CN115679370A - Transition metal catalyst and preparation method thereof - Google Patents
Transition metal catalyst and preparation method thereof Download PDFInfo
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- CN115679370A CN115679370A CN202211459644.8A CN202211459644A CN115679370A CN 115679370 A CN115679370 A CN 115679370A CN 202211459644 A CN202211459644 A CN 202211459644A CN 115679370 A CN115679370 A CN 115679370A
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- metaphosphate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 62
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 29
- 125000005341 metaphosphate group Chemical group 0.000 claims abstract description 17
- 238000004070 electrodeposition Methods 0.000 claims abstract description 15
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 71
- 229910052759 nickel Inorganic materials 0.000 claims description 59
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 43
- 229910052707 ruthenium Inorganic materials 0.000 claims description 39
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 239000002923 metal particle Substances 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 41
- 239000001257 hydrogen Substances 0.000 abstract description 41
- 239000002245 particle Substances 0.000 abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000003792 electrolyte Substances 0.000 abstract description 12
- 239000012266 salt solution Substances 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 42
- 239000002184 metal Substances 0.000 description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 230000004075 alteration Effects 0.000 description 12
- 239000010439 graphite Substances 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 9
- 230000010287 polarization Effects 0.000 description 9
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- -1 carbon nitrides Chemical class 0.000 description 7
- 239000002135 nanosheet Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 230000005469 synchrotron radiation Effects 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910000398 iron phosphate Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 238000004832 voltammetry Methods 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000013211 curve analysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- RMLYXMMBIZLGAQ-UHFFFAOYSA-N (-)-monatin Natural products C1=CC=C2C(CC(O)(CC(N)C(O)=O)C(O)=O)=CNC2=C1 RMLYXMMBIZLGAQ-UHFFFAOYSA-N 0.000 description 1
- RMLYXMMBIZLGAQ-HZMBPMFUSA-N (2s,4s)-4-amino-2-hydroxy-2-(1h-indol-3-ylmethyl)pentanedioic acid Chemical compound C1=CC=C2C(C[C@](O)(C[C@H](N)C(O)=O)C(O)=O)=CNC2=C1 RMLYXMMBIZLGAQ-HZMBPMFUSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002953 phosphate buffered saline Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
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- 230000001360 synchronised effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
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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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Catalysts (AREA)
Abstract
The invention provides a metaphosphate supported transition metal catalyst and a preparation method thereof, belonging to the field of electrocatalytic water decomposition. The catalyst is prepared by preparing a transition metal hydroxide array, preparing a transition metal metaphosphate array carrier from the transition metal hydroxide array by a chemical vapor deposition method, and then preparing the transition metal catalysts loaded with monatomic type metaphosphate, cluster type metaphosphate and particle type metaphosphate by an electrodeposition technology by respectively using the transition metal metaphosphate array carrier and a transition metal salt solution as a working electrode and an electrolyte. The prepared metaphosphate-loaded transition metal catalyst is applied to an electrolytic cell in a full pH range and has excellent electro-catalytic hydrogen evolution performance.
Description
Technical Field
The invention relates to the field of hydrogen production by electrocatalytic water decomposition, in particular to a transition metal catalyst and a preparation method thereof.
Background
Excessive consumption of fossil fuels causes problems of global warming and environmental pollution, and hydrogen is considered as an ideal substitute for fossil fuels as a green energy source. From the aspect of the hydrogen production method, the hydrogen production by water electrolysis is a safe and environment-friendly way, and can be combined with renewable energy sources such as solar energy, wind energy and the like so as to improve the utilization efficiency of the energy sources. So far, the hydrogen evolution performance of platinum-based materials in all pH solutions is still the best. However, the high price and susceptibility to poisoning of platinum-based materials have hindered their large-scale commercial use. An ideal hydrogen evolution electrocatalyst should have low cost, high stability characteristics, and operate efficiently over a wide pH range. The challenge in developing pH-universal electrocatalysts stems from the different reaction mechanisms of the hydrogen evolution reaction in different chemical environments. In an acidic medium, the material is coupled to protons (H) 3 O + ) The adsorption capacity determines the rate of the hydrogen evolution reaction. In neutral and alkaline media, however, protons are supplied by water molecules, so that the electrocatalyst is required to have good water molecule adsorption and dissociation capabilities in the rate-limiting step of the reaction, the Volmer step. This task is extremely challenging but meaningless in order to obtain electrocatalysts with hydrogen evolution performance exceeding that of platinum-based materials over all pH ranges, taking into account intrinsic thermodynamic properties and structure-activity relationships.
Supported metal catalysts, in which both the support and the metal are very important, have played a critical role in various nanotechnology applications. As active centers, changes in the size of the metal (from single atoms, clusters to nanoparticles) generally affect surface electronegativity, energy, and interfacial reactivity. Meanwhile, the support is generally not inert, which can modulate the spatial distribution of the metal, charge transfer, interfacial perimeter, and metal morphology through metal support interactions. Specifically, orbital hybridization and charge transfer between the carrier and the metal adjust the d-band center of the metal, and the adsorption capacity of the reaction intermediate is enhanced, so that the energy barrier is reduced, and the rate determining step is accelerated. Carbon materials, carbon nitrides, sulfides, nitrides, and the like can be used as the support for the metal. However, most of them cannot achieve hydrogen evolution activity and long-term stability beyond platinum carbon, limited by interfacial instability such as metal particle agglomeration and sensitivity to pH change.
Disclosure of Invention
The invention aims to provide a transition metal catalyst for solving the technical problems that the existing catalyst is low in catalytic activity, relatively poor in stability and incapable of carrying out effective hydrogen evolution reaction in a full pH range. The catalyst consists of a cyclic P 4 O 12 By M-O-P with MO 6 The carrier formed by connecting the polyhedrons loads the transition metal N, so that the stability of the transition metal catalyst is greatly improved.
In particular, the invention uses cyclic P 4 O 12 By M-O-P with MO 6 Carriers formed by joining polyhedrons, both containing POs sharing an infinite corner 4 3- Tetrahedral chains, also comprising POs sharing limited 3, 4, 6 and 12 angles 4 3- And (4) a ring. The unique chain structure makes it have good conductivity. And Metal Oxide (MO) -Phosphate (PO) 4 ) 3- The presence of M in the unit also ensures the stability of the vector itself. Further, the phosphate group may not only act as a proton acceptor, but its local metal geometry inducing twist favors the adsorption of water molecules, both of which favor the progress of the hydrogen evolution reaction. PO on the surface of a support 3 3- The group can play a role in protecting, prevent the corrosion of the solution to the catalyst in the reaction process, and can also firmly anchor the metal material attached to the surface, prevent the dissolution or aggregation of the metal, thereby improving the stability of the material.
As is apparent from the above description, the ring-shaped P of the present invention 4 O 12 By M-O-P with MO 6 The carrier formed by polyhedral ligation includes metaphosphate, but is not limited thereto. The transition metal N is selected from iron, cobalt, nickel, platinum, ruthenium, iridium and palladium; the transition metal M is selected from iron, cobalt and nickel. The transition metal N may be in any form, including but not limited to transition metalsMonoatomic, transition metal cluster, or transition metal particle.
In order to ensure a larger contact area with the solution and to reduce the amount of metal used, the size of the transition metal N is less than 10nm.
In certain preferred embodiments, the support has a rich microstructure to increase the specific surface area; for example, a rod array structure, with transition metals supported on the rod surface.
The high-stability catalyst of the invention is obtained by taking metaphosphate as a carrier through the following steps:
the method comprises the following steps: preparing a transition metal M hydroxide array;
step two: preparing a metaphosphate array of the transition metal M from the transition metal hydroxide array prepared in the step one by a chemical vapor deposition method;
step three: preparing a metal single atom, cluster and particle array catalyst loaded with metal metaphosphate by using the transition metal metaphosphate array and the metal N salt solution obtained in the step two as a working electrode and electrolyte respectively through an electrodeposition technology;
according to the present invention, a transition metal hydroxide array is prepared, and the preparation method of the transition metal hydroxide array is not particularly limited, and a hydrothermal method, a solvothermal method, a chemical vapor deposition method, a chemical deposition method, or an electrodeposition method, which is well known to those skilled in the art, is used, and preferably, the hydrothermal method or the electrodeposition method is used.
Preferably, the hydrothermal method comprises the steps of dissolving a metal salt solution of M in a solvent in a reaction kettle, fully dissolving the metal salt solution, cleaning a conductive substrate with dilute hydrochloric acid, ethanol and deionized water, and obliquely inserting the conductive substrate into the reaction kettle; sealing the reaction kettle, placing the reaction kettle into a blast oven to react for 5 hours at the temperature of 100-200 ℃, preferably at the temperature of 110 ℃, and repeatedly washing the reaction kettle with ethanol and deionized water after natural cooling to obtain the transition metal hydroxide array. The metal salt in the metal salt solution of M is preferably one of nitrate and chloride of iron, cobalt or nickel, and more preferably cobalt nitrate, nickel nitrate, ferrous sulfate or nickel sulfate; the solvent is preferably urea and ammonium fluoride; the conductive substrate is preferably carbon cloth, carbon paper, a nickel net, a copper net, a titanium net or a titanium sheet.
According to the invention, the prepared transition metal hydroxide array is used for preparing a transition metal metaphosphate array by a chemical vapor deposition method; specifically, it is preferable that: and (3) placing the obtained transition metal hydroxide array in one magnetic boat, placing non-metal powder in the other magnetic boat, placing the two magnetic boats in a tubular furnace to react for 1-3 hours at 250-600 ℃, preferably at 300-500 ℃, cooling and taking out to obtain the transition metal metaphosphate array. The non-metal powder is preferably sodium hypophosphite, and 1.5g of the non-metal powder is matched with each 2cm multiplied by 4cm transition metal hydroxide array.
According to the invention, the transition metal metaphosphate array obtained by the method is used as a working electrode, a graphite sheet is used as a counter electrode, and silver/silver chloride is used as a reference electrode in a three-electrode system, the electrochemical workstation of CHI760E is used for carrying out electrodeposition, the electrolyte is N metal salt solution, the electrodeposition temperature is preferably 25-35 ℃, the number of electrodeposition cycles is 2-30, more preferably 5-15, and most preferably 15, the electrodeposition method is preferably cyclic voltammetry, the voltage is preferably-0.2-1.4V, and the metal monoatomic, cluster and particle array catalyst loaded with the metal metaphosphate can be obtained after a deposited sample is washed by deionized water and ethanol. The metal salt in the metal salt solution of N is preferably cobalt chloride, nickel nitrate, cobalt sulfate, ferrous sulfate, nickel sulfate, chloroplatinic acid, ruthenium chloride, iridium chloride, and palladium chloride.
The invention also provides the application of the metal monatomic, cluster and particle array catalyst loaded with the metal metaphosphate in an electrolytic cell in the full pH range, and the electrocatalytic hydrogen evolution performance of the metal monatomic, cluster and particle array catalyst loaded with the metal metaphosphate in the electrolyte in the full pH range is tested by using a CHI760E type electrochemical workstation.
The invention has the beneficial effects that:
the invention is characterized by consisting of a cyclic P 4 O 12 By M-O-P with MO 6 The carrier loaded metal catalyst formed by polyhedral connection greatly improves the stability of the catalyst in acidity and alkalinityAnd the stability of the catalyst in a neutral solution can reach thousands of hours, and the activity of the catalyst can exceed that of commercial platinum carbon within the full pH range and reach the international leading level.
Drawings
FIG. 1 is a scanning electron micrograph of a metallic nickel hydroxide nanosheet array prepared in example 1;
FIG. 2 is an infrared spectrum and corresponding unit cell schematic of a nickel metaphosphate array catalyst prepared in example 1 and a ruthenium monatin catalyst supported on nickel metaphosphate prepared in example 2;
FIG. 3 is a diagram of a nickel metal metaphosphate array catalyst prepared in example 1;
FIG. 4 is an electron micrograph of a nickel metaphosphate supported ruthenium monoatomic catalyst prepared in example 2;
FIG. 5 is a photograph of a spherical aberration electron microscope photograph of the ruthenium cluster catalyst supported on nickel metaphosphate prepared in example 3;
FIG. 6 is an electron micrograph of a nickel metaphosphate supported ruthenium particle catalyst prepared in example 4;
FIG. 7 is a graph of hydrogen evolution polarization under acidic conditions for the nickel metaphosphate array catalyst prepared in example 1 and the metal metaphosphate supported ruthenium monatomic, cluster and particle array catalysts prepared in examples 3, 4 and 5; wherein s represents a monoatomic atom c represents a cluster, and n represents a particle;
FIG. 8 is a hydrogen evolution polarization curve diagram of the nickel metaphosphate supported ruthenium particle catalyst prepared in example 5 under neutral conditions;
FIG. 9 is a hydrogen evolution polarization curve diagram of the nickel metaphosphate supported ruthenium particle catalyst prepared in example 5 under alkaline conditions;
fig. 10 is a graph of synchrotron radiation data of the metallic nickel metaphosphate array catalyst prepared in example 1, the nickel metaphosphate supported ruthenium monatomic catalyst prepared in example 2, the nickel metaphosphate supported ruthenium cluster catalyst prepared in example 3, and the nickel metaphosphate supported ruthenium particulate catalyst prepared in example 4.
Detailed Description
The present invention is further illustrated in detail below with reference to examples, in which the starting materials are all commercially available.
EXAMPLE 1 preparation of Metal Nickel Meta-phosphate array catalyst
The method comprises the following steps: preparation of transition Metal Nickel hydroxide arrays
1.2 mmol of nickel nitrate, 6 mmol of urea and 2.4 mmol of ammonium fluoride were dissolved in 30 ml of deionized water and stirred for 20 minutes to mix the solution uniformly. Next, the solution was transferred to a 50 ml reaction kettle. Cleaning the carbon cloth with diluted hydrochloric acid, ethanol and deionized water, obliquely inserting the carbon cloth into a reaction kettle with the size of 2cm multiplied by 4cm, sealing, and placing the reaction kettle into a forced air oven to react for 5 hours at the temperature of 110 ℃. And after natural cooling, repeatedly washing and drying by using ethanol and deionized water to obtain the nickel hydroxide nanosheet array. FIG. 1 is a scanning electron micrograph of the prepared metallic nickel hydroxide nanosheet array, wherein a is a scanning electron micrograph under a 10 micron scale, and b is a scanning electron micrograph under a 2 micron scale, which shows that the carbon cloth is completely covered by the extremely thin nickel hydroxide nanosheet array.
Step two: preparation of metal nickel metaphosphate array catalyst
Putting the nickel hydroxide nanosheet array obtained in the step one into a porcelain boat, putting 1.5g of sodium hypophosphite powder into another porcelain boat, then putting the two porcelain boats into a quartz tube, wherein the magnetic boat containing the nickel hydroxide nanosheet array is placed in a high-temperature area, the magnetic boat containing the sodium hypophosphite powder is placed in a low-temperature area, heating is carried out at 350 ℃ for 2 hours under the protection of argon, and cooling to room temperature is carried out, so that the metal nickel metaphosphate array catalyst is obtained.
The nickel metaphosphate array catalyst prepared in example 1 has a unit cell pattern as shown in FIG. 2b as determined by infrared spectroscopy (FIG. 2 a), and it can be seen from this structure that the nickel metaphosphate array catalyst is formed of a cyclic P 4 O 12 By M-O-P and MO 6 A structure formed by connecting polyhedrons. FIG. 3 is a scanning electron micrograph of a nickel metaphosphate array catalyst, wherein a is a 5 micron scale and b is a 1 micron scale, and the results show that during the high temperature phosphating processThe original flaky nickel hydroxide nanosheet is converted into a nickel metaphosphate array with a three-dimensional framework structure.
Example 2 preparation of nickel metaphosphate Supported ruthenium monatomic catalyst
The method comprises the following steps: preparing a transition metal nickel hydroxide array;
this step is the same as the first step in example 1.
Step two: preparing a metal nickel metaphosphate array catalyst;
this step is the same as step two in example 1.
Step three: preparing a ruthenium monatomic catalyst loaded on nickel metaphosphate;
and D, performing electrodeposition in a three-electrode system with the nickel metaphosphate array catalyst obtained in the step two as a working electrode, the graphite sheet as a counter electrode and the saturated calomel electrode as a reference electrode. The electrolyte was a 1mM ruthenium chloride and 0.1M sulfuric acid solution. In the Cyclic Voltammetry mode of an electrochemical workstation of the type CHI760E, 5 cycles were deposited at 30 ℃ with a potential interval of-0.5 to 0.4 volts relative to a saturated calomel electrode. And washing the electrodeposited sample by ethanol and water to obtain the nickel metaphosphate supported ruthenium monatomic catalyst.
Fig. 4 is a photograph of a spherical aberration electron microscope of the ruthenium monatomic catalyst supported by nickel metaphosphate prepared in example 2, wherein a is a photograph of a spherical aberration electron microscope under a 5 nm scale, b is a photograph of a spherical aberration electron microscope under a 2 nm scale, and bright spots in the photograph are ruthenium atoms distributed in a monatomic state. From the synchrotron radiation data (fig. 10), it was confirmed that ruthenium atoms were supported on the rod-shaped nickel metaphosphate surface.
Example 3 preparation of nickel metaphosphate Supported ruthenium Cluster catalyst
The method comprises the following steps: preparing a transition metal nickel hydroxide array;
this step is the same as step one in example 1.
Step two: preparing a metal nickel metaphosphate array catalyst;
this step is the same as step two in example 1.
Step three: preparing a ruthenium cluster catalyst loaded on nickel metaphosphate;
and D, performing electrodeposition in a three-electrode system with the nickel metaphosphate array catalyst obtained in the step two as a working electrode, the graphite sheet as a counter electrode and the saturated calomel electrode as a reference electrode. The electrolyte was a 1mM ruthenium chloride and 0.1M sulfuric acid solution. In the Cyclic Voltammetry mode of an electrochemical workstation of the type CHI760E, 10 cycles are deposited at 30 ℃ with a potential interval of-0.5 to 0.4 volts relative to a saturated calomel electrode. And cleaning the electrodeposited sample by ethanol and water to obtain the nickel metaphosphate supported ruthenium cluster catalyst.
Fig. 5 is a photograph of a spherical aberration electron microscope photograph of the nickel metaphosphate-supported ruthenium cluster catalyst prepared in example 3, in which fig. a is a spherical aberration electron microscope photograph on a scale of 5 nm, and fig. b is a spherical aberration electron microscope photograph on a scale of 2 nm, and it can be seen from the figure that ruthenium atoms are aggregated into clusters having a particle diameter of about 1 nm, but there is no distinct lattice structure, and there is no crystal phase, and the clusters are ruthenium clusters. According to the synchrotron radiation data, the ruthenium cluster is supported on the surface of the rod-shaped nickel metaphosphate.
Example 4 preparation of a Nickel Meta-phosphate Supported ruthenium particulate catalyst
The method comprises the following steps: preparing a transition metal nickel hydroxide array;
this step is the same as the first step in example 1.
Step two: preparing a metal nickel metaphosphate array catalyst;
this step is the same as step two in example 1.
Step three: preparing a ruthenium cluster catalyst loaded on nickel metaphosphate;
and D, performing electrodeposition in a three-electrode system with the nickel metaphosphate array catalyst obtained in the step two as a working electrode, the graphite sheet as a counter electrode and the saturated calomel electrode as a reference electrode. The electrolyte was a 1mM ruthenium chloride and 0.1M sulfuric acid solution. 15 cycles were deposited at 30 ℃ in the Cyclic Voltammetry mode of an electrochemical workstation of the type CHI760E at a potential interval of-0.5 to 0.4 volts relative to the saturated calomel electrode. And washing the electrodeposited sample by ethanol and water to obtain the nickel metaphosphate supported ruthenium particle catalyst.
Fig. 6 is a photograph of the nickel metaphosphate-supported ruthenium particle catalyst obtained in example 4 by using a spherical aberration electron microscope, wherein a is a photograph of the catalyst on a 5 nm scale by using a spherical aberration electron microscope, and b is a photograph of the catalyst on a 2 nm scale by using a spherical aberration electron microscope, and as can be seen from the figure, the ruthenium particle has a particle size of about 2 nm, has a distinct lattice structure, and is a ruthenium particle with good crystallinity. The lattice spacing of 0.22 nm in panel b corresponds to the 111 plane of ruthenium metal. From the synchrotron radiation data, it can be determined that the ruthenium particles are supported on the rod-shaped nickel metaphosphate surface.
Example 5 preparation of cobalt metaphosphate Supported platinum Mono-atom catalyst
The method comprises the following steps: preparing a transition metal cobalt hydroxide array;
this procedure is identical to the first procedure in example 1, with the only difference that 1.2 millimoles of nickel nitrate were replaced by cobalt nitrate.
Step two: preparing a metal cobalt metaphosphate array catalyst;
this step is the same as step two in example 1.
The prepared cobalt metaphosphate array catalyst has a unit cell model diagram similar to that shown in FIG. 1b by infrared spectroscopy, and it can be seen from this structure that the cobalt metaphosphate array catalyst is formed of a cyclic P 4 O 12 By M-O-P with MO 6 A structure formed by connecting polyhedrons.
Step three: preparing a cobalt metaphosphate supported platinum single-atom catalyst;
and D, performing electrodeposition in a three-electrode system with the cobalt metaphosphate array catalyst obtained in the step two as a working electrode, the graphite sheet as a counter electrode and the saturated calomel electrode as a reference electrode. The electrolyte was 1mM chloroplatinic acid and 0.1M sulfuric acid solution. In the Cyclic Voltammetry mode of an electrochemical workstation of the type CHI760E, 5 cycles were deposited at 30 ℃ with a potential interval of-0.5 to 0.4 volts relative to a saturated calomel electrode. And washing the electrodeposited sample by ethanol and water to obtain the cobalt metaphosphate supported platinum monatomic catalyst.
And (3) characterization: according to the photograph of the spherical aberration electron microscope, platinum is distributed in a monoatomic state, and the monoatomic load of platinum on the surface of the rodlike cobalt metaphosphate can be determined according to synchrotron radiation data.
Example 6 preparation of Iridium monatomic catalyst Supported with iron Meta-phosphate
The method comprises the following steps: preparing a transition metal ferric hydroxide array;
this procedure is identical to the first procedure in example 1, with the only difference that 1.2 millimoles of nickel nitrate were replaced by ferric nitrate.
Step two: preparing a metal meta-iron phosphate array catalyst;
this step is the same as step two in example 1.
The prepared metal meta-iron phosphate array catalyst has a unit cell model diagram similar to that shown in figure 1b by infrared spectrometry, and can be seen from the structure that the metal meta-iron phosphate array catalyst is formed by a ring P 4 O 12 By M-O-P with MO 6 A structure formed by connecting polyhedrons.
Step three: preparing an iridium monatomic catalyst loaded by ferric metaphosphate;
and D, performing electrodeposition in a three-electrode system with the metal iron metaphosphate array catalyst obtained in the step two as a working electrode, the graphite sheet as a counter electrode and the saturated calomel electrode as a reference electrode. The electrolyte was a 1mM solution of chloroiridic acid and 0.1M sulfuric acid. In the Cyclic voltametry mode of an electrochemical workstation of the model CHI760E, 5 cycles were deposited at 30 ℃ at a potential interval of-0.5 to 0.4 volts relative to a saturated calomel electrode. And washing the electrodeposited sample by ethanol and water to obtain the iridium monatomic catalyst loaded with the ferric metaphosphate.
And (3) characterization: according to the photograph of the spherical aberration electron microscope, the iridium is distributed in a monoatomic state, and the iridium monoatomic state is loaded on the surface of the rodlike iron metaphosphate according to the synchronous radiation data.
Performance characterization
(1) The catalysts were tested for hydrogen evolution performance in acidic solution (pH = 0)
The catalysts obtained in examples 2 to 6 were used as cathodes, graphite sheets as counter electrodes, and saturated calomel electrodes as reference electrodes, respectively, in a three-electrode system for hydrogen evolution performance test. The electrolyte was a 0.5M sulfuric acid solution. The materials were tested for hydrogen evolution in the Linear Sweep voltametry mode at an electrochemical workstation model CHI 760E.
It can be determined by hydrogen evolution polarization curve analysis that the catalysts prepared in examples 2 to 6 of the present invention all exhibit excellent hydrogen evolution performance under acidic conditions. Figure 7 shows hydrogen evolution polarization curves under acidic conditions for the nickel metaphosphate supported ruthenium monatomic, cluster and particle array catalysts of examples 2-4, all of which had a degree of performance improvement over the control sample carbon cloth and nickel metaphosphate, where the nickel metaphosphate supported ruthenium particles had the best hydrogen evolution performance, requiring only 23.3 mv of overpotential to achieve a current density of 10 ma/cm, and even better than the catalytic performance of commercial platinum carbon (requiring 25.0 mv of overpotential to achieve a current density of 10 ma/cm). Nickel metaphosphate supported ruthenium particles were shown to have the potential to replace commercial platinum carbon.
(2) The catalysts were tested for hydrogen evolution performance in neutral solution (pH = 7)
The catalysts obtained in examples 2 to 6 were used as cathodes, graphite sheets as counter electrodes, and saturated calomel electrodes as reference electrodes, respectively, in a three-electrode system for hydrogen evolution performance test. The electrolyte is 1M phosphate buffered saline. The materials were tested for hydrogen evolution in the Linear Sweep voltametry mode at an electrochemical workstation model CHI 760E.
It can be determined by hydrogen evolution polarization curve analysis that the catalysts prepared in examples 2 to 6 of the present invention all exhibit excellent hydrogen evolution performance under neutral conditions. Fig. 8 shows hydrogen evolution polarization curves for neutral conditions for the nickel metaphosphate supported ruthenium particle array catalyst obtained in example 4 and the prior art catalyst, where the nickel metaphosphate supported ruthenium particles have the best hydrogen evolution performance, requiring only 35.4 mv of overpotential to achieve a current density of 10 ma/cm, superior to that of commercial platinum carbon (43.2 mv of overpotential to achieve a current density of 10 ma/cm). The result shows that the ruthenium particles loaded by the nickel metaphosphate still have good hydrogen evolution performance under the acidic condition.
(3) The catalysts were tested for hydrogen evolution performance in alkaline solution (pH = 14)
The catalysts obtained in examples 2 to 6 were used as cathodes, graphite sheets as counter electrodes, and saturated calomel electrodes as reference electrodes, respectively, in a three-electrode system for hydrogen evolution performance test. The electrolyte was 1M potassium hydroxide solution. The materials were tested for hydrogen evolution in the Linear Sweep volt measurement mode at an electrochemical workstation of type CHI 760E.
It can be confirmed by analysis of hydrogen evolution polarization curves that the catalysts prepared in examples 2 to 6 of the present invention all exhibit excellent hydrogen evolution performance under alkaline conditions. Fig. 9 shows hydrogen evolution polarization curves of the nickel metaphosphate supported ruthenium particle array catalyst obtained in example 4 and the existing catalyst under alkaline conditions, wherein the nickel metaphosphate supported ruthenium particles have the best hydrogen evolution performance, which requires only 35.9 mv of overpotential to reach a current density of 10 ma/cm, and is also superior to the catalytic performance of commercial platinum carbon (40.3 mv of overpotential to reach a current density of 10 ma/cm). Indicating that the nickel metaphosphate loaded ruthenium particles still have hydrogen evolution performance exceeding that of commercial platinum carbon under alkaline conditions.
The embodiment of the invention discloses a novel nickel metaphosphate supported ruthenium single atom, cluster and particle array catalyst and a preparation method thereof.
The experimental results show that the hydrogen evolution performance of the novel nickel metaphosphate supported ruthenium monoatomic, cluster and particle array catalyst can exceed that of the commercialized platinum carbon by controlling the experimental parameters and changing the experimental conditions.
Claims (12)
1. A transition metal catalyst comprising a transition metal N and a carrier supporting the transition metal N, wherein the carrier is composed of a cyclic P 4 O 12 By M-O-P and MO 6 The polyhedron is connected; the size of the transition metal N is less than 10nm; wherein M is a transition metal.
2. The catalyst according to claim 1, wherein the support has a rod array structure; the transition metal is supported on the rod-shaped surface.
3. The catalyst according to claim 1, wherein the transition metal N is selected from iron, cobalt, nickel, platinum, ruthenium, iridium or palladium; the transition metal M is selected from iron, cobalt and nickel.
4. The catalyst according to claim 1, wherein the transition metal N is a transition metal monoatomic atom, a transition metal cluster, or a transition metal particle.
5. A method for preparing the catalyst of claim 1, wherein the transition metal N is deposited on the support by electrodeposition.
6. The method according to claim 5, wherein the carrier is prepared by the following method:
the method comprises the following steps: preparing transition metal M hydroxide;
step two: and (4) preparing the transition metal metaphosphate from the transition metal M hydroxide prepared in the first step by a chemical vapor deposition method.
7. The method according to claim 6, wherein the product obtained in the first step is a transition metal M hydroxide array.
8. The method according to claim 7, wherein the transition metal M hydroxide array is prepared by: fully dissolving a transition metal M salt in a reaction kettle, and then obliquely inserting a conductive substrate into the reaction kettle; reacting for 5 hours at 100-200 ℃; and after natural cooling, cleaning to obtain the transition metal M hydroxide array.
9. The method according to claim 8, wherein the conductive substrate is carbon cloth, carbon paper, nickel mesh, copper mesh, titanium mesh or titanium sheet.
10. The method according to claim 8, wherein the transition metal M salt is selected from cobalt nitrate, nickel nitrate, ferrous sulfate, and nickel sulfate.
11. The preparation method according to claim 6, wherein the second step is specifically: respectively placing the transition metal M hydroxide array and the hypophosphite into two magnetic boats, and placing the two magnetic boats into a tubular furnace to react for 1-3 hours at the temperature of 250-600 ℃; and cooling and taking out to obtain the metaphosphate array.
12. The method of claim 5, wherein the electrodeposition temperature is 25 to 35 ℃.
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| CN114807996A (en) * | 2022-04-13 | 2022-07-29 | 北京工业大学 | Preparation method of monatomic platinum-loaded transition metal phosphide hydrogen evolution catalyst |
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