CN110943234A - High-performance platinum alloy catalyst based on magnetic regulation and control and preparation method thereof - Google Patents
High-performance platinum alloy catalyst based on magnetic regulation and control and preparation method thereof Download PDFInfo
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- CN110943234A CN110943234A CN201911420894.9A CN201911420894A CN110943234A CN 110943234 A CN110943234 A CN 110943234A CN 201911420894 A CN201911420894 A CN 201911420894A CN 110943234 A CN110943234 A CN 110943234A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 39
- 229910001260 Pt alloy Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 87
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 10
- 230000005292 diamagnetic effect Effects 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 150000003057 platinum Chemical class 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 230000005294 ferromagnetic effect Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000004687 hexahydrates Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical group 0.000 claims 1
- 239000011833 salt mixture Substances 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 14
- 239000000446 fuel Substances 0.000 abstract description 10
- 230000005389 magnetism Effects 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910002058 ternary alloy Inorganic materials 0.000 abstract description 4
- 238000012216 screening Methods 0.000 abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 2
- 229910001092 metal group alloy Inorganic materials 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000000956 alloy Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910002520 CoCu Inorganic materials 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910001339 C alloy Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910005578 NiBi Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005307 ferromagnetism Effects 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 238000003775 Density Functional Theory Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910015221 MoCl5 Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000003244 pro-oxidative effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a fuel cell catalyst material preparation theory and a method based on modulation of an internal electronic structure of a metal alloy by using macroscopic magnetism of the material as a screening means. In particular to a ternary alloy catalyst with a PtAB structure, which is characterized in that the A site is strong magnetic metal such as cobalt, iron, nickel, manganese, gadolinium and the like and accounts for 1 to 35at percent; the B site is non-magnetic or diamagnetic metal such as copper, silver, bismuth and the like, and accounts for 12-45 at%. The ternary alloy or the multi-element platinum alloy catalyst derived from the characteristic composition structure of the ternary alloy has the catalytic performance which is several times that of pure platinum nano particles by being loaded on a carbon carrier with high specific surface area, and has good application prospect in low-temperature fuel cells, particularly low-cost and high-power proton exchange membrane fuel cell stacks.
Description
Technical Field
The invention relates to a high-performance platinum alloy catalyst based on magnetic regulation and a preparation method thereof, belonging to the field of new energy materials and application.
Background
Hydrogen fuel cells are a new type of efficient, pollution-free power generation device, and in recent years, with the continuous progress of hydrogen fuel cell technology, especially low temperature Proton Exchange Membrane Fuel Cell (PEMFC), this new generation of energy conversion device has begun to enter a large-scale commercialization stage.
The manufacture of Membrane Electrode Assemblies (MEAs) has been the core technology in the field of PEMFC fuel cells, the performance of which almost determines the overall power generation capability of the assembled PEMFC fuel cell stack. The structure of the MEA is mainly composed of a proton exchange membrane, a cathode-anode catalyst and a gas diffusion component, wherein the cost of the catalyst is about half of the cost of the whole MEA due to the noble metal platinum, so that the development of the PEMFC catalyst with high performance and low noble metal content and the preparation method thereof have important significance. In the research of pure platinum catalyst and the research of ORR reaction mechanism, Density Functional Theory (DFT) calculation shows that the electronic state of the effective oxygen reduction catalyst surface is beneficial to the adsorption of oxygen molecules and the breaking of O = O double bonds, and is beneficial to the separation of reaction intermediate products from the catalyst surface, so that the reaction is smoothly carried out. The binding energy of the surface of pure metal platinum to oxygen molecules is too strong, and the platinum catalyst is reasonably regulated and controlled, so that the adsorption energy of the surface to oxygen is lower than that of a Pt {111} crystal face by about 0.2 eV, and the catalytic activity of the platinum catalyst is improved. The purpose of modulating the electronic state of the surface of the catalyst can be achieved by alloying the platinum catalyst, and in the conventional research and material development, the electronic state of the catalyst is often changed by adjusting the stress among catalyst atoms to cause lattice shrinkage. However, recent studies have shown that the power generation performance of the catalyst, particularly the pro-oxidant catalytic performance (ORR), can also be greatly improved by bonding a transition metal having different magnetic characteristics with the platinum metal. This is because the magnetic properties of metal atoms are generated in relation to their internal electronic structure. Magnetism is derived from unpaired electrons in atoms, and magnetic moments generated by electron spins are superimposed/cancelled with each other according to the number of electrons in forward and reverse spins, thereby presenting macroscopic magnetic/non-magnetic characteristics. The internal electronic structure of the atom modulated according to the magnetic characteristics can effectively promote the performance optimization of the platinum alloy catalyst.
Disclosure of Invention
The invention provides a material design and preparation method of a high-performance platinum alloy catalyst based on magnetic regulation. The performance of the synthesized fuel cell catalyst can be greatly improved by using the macroscopic magnetism of the material as a screening means and based on the material preparation theory and the method for modulating the internal electronic structure of the metal alloy.
In a first aspect of the present invention, there is provided:
a high-performance platinum alloy catalyst based on magnetic regulation is characterized in that carbon is used as a carrier, and the general formula of active components is as follows: PtAB; the A bit element is selected from ferromagnetic metal elements; the B-site element is selected from nonmagnetic or diamagnetic metal elements.
In one embodiment, the A-bit element has a magnetic property in the range of 1-1.5emu/g and the B-bit element has a magnetic property in the range of 0.004-0.034 emu/g.
In one embodiment, the magnetic strength of the high performance platinum alloy catalyst as a whole is from 0.02 to 0.08 emu/g.
In one embodiment, the support is present in the catalyst in a mass ratio of 20 to 80 wt%.
In one embodiment, the a-site element is selected from one or a mixture of cobalt, iron, nickel, manganese or gadolinium.
In one embodiment, the B site element is selected from one or a mixture of copper, silver or bismuth.
In a second aspect of the present invention, there is provided:
a preparation method of a high-performance platinum alloy catalyst based on magnetic regulation comprises the following steps:
and 3, adding hydrochloric acid into the dispersion liquid obtained in the step 2 for washing, filtering out black precipitates in the solution, washing with deionized water, and performing vacuum drying to obtain the product.
In one embodiment, the platinum salt is selected from chloroplatinic acid hexahydrate, potassium chloroplatinate, and platinum nitrate, with the platinum atom proportion being 30-70 at%.
In one embodiment, the A site element salt is selected from nitrate or chloride of strong magnetic metal such as cobalt, iron, nickel, manganese or gadolinium, and the A site element accounts for 1-35 at%.
In one embodiment, the B site element salt is selected from nitrate or chloride of non-magnetic or diamagnetic metal such as copper, silver, bismuth, etc., and the B site element accounts for 12-45 at%.
In one embodiment, the solvent includes, but is not limited to, water, ethanol, glycol, oleylamine, and other polar solvents and mixtures thereof, which can dissolve the above salt solution.
In one embodiment, the support comprises carbon materials such as, but not limited to, XC-72R, EC-300J, EC-600J, and the like.
In one embodiment, the mass of the added sodium borohydride reducing agent is controlled to be 5 to 20 times of the sum of atomic masses of Pt, A element and B element.
Advantageous effects
The invention provides a method for conveniently and rapidly screening the high-performance platinum ternary catalyst with the specified components by adopting the macroscopic magnetism of the catalyst as a parameter index and combining with the experimental research foundation of the interrelation between the electronic structure and the magnetism of the components of the PtAB type ternary alloy, and the method is accurate and synthesized in a large scale through the liquid phase reduction preparation method disclosed in the patent, and has important application prospect and commercial value.
Drawings
FIG. 1 shows Pt prepared in example 13TEM image of CoCu/C.
FIG. 2 shows Pt prepared in example 13LSV performance curve of CoCu/C.
FIG. 3 is Pt prepared in example 23CoCu3CV performance curve of/C.
FIG. 4 is Pt prepared in example 23CoCu3The fuel cell performance curve of/C.
FIG. 5 is Pt prepared in example 33SEM image of NiBi/C.
FIG. 6 is Pt prepared in example 43Mn(AgCu)3XRD pattern of/C.
FIG. 7 shows Pt prepared in example 43Mn(AgCu)3LSV performance plot of/C.
FIG. 8 is Pt, a material of example 13Hysteresis loop plot (VSM) of CoCu.
FIG. 9 is Pt, a material of example 23CoCu3Magnetic hysteresis loop map (VSM).
FIG. 10 shows Pt as a material of comparative example 13Hysteresis curve (VSM) of Co.
Detailed Description
Example 1
Using XC-72R as carbon substrate, H2PtCl6·6H2O and Co (NO)3)2·6H2O，CuCl2·2H2Synthesis of Pt from O as precursor of platinum, cobalt and copper3CoCu/C (Pt content 20 wt%) alloy catalyst. 80mg of XC-72R and 53.3mg of H2PtCl6·6H2O，10mg Co(NO3)2·6H2O，5.86mg CuCl2·2H2Adding O into 20ml of Ethylene Glycol (EG), pouring into a beaker after the O is uniformly dispersed in an ultrasonic dispersion machine, stirring for 5h, then slowly adding 0.166g of sodium borohydride into the beaker, stirring vigorously until no bubbles exist, then continuing stirring the beaker for 4h, pouring 20ml of 10% HCl into the beaker after the solution is stirred, after the reaction is finished, centrifugally separating the solution with black precipitates at 8000rpm, washing the solution with a large amount of ultrapure water, and finally placing the sample after the centrifugation into a vacuum drying box for overnight collection. Collecting the obtained product Pt3The magnetic strength of CoCu/C (platinum content: 20 wt%) was 0.03emu g-1The proportion of Pt in the alloy (charge ratio) is 60at%, and the proportion of Co in the alloyThe ratio is 20at%, and the Cu content is 20 at%. The TEM image is shown in FIG. 1, and it can be seen that the platinum alloy has good dispersibility on the carbon substrate and uniform particle diameters of about 3 to 5 nm. The product catalyst is subjected to electrochemical performance test of a three-electrode system, and FIG. 2 shows Pt3LSV performance curve of CoCu/C, and Pt can be calculated from the curve in the figure3The specific mass activity of the CoCu/C catalyst was 0.4A mg-1 PtCommercial JM platinum carbon catalyst (0.089 Amg)-1 Pt) 4.5 times of the total weight of the powder. FIG. 8 shows Pt as a material in example 13The hysteresis loop plot (VSM) of CoCu shows weak ferromagnetism against the magnetic background. The magnetic strength was 0.03 emu/g.
Example 2
Using XC-72R as carbon substrate, H2PtCl6·6H2O and Co (NO)3)2·6H2O，CuCl2·2H2Synthesis of Pt from O as precursor of platinum, cobalt and copper3CoCu3Alloy catalyst/C (Pt content 20 wt%). 80mg of XC-72R and 53.3mg of H2PtCl6·6H2O，10mg Co(NO3)2·6H2O，17.6mg CuCl2·2H2Adding O into 20ml of Ethylene Glycol (EG), pouring into a beaker after the O is uniformly dispersed in an ultrasonic dispersion machine, stirring for 10h, slowly adding 0.213g of sodium borohydride into the beaker, stirring vigorously until no bubbles exist, then continuing stirring the beaker for 4h, pouring 20ml of 10% HCl into the beaker after the solution is stirred, after the reaction is finished, carrying out suction filtration and separation on the solution with black precipitates, washing the solution with a large amount of ultrapure water, and finally placing a sample after centrifugation in a vacuum drying oven for overnight collection. Collecting the obtained product Pt3CoCu3Magnetic Strength of 0.02 emu g/C (platinum content 20 wt%)-1In the alloy, the proportion of Pt (charge ratio) is 43at%, that of Co is 14at%, and that of Cu is 43 at%. The catalyst was subjected to electrochemical performance test, and its CV curve is shown in FIG. 3, from which the electrochemical specific surface area of the catalyst was calculated to be 41m2g-1Mixing Pt3CoCu3the/C catalyst is assembled into a membrane electrode for single cell test, wherein Pt3CoCu3a/C cathodeThe platinum supporting amount of (2) is 0.2mg cm-2As can be seen from FIG. 4, the current density at 0.6V was 2.37A cm-2The power density is 1.42W cm-2Maximum power of 1.62W cm-2. FIG. 9 shows Pt as a material in example 23CoCu3The hysteresis loop map (VSM) of (1) also shows weak ferromagnetism under a diamagnetic back, but the magnetic strength is reduced to 0.02 emu/g because of the increase of diamagnetic substances at the B site.
Example 3
EC-600J as carbon substrate, H2PtCl6·6H2O and Ni (NO)3)2·6H2O，Bi(NO3)3·5H2Synthesis of Pt with O as precursor of platinum, nickel and bismuth3NiBi/C (Pt content 20 wt%) alloy catalyst. 80mg of EC-600J and 53.3mg of H2PtCl6·6H2O，10mg Ni(NO3)2·6H2O，16.61mg Bi(NO3)3·5H2Adding O into 20ml Ethylene Glycol (EG), pouring into a beaker after the O is uniformly dispersed in an ultrasonic dispersion machine, stirring for 10h, slowly adding 0.166g of sodium borohydride into the beaker, stirring vigorously until no bubbles exist, continuing stirring the beaker for 4h, pouring 20ml10% HCl into the beaker after the solution is stirred, after the reaction is finished, carrying out suction filtration and separation on the solution with black precipitates, washing with a large amount of ultrapure water, and finally placing a sample after centrifugation in a vacuum drying oven for overnight collection to obtain Pt3The NiBi/C alloy catalyst product, in which the Pt content (charge ratio) is 60at%, the Ni content is 20at%, and the Bi content is 20at%, is shown in FIG. 5 as an SEM image of the catalyst powder.
Example 4
Using XC-72R as carbon substrate, H2PtCl6·6H2O and Mn (NO)3)2·6H2O，AgNO3，CuCl2·2H2Synthesis of Pt from O as precursor of platinum, manganese, silver and copper3Mn(AgCu)3Alloy catalyst/C (Pt content 20 wt%). 80mg of XC-72R and 53.3mgH2PtCl6·6H2O，9.88mg Mn(NO3)2·6H2O，17.56mg AgNO3，17.6mgCuCl2·2H2Adding O into 20ml Ethylene Glycol (EG), pouring into a beaker after the O is uniformly dispersed in an ultrasonic dispersion machine, stirring for 10h, then slowly adding 0.4g sodium borohydride into the beaker, stirring vigorously until no bubbles exist, then continuing stirring the beaker for 4h, pouring 20ml10% HCl into the beaker after the solution is stirred, after the reaction is finished, centrifugally separating the solution with black precipitate at 8000rpm and washing with a large amount of ultrapure water, finally placing the sample after the centrifugation in a vacuum drying box, and collecting overnight to obtain the Pt3Mn(AgCu)3a/C alloy catalyst product. The XRD of the catalyst powder is shown in fig. 6, and the crystal structure and peak pattern are typical fcc face-centered cubic structure, and the peak position is shifted to a high angle with respect to pure platinum, which is a typical characteristic of lattice shrinkage after Pt alloying. The product catalyst was subjected to electrochemical performance testing of a three-electrode system, and FIG. 7 is Pt3Mn(AgCu)3LSV performance curve of/C, from which Pt can be calculated3Mn(AgCu)3The specific mass activity of the/C catalyst was 0.387A mg-1 PtCommercial JM platinum-carbon catalyst (0.089A mg)-1 Pt) 4.3 times of the total weight of the powder.
Example 5
EC-300J as carbon substrate, H2PtCl6·6H2O and Fe (NO)3)3·9H2O，MoCl5The PtFeMo/C (Pt content is about 80 wt%) alloy catalyst is synthesized as a precursor of platinum, iron and molybdenum. 20mg of EC-300J and 53.3mg of H2PtCl6·6H2O，41.5mg Fe(NO3)3·9H2O，28.1mg MoCl5Adding into 20ml Ethylene Glycol (EG), dispersing uniformly in an ultrasonic disperser, pouring into a beaker, stirring for 10h, slowly adding 0.4g sodium borohydride into the beaker, stirring vigorously until no bubbles exist, continuing stirring the beaker for 4h, pouring 20ml10% HCl into the beaker after the solution is stirred, centrifugally separating the solution with black precipitate at 8000rpm after the reaction is finishedAnd washing with a large amount of ultrapure water, and finally placing the centrifuged sample in a vacuum drying box for overnight collection to obtain the PtFeMo/C alloy catalyst product. In the alloy, the proportion of Pt (charge ratio) is 34at%, the proportion of Fe is 33at%, the proportion of Mo is 33at%, and the magnetic strength of the collected product PtFeMo/C is 0.08emu g-1。
Comparative example 1
The differences from example 1 are: CuCl is not added during the preparation of the catalytic material2·2H2O, and preparing Pt supported on carbon3Co is used as the catalyst of the active component.
Using XC-72R as carbon substrate, H2PtCl6·6H2O and Co (NO)3)2·6H2Synthesis of Pt by taking O as precursor of platinum and cobalt3Co/C alloy catalyst. 80mg of XC-72R and 53.3mg of H2PtCl6·6H2O，10mg Co(NO3)2·6H2Adding O into 20ml of Ethylene Glycol (EG), pouring into a beaker after the O is uniformly dispersed in an ultrasonic dispersion machine, stirring for 5h, then slowly adding 0.144g of sodium borohydride into the beaker, stirring vigorously until no bubbles exist, then continuing stirring the beaker for 4h, pouring 20ml of 10% HCl into the beaker after the solution is stirred, after the reaction is finished, centrifugally separating the solution with black precipitates at 8000rpm, washing the solution with a large amount of ultrapure water, and finally placing the sample after the centrifugation into a vacuum drying box for overnight collection. Collecting the obtained product Pt3The magnetic strength of Co/C was 0.08emu g-1The proportion of Pt in the alloy (charge ratio) is 75at%, and the proportion of Co in the alloy is 25 at%. FIG. 10 shows Pt as a material of comparative example 13The hysteresis curve (VSM) of Co also shows weak ferromagnetism under diamagnetic back, but the magnetic strength is reduced to 0.02 emu/g because of the increase of diamagnetic substances at B sites.
Claims (9)
1. A high-performance platinum alloy catalyst based on magnetic regulation and control is characterized in that carbon is used as a carrier, and the general formula of active ingredients is as follows: PtAB; the A bit element is selected from ferromagnetic metal elements; the B-site element is selected from nonmagnetic or diamagnetic metal elements.
2. The magnetic modulation-based high performance platinum alloy catalyst according to claim 1, wherein in one embodiment, the A-site element magnetic property ranges from 1 to 1.5emu/g, and the B-site element magnetic property ranges from 0.004 to 0.034 emu/g; in one embodiment, the high performance platinum alloy catalyst has a bulk magnetic strength of 0.02 to 0.08 emu/g; in one embodiment, the support is present in the catalyst in a mass ratio of 20 to 80 wt%.
3. The high-performance platinum alloy catalyst based on magnetic control as claimed in claim 1, wherein in one embodiment, the a site element is selected from one or a mixture of cobalt, iron, nickel, manganese or gadolinium; in one embodiment, the B site element is selected from one or a mixture of copper, silver or bismuth.
4. The preparation method of the high-performance platinum alloy catalyst based on magnetic regulation and control as claimed in claim 1, characterized by comprising the following steps:
step 1, mixing and dispersing platinum salt, A-site element salt and B-site element salt in a solvent, uniformly stirring until the mixture is clear, adding a carbon carrier with a high specific surface area in a fixed proportion, and performing ultrasonic dispersion;
step 2, adding a sodium borohydride reducing agent into the mixed solution obtained in the step 1 in the process of violent stirring to perform reduction reaction;
and 3, adding hydrochloric acid into the dispersion liquid obtained in the step 2 for washing, filtering out black precipitates in the solution, washing with deionized water, and performing vacuum drying to obtain the product.
5. The method for preparing a high performance platinum alloy catalyst based on magnetic regulation as claimed in claim 4, wherein in one embodiment, the platinum salt is selected from chloroplatinic acid hexahydrate, potassium chloroplatinate, and platinum nitrate, and the platinum atom proportion is 30-70 at%.
6. The preparation method of the high-performance platinum alloy catalyst based on magnetic regulation and control as claimed in claim 4, wherein in one embodiment, the A site element salt is selected from nitrates or chlorides of strong magnetic metals such as cobalt, iron, nickel, manganese or gadolinium, and the A site element proportion is 1-35 at%; in one embodiment, the B site element salt is selected from nitrate or chloride of non-magnetic or diamagnetic metal such as copper, silver, bismuth, etc., and the B site element accounts for 12-45 at%.
7. The method for preparing the high-performance platinum alloy catalyst based on magnetic control according to claim 4, wherein the solvent comprises, but is not limited to, water, ethanol, ethylene glycol, oleylamine, and other polar solvents capable of dissolving the salt solution, and mixtures thereof.
8. The method of claim 4, wherein the support comprises carbon materials selected from the group consisting of XC-72R, EC-300J, and EC-600J.
9. The preparation method of the high-performance platinum alloy catalyst based on magnetic regulation and control as claimed in claim 4, wherein in one embodiment, the added mass of the sodium borohydride reducing agent is controlled to be 5-20 times of the atomic mass sum of Pt, A element and B element.
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