CN117884145A - Ammonia oxidation and poisoning resistant Pt-based active catalyst and preparation method and application thereof - Google Patents
Ammonia oxidation and poisoning resistant Pt-based active catalyst and preparation method and application thereof Download PDFInfo
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- CN117884145A CN117884145A CN202410042210.0A CN202410042210A CN117884145A CN 117884145 A CN117884145 A CN 117884145A CN 202410042210 A CN202410042210 A CN 202410042210A CN 117884145 A CN117884145 A CN 117884145A
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- ammoxidation
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 49
- 230000003647 oxidation Effects 0.000 title claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 231100000572 poisoning Toxicity 0.000 title description 8
- 230000000607 poisoning effect Effects 0.000 title description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 16
- 239000000956 alloy Substances 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910002588 FeOOH Inorganic materials 0.000 claims description 6
- 229910002837 PtCo Inorganic materials 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002484 cyclic voltammetry Methods 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 10
- 239000000376 reactant Substances 0.000 abstract description 9
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 70
- 238000006243 chemical reaction Methods 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 239000000446 fuel Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000012041 precatalyst Substances 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 8
- 239000004471 Glycine Substances 0.000 description 7
- 239000006260 foam Substances 0.000 description 7
- 239000010411 electrocatalyst Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000011865 Pt-based catalyst Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910002835 Pt–Ir Inorganic materials 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000970 chrono-amperometry Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910019017 PtRh Inorganic materials 0.000 description 1
- 241000722270 Regulus Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- CTDPVEAZJVZJKG-UHFFFAOYSA-K trichloroplatinum Chemical compound Cl[Pt](Cl)Cl CTDPVEAZJVZJKG-UHFFFAOYSA-K 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6482—Vanadium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- 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
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- 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
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Abstract
The invention discloses an ammoxidation anti-poisoning Pt-based active catalyst which is an R-Pt-M catalyst or a Pt-M/MOOH catalyst prepared from Pt-M alloy through electrochemical reconstruction, wherein M is a transition metal element. The invention also discloses a preparation method and application of the ammonia oxidation anti-poisoning Pt-based active catalyst. The ammonia oxidation anti-poisoning Pt-based active catalyst has a defect-rich structure or a high specific surface area, can provide sufficient active sites for the adsorption of reactants, and the defect-rich structure or MOOH with an-OH group can adjust the electronic structure of Pt, so that the catalyst has excellent ammonia oxidation anti-poisoning performance, high electrochemical catalytic activity and stability, and has wide application prospect in electrochemical ammonia oxidation.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to an ammoxidation anti-poisoning Pt-based active catalyst, and a preparation method and application thereof.
Background
Ammonia electro-oxidation Reaction (AOR) has gained increasing attention for applications in low temperature Ammonia fuel cells, in situ high purity hydrogen production, ammonia treatment of wastewater, and the like. Ammonia is a carbon-free energy carrier with high hydrogen content (17.6 wt.%), high energy density (3000 Wh/Kg) and low production cost (1.2$/kWh) [ Catalysts,2017 (1): 23; international Journal of Hydrogen Energy,1984,9 (9): 759-766; journal of Power Sources,2006,162 (1): 198-206], and in addition, as one of the most important chemical commodities in the world, the infrastructure for ammonia synthesis, transport and distribution is well established.
The ammonia can be directly or indirectly used as fuel for fuel cell, in the reaction of direct ammonia fuel cell, the reaction product is nitrogen and water, and its peak power density can be up to 400mW cm at 100 deg.C -2 [Journal of Power Sources,2005,142(1-2):18-26]The method comprises the steps of carrying out a first treatment on the surface of the The indirect ammonia fuel cell is to couple electrolytic ammonia and hydrogen evolution reaction in an alkaline electrolytic tank to produce high-purity hydrogen,in an indirect manner to a fuel cell. In alkaline electrolyte, the potential of the electrolyzed ammonia is lower, and in theory, only 0.06V of external voltage is needed to electrolyze ammonia to produce nitrogen and hydrogen (reaction formula 1), which is far lower than the voltage (1.23V) needed to electrolyze water. In addition, the theoretical energy consumption required for ammonia electrolysis (assuming no kinetic limitation under thermodynamic conditions) can be calculated to be about 1.55Wh g based on the standard potential of the cell -1 H 2 While the electrolyzed water requires at least 33Wh g -1 H 2 This means that in theory ammonia electrolysis is 95% lower than water electrolysis energy consumption.
Anode reaction: 2NH 3，aq +6OH - →N 2，g +6H 2 O+6e - (-0.77V vs SHE)
Cathode reaction: 6H 2 O+6e - →2H 2，g +6OH - (-0.83V vs SHE)
Full reaction: 2NH 3，aq →N 2，g +3H 2，g (0.06V) (1)
The application prospect of ammonia in fuel cells is wide, but the anode reaction of the fuel cells is an ammoxidation reaction of six-electron transfer, the reaction process involves the formation of N≡N, the kinetics is extremely slow, the overpotential of ammonia oxidation is higher, the ammonia oxidation can generally take place only by the participation of a catalyst, and in addition, the surface adsorption poisoning exists, so that a plurality of electrocatalysts have no ammoxidation activity. Therefore, the development of an efficient and stable electrocatalyst has important significance in reducing the reaction overpotential, improving the current density and the like, so as to strive for early realization of the research of the ammonia fuel cell to enter a practical stage.
Among the numerous electrocatalysts reported, the noble metal Pt has been extensively focused and studied by having a suitable ammoxidation overpotential [ Journal of The Electrochemical Society,1963,110 (9): 1022;9-13; journal of the Electrochemical Society,2006,153 (10): a1894; ACS Catalysis,2020,10 (7): 3945-3957; advanced Functional Materials,2022,32 (13): 2110702]However, the scarcity and high cost of noble metals limit the large-scale application of this system. In addition, pt electrodes are extremely prone to poisoning during ammoxidation to lose electrochemical activityThe reason for this is that at the Pt catalyst active site, not only NH is present 3 And OH (OH) - Competitive adsorption of [ Journal of the Electrochemical Society,2006,153 (10): A1894]N, which is completely dehydrogenated simultaneously in the course of ammoxidation ad With higher adsorption energy to occupy the active site of Pt, N at this time ad Is easier to be OH - Oxidation to nitrite NO 2 - And nitrate NO 3 - Instead of forming N.ident.N bond to release green environment-friendly gas N 2 [The Journal of Physical Chemistry C,2015,119(18):9860-9878]。
For reasons such as high cost of Pt and poor durability in ammoxidation, researchers have adopted various modification measures to reduce the cost of Pt catalysts and to improve the activity and stability of the ammoxidation. Among them, the deposition of noble metals on inert substrates (such as Ni, ti and carbon-based materials) is a viable approach. RANEY Ni loaded Pt at 1M NH 3 CV test in-1M KOH solution, obvious ammoxidation peak at-0.2V vs. Hg/HgO potential, and shows that the electrocatalyst has ammoxidation activity, but Pt/RANEY Ni has the same electrochemical behavior of ammoxidation poisoning as pure Pt catalyst [ The Electrochemical Society, inc. ], 2004,517]。
Compared with pure Pt catalyst, the research shows that Pt-based metal alloy, metal oxide and other catalysts show higher activity on ammoxidation reaction. At present, more catalyst systems are researched to be Pt-based metal alloys, and the addition of binary or multi-element metals can not only effectively reduce the use amount of Pt, but also optimize the electronic structure of Pt, so that the electrochemical performance of the ammoxidation reaction of the catalyst is improved.
Ir and Ru elements are often used to alloy with Pt, mishima et al studied the ammoxidation of Pt black electrodes, ir black electrodes, mixtures of both, and electrochemically deposited Pt-Ir alloys in KOH solution, and found that the mixture of both Pt and Ir and the Pt-Ir alloy had a higher ammoxidation current at 0.6V vs. RHE potential than the Pt black electrodes and Ir black electrodes, but the ammoxidation electrochemical poisoning behavior was still present [ Electrochimica Acta,1998,43 (3-4): 395-404].
Wu et al synthesized PtIrNi-SiO with ternary metals supported on two substrates by ultrasonic reduction 2 CNT-COOH catalyst with peak current voltage at 0.68V vs. RHE, peak current density at 124.0A/g, stability test by Chronoamperometry (CA) at voltage 0.65V vs. RHE, found faster current decay, current decay at 500s [ ACS Catalysis,2020,10 (7): 3945-3957 ]]. The peak current potential and density of PtRh/C catalyst are-0.2V vs. Hg/HgO and 90mA/mg respectively, CA test is carried out under-0.3V vs. Hg/HgO voltage, and current density is only 0.05mA/mg after 120min [ Applied Catalysis B:environmental,2015,174:136-144]。
Another effective way to reduce the cost of electrocatalysts is to develop platinum-free electrocatalysts, i.e., widely available transition metal catalysts, primarily Ni-based catalysts. Ni catalysts are essentially inactive to ammoxidation [ Materials Chemistry and Physics,2008,108 (2-3): 247-250 ]]But is provided withEtc. found that Ni (OH) was produced by electrochemical oxidation of nickel electrode under alkaline conditions 2 Can catalyze the ammoxidation reaction, notably about 11% of the ammonia is oxidized to nitrate, the remainder being N 2 And NO x The main problem in this reaction is Ni/Ni (OH) 2 The potential of the electrode for ammoxidation reaction is higher, the initial potential is generally 0.50-0.60V vs. Hg/HgO, the stability performance is also poorer [ Electrochemistry Communications,2010,12 (1): 18-21 ]]。
Similarly, researchers have thought to improve the ammoxidation properties of Ni-based catalysts by binary or ternary alloy strategies, such as Huang et al, which have fabricated Ni (OH) in wire-in-plate structures by two-step hydrothermal methods 2 -Cu 2 O@CuO catalyst, the authors believe Ni (OH) 2 Nanoplatelets and Cu 2 Interfacial synergistic catalysis between O nanowires and Cu 2 The structural protection effect of the amorphous CuO interface on the surface of the O nanowire ensures the activity and stability of ammoxidation, but the potential of the ammoxidation reaction is still 060V vs. Hg/HgO above [ ACS Applied Energy Materials,2020,3 (5): 4108-4113]. It follows that transition metal catalysts, while having cost advantages, have too high a reaction voltage that is detrimental to fuel cell applications.
In summary, a need exists to explore novel ammoxidation catalysts that achieve suitable reaction potentials, high electrochemical activity and high stability of ammoxidation catalytic performance.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides an ammoxidation anti-poisoning Pt-based active catalyst which has ammoxidation anti-poisoning performance, high electrochemical catalytic activity and stability and can be used as an electrochemical ammoxidation hydrogen production catalyst.
The ammonia oxidation anti-poisoning Pt-based active catalyst is an R-Pt-M catalyst or a Pt-M/MOOH catalyst prepared from Pt-M alloy through electrochemical reconstruction, wherein M is a transition metal element.
The invention introduces low-cost and environment-friendly transition metal element M into a Pt-based catalyst system, and the novel R-Pt-M catalyst and transition metal oxyhydroxide catalyst Pt-M/MOOH are generated by using an in-situ reconstruction technology while reducing the cost of the catalyst.
Preferably, the transition metal element M includes Fe, co, mn, cu, V or Zn. According to the invention, the use amount of Pt is effectively reduced by introducing the transition metal element, so that the use cost of the catalyst is reduced.
Preferably, the molar ratio of Pt to the transition metal element M in the ammonia oxidation anti-poisoning Pt-based active catalyst is 0.1-3:1.
Preferably, the ammonia oxidation anti-poisoning Pt-based active catalyst may include a substrate material, and the Pt-M alloy is distributed on the substrate material.
Preferably, the substrate material comprises foam nickel, carbon cloth, carbon paper, foam copper, foam cobalt or foam titanium. The addition of the base material may further enhance the ammonia oxidation catalytic activity.
Preferably, a pair ofThe surface density of the Pt-M alloy on the substrate material is 0.1-3 mg/cm 2 。
The invention also provides a preparation method of the ammonia oxidation anti-poisoning Pt-based active catalyst. The preparation method of the catalyst is simple, feasible and safe, and has good universality.
The preparation method of the ammonia oxidation anti-poisoning Pt-based active catalyst comprises the following steps:
(1) Preparing Pt-M alloy by a hydrothermal method, wherein M is a transition metal element;
(2) Taking the Pt-M alloy prepared in the step (1) as a working electrode, taking a Pt sheet as a counter electrode, and assembling the counter electrode and a reference electrode into a three-electrode system, wherein the electrolyte is KOH-NH 3 ·H 2 O or NaOH-NH 3 ·H 2 O; and (3) carrying out cyclic voltammetry scanning on the three-electrode system, and carrying out electrochemical reconstruction to generate the ammonia oxidation anti-poisoning Pt-based active catalyst R-Pt-M or Pt-M/MOOH.
In the electrochemical scanning process, the catalyst is subjected to ammonia oxidation and simultaneously subjected to electrochemical reconstruction, in the electrochemical reaction process, the oxide of the transition metal usually generates a defect-rich structure or hydroxyl oxide through the electrochemical reconstruction of the pre-catalyst under alkaline conditions, and transition metal ions in the catalyst always undergo a leaching-deposition process to finally obtain an R-Pt-M catalyst with the defect-rich structure or a Pt-M/MOOH catalyst with a large specific surface area and MOOH groups. The electron structure of Pt can be regulated by the defect-rich structure or MOOH with-OH group to make dehydrogenation product N ad The Pt surface has proper adsorption energy to easily carry out N-to-N coupling, thereby improving the N-to-N 2 Thereby relieving NO and NO 2 - And NO 3 - Poor durability due to iso-poisoning species.
The ammonia oxidation anti-poisoning Pt-based active catalyst has higher specific surface area due to the generated defect-rich structure or MOOH, and can provide sufficient active sites for the adsorption of reactants.
Preferably, in the step (1), the method for preparing the Pt-M alloy by a hydrothermal method comprises the following steps: adding glycine, naI and PVP into deionized water, stirring to obtain a mixed solution, adding a Pt-containing compound and a transition metal element M-containing compound into the mixed solution, dripping ethanolamine, continuously stirring, performing hydrothermal reaction, washing the obtained product after the reaction is finished, and drying to obtain the Pt-M alloy.
Preferably, the Pt-containing compound includes chloroplatinic acid, platinic acid, platinum trichloride, platinum nitrate, or the like. The compound containing the transition metal element M comprises FeCl 3 ·6H 2 O、CoCl 2 ·6H 2 O、MnCl 2 ·4H 2 O、CuCl 2 ·2H 2 O、VCl 3 Or ZnCl 2 Etc.
Preferably, the temperature of the hydrothermal reaction is 80-160 ℃ and the time is 4-16 h.
Preferably, the drying temperature is 20-60 ℃.
Preferably, ethanolamine is dropwise added, and after continuous stirring, the washed base material is added to the obtained mixed solution, and then hydrothermal reaction is performed. The addition of the base material may further enhance the ammonia oxidation catalytic activity.
Preferably, in the step (2), KOH or NaOH and NH are contained in the electrolyte 3 ·H 2 The molar ratio of O is 0.1-14:1.
Preferably, in the step (2), the reference electrode is Hg/HgO electrode, the scanning voltage of the cyclic voltammetry scanning is-0.90-0.30V vs. Hg/HgO, the scanning period is 1-150 circles, and the scanning speed is 5-100 mV s -1 。
Preferably, the ammonia oxidation anti-poisoning Pt-based active catalyst Pt-M/MOOH comprises Pt 3 Fe/FeOOH catalyst.
The ammoxidation anti-poisoning Pt-based active catalyst Pt-M/MOOH is a transition metal oxyhydroxide with high specific surface area, the transition metal oxyhydroxide with an-OH group can adjust the electronic structure of Pt on one hand, the high specific surface area can provide more catalytic active sites on the other hand, the reconstructed catalyst Pt-M/MOOH can play a synergistic catalytic role, and adjust NH 3 And OH (OH) - Adsorption capacity in electrocatalytic ammoxidationIn the test, it has high electrocatalytic activity, stability and high N 2 And H 2 Selectivity.
Preferably, the ammonia oxidation anti-poisoning Pt-based active catalyst R-Pt-M comprises PtCo and Pt 3 Mn、PtCu、Pt 3 V or Pt 3 Zn catalyst.
The invention also provides application of the ammonia oxidation anti-poisoning Pt-based active catalyst in electrochemical ammonia oxidation hydrogen production. When the active catalyst is used for electrochemical ammoxidation, the active catalyst has ammoxidation antitoxic performance, high electrochemical activity and good stability, and has wide application prospect in electrochemical ammoxidation.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The ammonia oxidation anti-poisoning Pt-based active catalyst comprises an R-Pt-M catalyst and a Pt-M/MOOH catalyst, has a defect-rich structure or a larger specific surface area, and can provide sufficient active sites for the adsorption of reactants; the electron structure of Pt can be regulated by the defect-rich structure or MOOH with-OH group to make dehydrogenation product N ad The Pt surface has proper adsorption energy to easily carry out N-to-N coupling, thereby improving the N-to-N 2 Thereby relieving NO and NO 2 - And NO 3 - Poor durability due to iso-poisoning species.
(2) The preparation method of the catalyst is simple, feasible and safe, and has good universality.
(3) The invention introduces low-cost and environment-friendly transition metal M element into the Pt-based catalyst system, and can effectively reduce the dosage of Pt, thereby reducing the use cost of the catalyst. The addition of the substrate may further enhance the ammonia oxidation catalytic activity.
(4) The method can generate the transition metal oxyhydroxide with a defect-rich structure or high specific surface area on the surface of the catalyst through an electrochemical in-situ reconstruction strategy, and the in-situ reconstructed catalyst can play a synergistic catalysis role.
(5) The active catalyst has ammonia oxidation and poisoning resistance, high electrochemical catalytic activity and stability, does not have the ammonia oxidation poisoning behavior of the traditional Pt-based catalyst, has potential commercial value, and has wide application prospect in electrochemical ammonia oxidation.
Drawings
FIG. 1 is a scanning electron micrograph of an embodiment 1 of the present invention, wherein FIG. 1a is a precursor Pt 3 Scanning electron microscope photographs of Fe NF; FIG. 1b reconstructed catalyst Pt 3 Scanning electron micrographs of Fe/FeOOH NF.
FIG. 2 shows the CV curve of PtCo NF in example 2 of the present invention.
FIG. 3 is a Pt of example 3 of the present invention 3 CV curve of Mn NF.
Detailed Description
The microscopic morphology of the catalyst of each example was characterized by a Hitachi high resolution cold field emission scanning electron microscope (HEMT), the SEM instrument model was Hitachi Regulus 8230, the electron gun was a cold field emission gun, and the SE mode was employed with an operating voltage of 15kV.
The electrochemical test of the catalysts of the examples used a Solartron electrochemical workstation, a three electrode test system was used, the prepared catalyst was used as the working electrode, the Pt plate was the counter electrode, and Hg/HgO was the reference electrode. Before electrochemical testing, electrolyte KOH and KOH-NH 3 ·H 2 Introducing Ar gas into O to purge for 20-30 min to remove air, wherein Ar continuous purging is required in the test process, the CV voltage range is-0.90-0.30V vs. Hg/HgO, and the purging speed is 50mV s -1 。
Example 1
Preparation of Pre-catalyst Pt 3 Fe NF: the invention adopts a hydrothermal method to prepare the pre-catalyst Pt 3 Fe NF (Nickel Foam). First, oxides and residues on the surface of the NF substrate are removed by using 1M HCl, ethanol and deionized water, and a drying process is performed. During the experiment, 150mg glycine, 300mg NaI,100mg PVP were dissolved in 3.65ml deionized water and magnetically stirred, 40mg H was added 2 PtCl 6 ·6H 2 O and 7.0mg FeCl 3 ·6H 2 Adding O into the solution, dripping 0.35mL of ethanolamine, and continuously stirring the solution for 1hAfter that, the treated NF was added, and then the mixture was put into a hydrothermal oven at 160℃for 16 hours. After the reaction was completed, the residue on the surface of the reactant was rinsed with deionized water and dried in vacuum in an oven at 60 ℃.
Preparation of Pt 3 Fe/FeOOH NF: the prepared Pt was subjected to a H-type electrolytic cell 3 Fe NF is used as a working electrode, pt sheets are used as a counter electrode, hg/HgO is used as a reference electrode, and the electrolyte is KOH-NH 3 ·H 2 O or NaOH-NH 3 ·H 2 O, in the voltage range of-0.90 to 0.30V vs. Hg/HgO at 50mV s -1 Is scanned by CV, and the total period is 60 circles. In this process, pt 3 Fe NF is reconstructed in situ due to Fe 'leaching-redeposition', thereby generating Pt 3 Novel Fe/FeOOH NF catalyst.
Example 2
PtCo NF compound: preparation of precatalyst Pt by hydrothermal method 3 Co NF. During the experiment, 150mg glycine, 300mg NaI,100mg PVP was dissolved in 3.65ml deionized water and magnetically stirred to give 30mg H 2 PtCl 6 ·6H 2 O and 13.8mg of CoCl 2 ·6H 2 Adding O into the solution, dripping 0.35mL of ethanolamine, continuously stirring the solution for 1h, adding the treated foam nickel, and then placing the foam nickel into a hydrothermal oven for 10h at 140 ℃. After the reaction was completed, the residue on the surface of the reactant was rinsed with deionized water, and then placed in an oven at 40 ℃ for vacuum drying. In an H-type electrolytic cell, the prepared PtCo NF is taken as a working electrode, a Pt sheet is taken as a counter electrode, hg/HgO is taken as a reference electrode, and the electrolyte is KOH-NH 3 ·H 2 O or NaOH-NH 3 ·H 2 O, in the voltage range of-0.90 to 0.30V vs. Hg/HgO at 50mV s -1 Is scanned by CV, and the total period is 150 circles.
Example 3
Pt 3 Mn NF compound: preparation of precatalyst Pt by hydrothermal method 3 Mn NF. In the course of the experiment, 150mg glycine, 300mg NaI,100mg PVP were dissolved in 3.65ml deionized water and magnetically stirred to give 20mg H 2 PtCl 6 ·6H 2 O and 2.5mg of MnCl 2 ·4H 2 O is added into the solution and thenDropwise adding 0.35mL of ethanolamine, continuously stirring the solution for 1h, adding the treated NF, and then placing the mixture into a hydrothermal oven for heat preservation at 160 ℃ for 8h. After the reaction was completed, the residue on the surface of the reactant was rinsed with deionized water, and then placed in an oven at 20 ℃ for vacuum drying. In an H-type electrolytic cell, the prepared Pt 3 Mn NF is a working electrode, pt sheets are counter electrodes, hg/HgO is a reference electrode, and electrolyte is KOH-NH 3 ·H 2 O or NaOH-NH 3 ·H 2 O, in the voltage range of-0.90 to 0.30V vs. Hg/HgO at 50mV s -1 Is scanned by CV, and the total period is 150 circles.
Example 4
PtCu NF compound: the preparation method adopts a hydrothermal method to prepare the precatalyst PtCu NF. In the course of the experiment, 150mg glycine, 300mg NaI,100mg PVP were dissolved in 3.65ml deionized water and magnetically stirred to give 10mg H 2 PtCl 6 ·6H 2 O and 3.3mg of CuCl 2 ·2H 2 Adding O into the solution, dripping 0.35mL of ethanolamine, continuously stirring the solution for 1h, adding the treated NF, and then placing the solution into a hydrothermal oven for heat preservation at 100 ℃ for 8h. After the reaction was completed, the residue on the surface of the reactant was rinsed with deionized water and placed in an oven at 30 ℃ for vacuum drying. In the H-type electrolytic cell, the prepared PtCu NF is used as a working electrode, a Pt sheet is used as a counter electrode, hg/HgO is used as a reference electrode, and the electrolyte is KOH-NH 3 ·H 2 O or NaOH-NH 3 ·H 2 O, in the voltage range of-0.90 to 0.30V vs. Hg/HgO at 50mV s -1 Is scanned by CV, and the total period is 50 circles.
Example 5
Pt 3 V NF compound: preparation of precatalyst Pt by hydrothermal method 3 V NF. During the experiment, 150mg glycine, 300mg NaI,100mg PVP was dissolved in 3.65ml deionized water and magnetically stirred to give 50mg H 2 PtCl 6 ·6H 2 O and 5mg VCl 3 Adding into the solution, dripping 0.35mL of ethanolamine, continuously stirring the solution for 30min, adding the treated NF, and then placing into a hydrothermal oven for heat preservation at 120 ℃ for 10h. After the reaction is finished, the residue on the surface of the reactant is washed by deionized water and put into an oven at 20 DEG CAnd (5) performing vacuum drying. In the H-type electrolytic cell, pt 3 V NF is a working electrode, pt sheets are counter electrodes, hg/HgO is a reference electrode, and electrolyte is KOH-NH 3 ·H 2 O or NaOH-NH 3 ·H 2 O, in the voltage range of-0.90 to 0.30V vs. Hg/HgO, 50mV s -1 Is scanned by CV, and the total period is 100 circles.
Example 6
Pt 3 Zn NF compound: preparation of precatalyst Pt by hydrothermal method 3 Zn NF. In the course of the experiment, 150mg glycine, 300mg NaI,100mg PVP were dissolved in 3.65ml deionized water and magnetically stirred to give 20mg H 2 PtCl 6 ·6H 2 O and 1.7mg of ZnCl 2 Adding the solution, dropwise adding 0.35mL of ethanolamine, continuously stirring the solution for 1h, adding the treated NF, and then placing the solution into a hydrothermal oven for heat preservation at 150 ℃ for 16h. After the reaction was completed, the residue on the surface of the reactant was rinsed with deionized water and dried in vacuum in an oven at 60 ℃. In an H-type electrolytic cell, prepared Pt 3 Zn NF is a working electrode, pt sheets are counter electrodes, reference electrodes are Hg/HgO, and electrolyte is KOH-NH 3 ·H 2 O or NaOH-NH 3 ·H 2 O, in the voltage range of-0.90 to 0.30V vs. Hg/HgO at 50mV s -1 The CV scan is performed at a sweep rate for a total period of 60 turns.
FIG. 1 (a) shows the catalyst Pt in example 1 3 Fe NF is formed by nanospheres formed by aggregation of nano particles with smaller size, and Pt is subjected to electrochemical reconstruction 3 The Fe/FeOOH NF has completely different microcosmic morphologies, the lamellar structure morphology vertical to the substrate is generated by reconstructing the nano particles of the original sample, the specific surface area of the catalyst is increased, and the catalyst has high specific surface area which is one of the important reasons for high ammoxidation catalytic activity.
FIG. 2 is a CV curve of PtCo NF of example 2, an electrochemically reconstituted catalyst having an ammoxidation surface current density of 147mA/cm 2 The peak current voltage was 0.04V vs. Hg/HgO, and the ammoxidation surface current density of the initial catalyst was 48mA/cm 2 The peak current voltage was-0.07V vs. Hg/HgO.
FIG. 3 is a schematic diagram of a preferred embodiment of the present inventionExample 3 Pt 3 CV curve of Mn NF, catalyst subjected to electrochemical reconstruction has ammonia oxidation surface current density of 323mA/cm 2 The peak current voltage was 0.15V vs. Hg/HgO, and the ammoxidation surface current density of the initial catalyst was 103mA/cm 2 The peak current voltage was-0.09V vs. Hg/HgO.
Claims (10)
1. The ammonia oxidation anti-poisoning Pt-based active catalyst is characterized in that the ammonia oxidation anti-poisoning Pt-based active catalyst is an R-Pt-M catalyst or a Pt-M/MOOH catalyst prepared from a Pt-M alloy through electrochemical reconstruction, wherein M is a transition metal element.
2. The ammoxidation anti-poisoning Pt-based active catalyst of claim 1, wherein the mole ratio of Pt to transition metal element M in the ammoxidation anti-poisoning Pt-based active catalyst is 0.1-3:1.
3. The ammoxidation anti-poisoning Pt-based active catalyst of claim 1, further comprising a base material, wherein the Pt-M alloy is distributed on the base material.
4. The ammonia oxidation anti-poisoning Pt-based active catalyst of claim 3, wherein the Pt-M alloy on the substrate has an areal density of 0.1-3 mg/cm 2 。
5. The method for producing an ammoxidation anti-poisoning Pt-based active catalyst according to any one of claims 1 to 4, comprising the steps of:
(1) Preparing Pt-M alloy by a hydrothermal method, wherein M is a transition metal element;
(2) Taking the Pt-M alloy prepared in the step (1) as a working electrode, taking a Pt sheet as a counter electrode, and assembling the counter electrode and a reference electrode into a three-electrode system, wherein the electrolyte is KOH-NH 3 ·H 2 O or NaOH-NH 3 ·H 2 O; the three-electrode system is subjected to cyclic voltammetry scanningAnd (3) performing electrochemical reconstruction to generate the ammonia oxidation anti-poisoning Pt-based active catalyst R-Pt-M or Pt-M/MOOH.
6. The method according to claim 5, wherein KOH or NaOH and NH are contained in the electrolyte 3 ·H 2 The molar ratio of O is 0.1-14:1.
7. The method according to claim 5, wherein the reference electrode is Hg/HgO electrode, the cyclic voltammetry scanning voltage is-0.90-0.30V vs. Hg/HgO, the scanning period is 1-150 circles, and the scanning speed is 5-100 mV s -1 。
8. The method according to claim 5, wherein the ammonia oxidation anti-poisoning Pt-based active catalyst Pt-M/MOOH comprises Pt 3 Fe/FeOOH catalyst.
9. The preparation method according to claim 5, wherein the ammoxidation anti-poisoning Pt-based active catalyst R-Pt-M comprises PtCo, pt 3 Mn、PtCu、Pt 3 V or Pt 3 Zn catalyst.
10. Use of an ammoxidation anti-poisoning Pt-based active catalyst according to any one of claims 1-4 in electrochemical ammoxidation hydrogen production.
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