improving Proton Exchange Membrane Fuel Cells platinum alloy catalyst.
In one embodiment, the raising performance refers to the reunion for inhibiting catalyst granules or improves hydrogen reduction
Performance.
Beneficial effect
The present invention has the advantages that, using potassium chloride (KCl), lithium chloride (LiCl) is in high-temperature roasting using fused salt thermal bake-out method
The salt for becoming molten state in the process is coated on platinum alloy nano particle, forms one layer of barrier layer.It is this to be made of inorganic salts
Barrier layer can not only effectively facilitate the alloying of Pt nanoparticle, and the reunion of nanoparticle at high temperature can be prevented,
Later period by simply wash remove catalyst surface covering inorganic salts after, available cleaning, the catalyst table of high activity
Face.The platinum alloy catalyst prepared by this method is due to crystallinity height, the characteristics of nano particle is small, clean surface, table
Reveal excellent catalytic oxidation-reduction performance, has a good application prospect.
Detailed description of the invention
Fig. 1 is the XRD diagram of the PtFe/C alloy catalyst of fused salt thermal synthesis using ferric trichloride as raw material.
Fig. 2 is using ferric trichloride as raw material, and the TEM of the PtFe/C alloy catalyst of fused salt thermal synthesis schemes.
Fig. 3 is using ferric trichloride as raw material, and the LSV chemical property of the PtFe/C alloy catalyst of fused salt thermal synthesis is bent
Line.
Fig. 4 is the XRD diagram of the PtCo/C alloy catalyst of fused salt thermal synthesis using cobalt nitrate as raw material.
Fig. 5 is in reference examples 1, without the SEM for the Pristine-PtFe/C alloy catalyst that fused salt is heat-treated
Figure.
Fig. 6 is in reference examples 1, without the LSV electricity for the Pristine-PtFe/C alloy catalyst that fused salt is heat-treated
Chemical property curve.
Specific embodiment
The invention discloses a kind of high electrochemical activity for fuel cell, the nanometer alloy catalyst of low platinum carrying capacity
High-temperature molten salt hot preparation method.By the inorganic salt system with high-temperature fusion characteristic, in nanometer during high-temperature calcination
Particle surface forms one layer of barrier layer, can not only effectively facilitate the alloying of Pt nanoparticle, and can prevent nanoparticle
Reunion at high temperature, the later period, available cleaning was high after simply washing the inorganic salts for removing catalyst surface covering
Active catalyst surface.Excellent catalytic oxidation-reduction performance is shown by platinum alloy catalyst prepared by this method, is had
Good application prospect.
Embodiment 1
Accurate to measure platinum carbon (20wt%) 60 mg, 16.2 mg of Iron(III) chloride hexahydrate is dissolved in 10 mL deionized waters, sufficiently mixed
It is dried after conjunction, in H2/ Ar(volume ratio 1:9) gaseous mixture 2 h of the lower 150 DEG C of roastings of reducing atmosphere.Again by itself and potassium chloride 3000
Mg is dissolved in 20 mL deionized waters, uniform rear drying is mixed, in H2/ Ar(volume ratio 1:9) gaseous mixture reducing atmosphere under 600
DEG C carry out high-temperature molten salt thermal bake-out 3h.Product is sufficiently washed in the sulfuric acid of 0.5 M concentration finally, removes catalyst surface mistake
The metal salt and chloride of amount, and the not chloride ion-containing of the catalyst surface after washing, vacuum are determined with silver nitrate solution titration
PtFe/C alloy catalyst is obtained after drying.The XRD diagram of the catalyst is as shown in Figure 1, it can be seen from the figure that synthesis
PtFe/C is pure phase, and corresponding standard crystal card number is 96-900-4223, crystal structure fct.Fig. 2 is alloy catalysis
The images of transmissive electron microscope of agent, it can be seen that the granular size of PtFe Nanoalloy is about 5-7 nm, be distributed on the carbon carrier it is uniform,
Without obvious agglomeration.Show the PtFe/C alloy catalysis by the hot calcination method synthesis of fused salt by the electro-chemical test in Fig. 3
Under the same conditions, it is 0.905 V that test, which obtains half wave potential, under the conditions of 25-30 DEG C for agent, improves 31 than business Pt/C
MV effectively improves the quality specific activity of platinum catalyst.
Embodiment 2
Accurate to measure platinum carbon (60 wt%) 60 mg, 42.9 mg of cabaltous nitrate hexahydrate is dissolved in 10 mL deionized waters, sufficiently mixed
It is dried after conjunction, in pure H22 h of the lower 120 DEG C of roastings of reducing atmosphere.It is dissolved in 20 mL deionizations with 2000 mg of potassium chloride again
In water, uniform rear drying is mixed, in H2/ Ar(volume ratio 1:9) gaseous mixture reducing atmosphere lower 500 DEG C of progress high-temperature molten salt heat
Roast 3h.Finally product is sufficiently washed in the sulfuric acid of 0.5 M concentration, the excessive metal salt of removal catalyst surface and chlorination
Object, and the not chloride ion-containing of the catalyst surface after washing is determined with silver nitrate solution titration, PtCo/C is obtained after vacuum drying
Alloy catalyst, XRD diagram are as shown in Figure 4.
Embodiment 3
Accurate to measure platinum carbon (10 wt%) 60 mg, four hydration 2.48 mg of nickel acetate are dissolved in 10 mL deionized waters, sufficiently mixed
It is dried after conjunction, in H2/ Ar(volume ratio 1:9) gaseous mixture 2 h of the lower 150 DEG C of roastings of reducing atmosphere.Again by itself and potassium chloride 1300
Mg is dissolved in 20 mL deionized waters, uniform rear drying is mixed, in ammonia (NH3) the lower 800 DEG C of progress high temperature melting of reducing atmosphere
Salt thermal bake-out 3h.Finally product is sufficiently washed in the sulfuric acid of 0.5 M concentration, removal the excessive metal salt of catalyst surface and
Chloride, and the not chloride ion-containing of the catalyst surface after washing is determined with silver nitrate solution titration, it is obtained after vacuum drying
Pt3Ni/C alloy catalyst.
Reference examples 1
Difference with embodiment 1 is: after the surface of platinum carbon catalyst is mixed into Iron(III) chloride hexahydrate and dries, without fused salt
Cladding, directly progress calcination process.
As can be seen that being catalyzed without the platinum iron that fused salt coats protection processing from the scanning electron microscope image (Fig. 5) of product
There is apparent aggregate after high-temperature roasting in agent nano particle, illustrates that more serious group occurs in the particle of catalyst
Poly- phenomenon.The result of electrochemical property test further is carried out to product as shown in fig. 6, discovery is heat-treated without fused salt, directly
The half wave potential of the sample P-PtFe/C of calcining is 0.849 V, and the half wave potential than the product in embodiment 1 has dropped 56 mV.
And its carrying current drops to 5 mA cm-2, illustrate to be heat-treated without fused salt, the catalyst of dinectly bruning is on the carbon carrier
Dispersibility reduces, and the process that oxygen diffuses to catalyst surface is more difficult.
Claims (10)
1. a kind of platinum alloy catalyst, which is characterized in that it is obtained after the Alloying Treatment that have passed through transition metal with platinum carbon.
2. platinum alloy catalyst according to claim 1, which is characterized in that in one embodiment, the transition
Metal refers to VIIB race, VIII group or IB group 4 transition metal.
3. platinum alloy catalyst according to claim 1, which is characterized in that in one embodiment, the VIIB
Group 4 transition metal is preferably manganese；VIII group transition metal is preferably iron, cobalt or nickel；IB group 4 transition metal is preferably copper；One
In a embodiment, the platinum content in platinum carbon is 10-60%.
4. the preparation method of platinum alloy catalyst described in claim 1, which comprises the steps of:
Transition metal inorganic salts are uniformly mixed by step 1 in deionized water with platinum carbon, and evaporating water is heat-treated；
The product of step 1 is uniformly mixed, evaporating water in deionized water with metal halide salt, then is roasted by step 2
Processing, then the metal halide salt of surface is washed away, obtain platinum alloy catalyst.
5. the preparation method of platinum alloy catalyst according to claim 4, which is characterized in that in one embodiment,
Transition metal inorganic salts refer to the inorganic salts of VIIB race, VIII group or IB group 4 transition metal in the step 1；In a reality
It applies in mode, the transition metal inorganic salts are chloride, nitric acid compound or the carbonated of transition metal；In a reality
It applies in mode, the transition metal inorganic salts are chloride, nitric acid compound or the carbonic acid of the metals such as iron, nickel, cobalt, copper or manganese
Compound.
6. the preparation method of platinum alloy catalyst according to claim 4, which is characterized in that in one embodiment,
Heat treatment in the step 1 refers to 120~200 DEG C of calcining 2h, and heat treatment is carried out under reducing atmosphere；At one
In embodiment, transition metal inorganic salts and the ratio of platinum carbon are the atomic ratios according to transition metal and platinum in the step 1
1:1~3；In one embodiment, in the step 2, calcination process refers to 500~800 DEG C of roasting 3h, roasting be
It is carried out under reducing atmosphere.
7. the preparation method of platinum alloy catalyst according to claim 4, which is characterized in that in one embodiment,
In the step 2, metal halide salt is selected from the halide of IA race metal, preferably KCl or LiCl；In an embodiment party
In formula, reducing atmosphere is in the atmosphere such as hydrogen, hydrogen-argon-mixed or ammonia；In one embodiment, the step 2
In, washing refers to using weak acid scrubbing；In one embodiment, in the step 2, by the product of step 1 and metal halogen
Weight ratio 1:20~50 of compound salt.
8. a proton exchanging film fuel battery, in proton exchange membrane load have the right to require 1 described in platinum alloy catalysis
Agent.
9. application of the metal halide salt in the performance for improving Proton Exchange Membrane Fuel Cells platinum alloy catalyst.
10. application according to claim 9, which is characterized in that in one embodiment, the raising performance refers to
Inhibit the reunion of catalyst granules or improves hydrogen reduction performance.
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| CN113437318A (en) * | 2021-06-25 | 2021-09-24 | 北京大学 | Carbon-loaded noble metal alloy nanoparticle and preparation method and application thereof |
| CN114464823A (en) * | 2022-01-21 | 2022-05-10 | 先进能源产业研究院(广州)有限公司 | Oxygen reduction reaction catalyst and preparation method thereof |
| CN114566657A (en) * | 2022-02-23 | 2022-05-31 | 福州大学 | Platinum-based ordered alloy catalyst for fuel cell and preparation method thereof |
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| CN114566657B (en) * | 2022-02-23 | 2024-05-10 | 福州大学 | Platinum-based ordered alloy catalyst for fuel cell and preparation method thereof |
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