CN111545250A - Ruthenium catalyst with efficient electrocatalytic full-hydrolytic performance and application thereof - Google Patents
Ruthenium catalyst with efficient electrocatalytic full-hydrolytic performance and application thereof Download PDFInfo
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- CN111545250A CN111545250A CN202010435278.7A CN202010435278A CN111545250A CN 111545250 A CN111545250 A CN 111545250A CN 202010435278 A CN202010435278 A CN 202010435278A CN 111545250 A CN111545250 A CN 111545250A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 143
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 76
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 93
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000010453 quartz Substances 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001816 cooling Methods 0.000 claims abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 11
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 11
- 239000012498 ultrapure water Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 229940078494 nickel acetate Drugs 0.000 claims description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- NSNVGCNCRLAWOJ-UHFFFAOYSA-N [N+](=O)([O-])[O-].N(=O)[Ru+2].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].N(=O)[Ru+2].[N+](=O)([O-])[O-] NSNVGCNCRLAWOJ-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- RFYYQFJZJJCJNT-UHFFFAOYSA-N pentane-2,4-dione;ruthenium Chemical compound [Ru].CC(=O)CC(C)=O RFYYQFJZJJCJNT-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- 238000001075 voltammogram Methods 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000004744 fabric Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 229910021607 Silver chloride Inorganic materials 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 238000011056 performance test Methods 0.000 description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000001027 hydrothermal synthesis Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 7
- 229920000557 Nafion® Polymers 0.000 description 6
- 238000004502 linear sweep voltammetry Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 230000007547 defect Effects 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
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J35/23—
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- B01J35/33—
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- B01J35/399—
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- B01J35/615—
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- C—CHEMISTRY; METALLURGY
- 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
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- 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
- C25B11/095—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 of the compounds being organic
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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
Abstract
The invention discloses a ruthenium catalyst with high-efficiency electrocatalytic full-hydrolytic performance and application thereof, wherein the ruthenium catalyst comprises a ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst, and the preparation method comprises the following steps: dissolving cobalt metal salt, nickel metal salt and ruthenium metal salt in ultrapure water, dissolving aromatic carboxylic acid in an organic solvent, mixing the two solutions, heating for reaction, cooling, performing suction filtration, washing with water, and drying; and transferring the dried solid into a quartz boat, then placing the quartz boat into a tube furnace, carrying out high-temperature calcination in an ammonia atmosphere, and then naturally cooling to room temperature to obtain the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst. The catalyst has high specific surface area and a porous structure, and the reaction process is green and pollution-free and has good full hydrolysis reaction effect.
Description
Technical Field
The invention belongs to the field of nano materials and electrochemistry, and particularly relates to a ruthenium catalyst with high-efficiency electrocatalytic full-hydrolytic performance and application thereof.
Background
At present, with the continuous use of fossil fuels, fossil fuels face the problem of exhaustion. Meanwhile, environmental problems due to excessive use of fossil fuels are also becoming more serious. Therefore, a clean and sustainable energy utilization method is sought. The hydrogen has the characteristics of cleanness, high energy efficiency and the like, and is an ideal energy source in the future. Oxygen is not only a substance necessary for organisms, but also an important raw material in chemical production. The electrochemical full-hydrolytic water has the advantages of low cost and high efficiency, and is a promising method for producing high-purity hydrogen and oxygen. However, the practical application of the full-hydrolyzed water for large-scale hydrogen and oxygen production is greatly hindered due to the large overpotential required by the two half reactions (hydrogen evolution reaction and oxygen evolution reaction) in the electrochemical full-hydrolyzed water. At present, most of electrochemical full-hydrolytic catalysts are noble metal catalysts, such as Pt-based materials, which have excellent electrocatalytic Hydrogen Evolution Reaction (HER) performance; oxides of Ru and Ir have excellent electrocatalytic Oxygen Evolution Reaction (OER) performance. However, the noble metal catalysts have limited applications due to their disadvantages of high cost, low storage capacity, poor catalytic stability, etc. Based on this, it is a very desirable new way to develop a highly efficient electrocatalytic total hydrolysis.
Electrocatalytic total hydrolysis has been studied extensively in recent years. At present, the research on the catalysts based on two-dimensional Metal Organic Framework (MOF) applied to electrocatalysis is less, and the catalytic activity of the catalysts is to be improved.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a ruthenium catalyst with high-efficiency electrocatalytic full-hydrolytic performance and application thereof.
The ruthenium catalyst with high-efficiency electrocatalytic full-hydrolytic performance is characterized by comprising a ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst, and the preparation method comprises the following steps:
1) dissolving cobalt metal salt, nickel metal salt and ruthenium metal salt in ultrapure water, dissolving aromatic carboxylic acid in an organic solvent, adding the two solutions into a reaction kettle, uniformly mixing, heating for reaction, and cooling to room temperature after the reaction is finished;
2) carrying out suction filtration on the reaction liquid cooled in the step 1), washing filter residues with water, and finally carrying out vacuum drying;
3) and (3) transferring the solid obtained by drying in the step 2) into a quartz boat, then placing the quartz boat into a tube furnace, carrying out high-temperature calcination in an ammonia atmosphere, and then naturally cooling to room temperature to obtain the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst.
The ruthenium catalyst with high-efficiency electrocatalytic full-hydrolytic performance is characterized in that in the step 1), cobalt metal salt is cobalt acetate, cobalt nitrate or cobalt chloride; the nickel metal salt is nickel acetate, nickel nitrate or nickel chloride; the ruthenium metal salt is ruthenium trichloride, nitrosyl ruthenium nitrate or acetylacetone ruthenium; the aromatic carboxylic acid is terephthalic acid; the organic solvent is N, N-dimethylacetamide, chloroform, dichloromethane, methanol or ethanol.
The ruthenium catalyst with high-efficiency electrocatalytic full-hydrolytic performance is characterized in that in the step 1), the heating reaction temperature is 100-200 ℃, and preferably 150 ℃; the heating reaction time is 1-5 h, preferably 3 h.
The ruthenium catalyst with high-efficiency electrocatalytic full-hydrolytic performance is characterized in that in the step 1), the molar ratio of the cobalt metal salt to the nickel metal salt to the ruthenium metal salt to the aromatic carboxylic acid is 1: 0.5-1.5: 8-12, and the preferred molar ratio is 1: 1: 1: 10.
The ruthenium catalyst with high-efficiency electrocatalytic full-hydrolytic performance is characterized in that in the step 3), the high-temperature calcination temperature is 550-650 ℃, and preferably 600 ℃; the calcination time is 1-5 h, preferably 3 h.
The ruthenium catalyst with high-efficiency electrocatalytic full-hydrolytic performance is characterized by also comprising a ruthenium-loaded two-dimensional metal organic framework catalyst, and the preparation method of the ruthenium-loaded two-dimensional metal organic framework catalyst comprises the following steps:
s1: mixing the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst and Ru (acac)3Putting the mixture into a mortar and fully grinding;
s2: and (4) transferring the mixture obtained by grinding in the step (S1) to a quartz boat, then placing the quartz boat in a tube furnace, carrying out high-temperature calcination in a nitrogen atmosphere, and finally naturally cooling to room temperature to obtain the ruthenium-loaded two-dimensional metal organic framework catalyst.
The ruthenium catalyst with high-efficiency electrocatalytic full-hydrolytic performance is characterized in that in step S1, the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst and Ru (acac)3The mass ratio of (A) to (B) is 1-5: 1, preferably 2.5: 1; in the step S2, the high-temperature calcination temperature is 250-350 ℃, and preferably 300 ℃; the high-temperature calcination time is 2-5 h, preferably 3 h.
The ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst and the ruthenium-loaded two-dimensional metal organic framework catalyst prepared by the invention can be applied to electrolytic water reaction.
Wherein, when the ruthenium doped nickel-cobalt two-dimensional metal organic framework catalyst is independently applied: a three-electrode system testing device is adopted, a platinum sheet is used as a counter electrode, the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, and inorganic alkaline aqueous solution is used as electrolyte to carry out OER reaction.
Wherein when the ruthenium-supported two-dimensional metal organic framework catalyst is independently applied: a three-electrode system testing device is adopted, a carbon rod is used as a counter electrode, the ruthenium-loaded two-dimensional metal organic framework catalyst is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, and inorganic alkaline aqueous solution is used as electrolyte to carry out HER reaction.
When the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst and the ruthenium-loaded two-dimensional metal organic framework catalyst prepared by the invention are applied together: the method comprises the steps of taking a ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst as a cathode catalyst, taking a ruthenium-loaded two-dimensional metal organic framework catalyst as an anode catalyst, and taking an inorganic alkali aqueous solution as an electrolyte to carry out full hydrolysis reaction.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
(1) the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst prepared by the invention is of a two-dimensional layered structure, and has smaller porosity and larger external surface area; the introduction of trace ruthenium element generates Co-Ru bond, which reduces the free energy delta G of the speed-determining step (OOH generation) of OER reaction, and the OER performance of the ruthenium doped nickel-cobalt two-dimensional metal organic framework catalyst is obviously improved. The prepared ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst is further loaded with ruthenium, the metal particles of the loaded ruthenium catalyst are small, the dispersion degree of metal ions is high, and the catalytic cycle stability is good, the catalyst is used for electrocatalytic full-hydrolytic reaction, electrons which are not coordinated by trivalent ruthenium provide anchoring sites for ruthenium cluster loading, and the ruthenium nanoparticles are also active sites of cathode reaction HER; the two catalysts respectively have excellent OER and HER catalytic performances, and the electrocatalytic full-hydrolysis potential of the two catalysts is superior to that of most reported ruthenium-based catalysts.
(2) According to the invention, the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst is successfully synthesized by carrying out heteroatom doping on the known synthesized two-dimensional metal organic framework in a simple hydrothermal mode to cause point defects, the two-dimensional structure of the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst is not damaged after doping, the performance of the OER under an alkaline condition is also improved, the preparation method is simple, and complex and high-price auxiliary equipment is not needed.
Drawings
FIG. 1a is an SEM image at 500nm of a ruthenium doped nickel-cobalt two-dimensional metal organic framework catalyst powder prepared in example 1;
FIG. 1b is an SEM image at 200nm of the ruthenium doped nickel-cobalt two-dimensional metal organic framework catalyst powder prepared in example 1;
FIG. 1c is an SEM image of the ruthenium doped nickel-cobalt two-dimensional metal organic framework catalyst powder prepared in example 1 at 100 nm;
FIG. 2 is an SEM image at 200nm of the ruthenium supported two-dimensional metal organic framework catalyst powder prepared in example 1;
FIG. 3a is a TEM image at 20nm of a ruthenium-supported two-dimensional metal-organic framework catalyst powder prepared in example 1;
FIG. 3b is a TEM image at 10nm of a ruthenium-supported two-dimensional metal-organic framework catalyst powder prepared in example 1;
FIG. 4 shows the nickel-cobalt two-dimensional metal organic framework catalyst of example 2, the ruthenium doped nickel-cobalt two-dimensional metal organic framework catalysts of examples 1, 3 and 4, and the RuO of example 52Linear sweep voltammogram of OER for/C catalyst;
FIG. 5 is a plot of linear sweep voltammetry for HER for the ruthenium supported two-dimensional metal organic framework catalysts of examples 1-4 and the Pt/C catalyst of example 5;
FIG. 6 shows an electrode prepared in example 1 and using commercial Pt/C RuO2the/C and carbon cloth are used as a control, and the linear sweep voltammogram is applied to the full water splitting.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
1) dissolving 124.5 mg of cobalt acetate, 88.3 mg of nickel acetate and 10.4 mg of ruthenium trichloride in 15.0 mL of ultrapure water; 3.0 mg of terephthalic acid was dissolved in 15.0 mL of N, N-dimethylacetamide.
2) Mixing the two solutions obtained in the step 1) and placing the two solutions in a hydrothermal kettle with the capacity of 50 mL, then placing the hydrothermal kettle in an oven, carrying out hydrothermal reaction at 150 ℃, and cooling the reaction liquid to room temperature after the reaction is finished;
3) carrying out suction filtration on the reaction liquid cooled in the step 2) to obtain a product after hydrothermal reaction, washing the product with ultrapure water, and finally putting the product into a vacuum drying oven for vacuum drying at 60 ℃;
4) putting the solid obtained by drying in the step 3) into a quartz boat, then putting the quartz boat into a tube furnace, keeping the temperature of the quartz boat at 600 ℃ for 3h under the atmosphere of ammonia gas, and then naturally cooling the quartz boat to room temperature to obtain the ruthenium doped nickel-cobalt two-dimensional metal organic framework catalyst powder (characterized by BET, and the specific surface area of the ruthenium doped nickel-cobalt two-dimensional metal organic framework catalyst powder is 253.41 m/g);
5) mixing the ruthenium doped nickel-cobalt two-dimensional metal organic framework catalyst powder obtained in the step 4) with Ru (acac)3Placing the mixture powder in a mortar and fully grinding the mixture powder in a mass ratio of 5:2, placing the ground mixture powder in a quartz boat, heating the quartz boat for 3 hours at 300 ℃ in a nitrogen atmosphere, and finally naturally cooling the quartz boat to room temperature to obtain the ruthenium-supported two-dimensional metal organic framework catalyst (characterized by BET and having a specific surface area of 219.73 m/g).
SEM images of the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst obtained in step 4) of example 1 at 500nm, 200nm, and 100nm are respectively shown in fig. 1a, 1b, and 1c, and it can be seen that the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst obtained in example 1 has a multilayer nanosheet structure, that is, the two-dimensional MOF material is obtained in this example.
SEM observation of the ruthenium-supported two-dimensional metal organic framework catalyst obtained in step 5) of example 1 was performed, and the result is shown in fig. 2. As can be seen from fig. 2, the ruthenium supported two-dimensional metal organic framework catalyst has a sheet structure, indicating that the sheet structure is not destroyed after further calcination treatment under nitrogen atmosphere. Then, for the ruthenium-supported two-dimensional metal organic framework catalyst obtained in step 5) of example 1, the results of TEM images at 20nm, 10nm and 5nm are shown in FIG. 3a and FIG. 3b, respectively. As can be seen from fig. 3a and 3b, the support of the catalyst exhibits an unordered sheet structure, and the supported ruthenium nanoparticles are uniformly distributed on the support.
The catalytic performance of the catalyst prepared in example 1 was tested by the following specific method:
the preparation of the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst electrode comprises the steps of weighing 4 mg of the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst prepared in the step 4) of the embodiment 1, adding 900 mu L of ethanol and 100 mu L of Nafion solution (the mass fraction of the Nafion solution is 5 percent), carrying out ultrasonic treatment for 0.5 hour, completely dispersing the catalyst in the ethanol to obtain uniform catalyst slurry, cutting the carbon cloth to about 1 × 1 cm2And (3) taking 0.2 mu L of the prepared catalyst slurry, uniformly dripping the catalyst slurry on carbon cloth, and directly taking the catalyst slurry as a working electrode after natural drying.
A ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst electrode is used as a working electrode, a platinum sheet is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. The electrocatalytic performance test was performed at room temperature using the CHI760E three-electrode electrolytic cell system of shanghai chenghua; the electrolyte used was a 1mol/L KOH aqueous solution, oxygen was first introduced for 0.5 hour before OER measurement to saturate the solution with oxygen, the sweep rate of linear sweep voltammetry was 5mV/s, and the linear sweep voltammogram of the Ru-doped Ni-Co two-dimensional metal-organic framework catalyst of example 1 for OER reaction is shown in FIG. 4.
The preparation process of the ruthenium-loaded two-dimensional metal organic framework catalyst electrode is the same as that of the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst electrode, and the difference is only that the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst is replaced by the ruthenium-loaded two-dimensional metal organic framework catalyst with the same quality.
A ruthenium-loaded two-dimensional metal organic frame catalyst electrode is used as a working electrode, a carbon rod is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. The electrocatalytic performance test was performed at room temperature using the CHI760E three-electrode electrolytic cell system of shanghai chenghua; the electrolyte used was 1mol/L KOH aqueous solution, and hydrogen was first introduced for 0.5 hour before HER test to saturate the solution with oxygen, the sweep rate of linear sweep voltammetry was 5mV/s, and the linear sweep voltammogram of the ruthenium supported two-dimensional metal organic framework catalyst of example 1 for HER reaction is shown in FIG. 5.
The ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst electrode and the ruthenium-supported two-dimensional metal organic framework catalyst electrode prepared in example 1 were applied to electrolyzed water: the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst electrode is used as an anode, the ruthenium-loaded two-dimensional metal organic framework catalyst electrode is used as a cathode, and the Ag/AgCl electrode is used as a reference electrode. The electrocatalytic performance test was performed at room temperature using the CHI760E three-electrode electrolytic cell system of shanghai chenghua; the electrolyte used was a 1mol/L KOH aqueous solution, the sweep rate of linear sweep voltammetry was 5mV/s, and the results of the linear sweep voltammogram are shown in FIG. 6.
Using commercial Pt/C RuO2the/C electrode pair was applied together to electrolyze water for comparison: wherein Pt/C electrode (Pt loading is 20%) is used as a cathode, and RuO is used2the/C electrode is used as an anode, and the Ag/AgCl electrode is used as a reference electrode. The electrocatalytic performance test was performed at room temperature using the CHI760E three-electrode electrolytic cell system of shanghai chenghua; the electrolyte used was a 1mol/L KOH aqueous solution, the sweep rate of linear sweep voltammetry was 5mV/s, and the results of the linear sweep voltammogram are shown in FIG. 6.
The carbon cloth electrode is applied to electrolyzed water for comparison: the anode and the cathode both adopt carbon cloth electrodes, and an Ag/AgCl electrode is used as a reference electrode. The electrocatalytic performance test was performed at room temperature using the CHI760E three-electrode electrolytic cell system of shanghai chenghua; the electrolyte used was a 1mol/L KOH aqueous solution, the sweep rate of linear sweep voltammetry was 5mV/s, and the results of the linear sweep voltammogram are shown in FIG. 6.
The electrode prepared from this example 1 was used with commercial Pt/C RuO2The linear sweep voltammogram for the application to full hydrolysis of water is shown in FIG. 6, using/C and carbon cloth as controls. As can be seen from fig. 6, the electrode prepared in example 1 has a better catalytic reaction effect in the full hydrolysis reaction.
Example 2:
1) dissolving 124.5 mg of cobalt acetate and 88.3 mg of nickel acetate in 15.0 mL of ultrapure water; dissolving 3.0 mg of terephthalic acid in 15.0 mL of N, N-dimethylacetamide;
2) mixing the two solutions obtained in the step 1) and placing the two solutions in a hydrothermal kettle with the capacity of 50 mL, then placing the hydrothermal kettle in an oven, carrying out hydrothermal reaction at 150 ℃, and cooling the reaction liquid to room temperature after the reaction is finished;
3) carrying out suction filtration on the reaction liquid cooled in the step 2) to obtain a product after hydrothermal reaction, washing the product with ultrapure water, and finally putting the product into a vacuum drying oven for vacuum drying at 60 ℃;
4) placing the solid obtained by drying in the step 3) into a quartz boat, placing the quartz boat into a tube furnace, keeping the quartz boat at 600 ℃ for 3h in an ammonia atmosphere, and then naturally cooling to room temperature to obtain an ammonia-treated nickel-cobalt two-dimensional metal organic framework catalyst;
5) mixing the nickel-cobalt two-dimensional metal organic framework catalyst powder obtained in the step 4) with Ru (acac)3And (2) fully grinding the mixture in a mortar according to the mass ratio of 5:2, placing the ground mixture powder in a quartz boat, heating the quartz boat for 3 hours at the temperature of 300 ℃ in a nitrogen atmosphere, and finally naturally cooling the quartz boat to room temperature to obtain the ruthenium-loaded two-dimensional metal organic framework catalyst.
Example 2 electrode preparation and electrode testing process conditions the same as in example 1, the linear sweep voltammogram of the nickel-cobalt two-dimensional metal organic framework catalyst of example 2 for OER reaction is shown in fig. 4, and the linear sweep voltammogram of the ruthenium supported two-dimensional metal organic framework catalyst of example 2 for HER reaction is shown in fig. 5.
Example 3:
1) dissolving 124.5 mg of cobalt acetate, 88.3 mg of nickel acetate and 5.2 mg of ruthenium trichloride in 15.0 mL of ultrapure water; dissolving 3.0 mg of terephthalic acid in 15.0 mL of N, N-dimethylacetamide;
2) mixing the two solutions obtained in the step 1) and placing the two solutions in a hydrothermal kettle with the capacity of 50 mL, then placing the hydrothermal kettle in an oven, carrying out hydrothermal reaction at 150 ℃, and cooling the reaction liquid to room temperature after the reaction is finished;
3) carrying out suction filtration on the reaction liquid cooled in the step 2) to obtain a product after hydrothermal reaction, washing the product with ultrapure water, and finally putting the product into a vacuum drying oven for vacuum drying at 60 ℃;
4) putting the solid obtained by drying in the step 3) into a quartz boat, then putting the quartz boat into a tube furnace, keeping the quartz boat at 600 ℃ for 3h in an ammonia atmosphere, and then naturally cooling to room temperature to obtain ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst powder treated by ammonia;
5) mixing the ruthenium doped nickel-cobalt two-dimensional metal organic framework catalyst powder obtained in the step 4) with Ru (acac)3Placing into a mortar at a mass ratio of 5:2, grinding, placing the ground mixture powder into a quartz boat, and adding into the quartz boat under nitrogen atmosphere at 300 deg.CHeating for 3h, and finally naturally cooling to room temperature to obtain the ruthenium-loaded two-dimensional metal organic framework catalyst.
Example 3 electrode preparation and electrode testing process conditions the same as in example 1, the linear sweep voltammogram for the OER reaction using the ruthenium doped nickel-cobalt two-dimensional metal organic framework catalyst of example 3 is shown in fig. 4, and the linear sweep voltammogram for the HER reaction using the ruthenium supported two-dimensional metal organic framework catalyst of example 3 is shown in fig. 5.
Example 4:
1) dissolving 124.5 mg of cobalt acetate, 88.3 mg of nickel acetate and 15.6 mg of ruthenium trichloride in 15.0 mL of ultrapure water; dissolving 3.0 mg of terephthalic acid in 15.0 mL of N, N-dimethylacetamide;
2) mixing the two solutions obtained in the step 1) and placing the two solutions in a hydrothermal kettle with the capacity of 50 mL, then placing the hydrothermal kettle in an oven, carrying out hydrothermal reaction at 150 ℃, and cooling the reaction liquid to room temperature after the reaction is finished;
3) carrying out suction filtration on the reaction liquid cooled in the step 2) to obtain a product after hydrothermal reaction, washing the product with ultrapure water, and finally putting the product into a vacuum drying oven for vacuum drying at 60 ℃;
4) putting the solid obtained by drying in the step 3) into a quartz boat, then putting the quartz boat into a tube furnace, keeping the quartz boat at 600 ℃ for 3h in an ammonia atmosphere, and then naturally cooling to room temperature to obtain ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst powder treated by ammonia;
5) mixing the ruthenium doped nickel-cobalt two-dimensional metal organic framework catalyst powder obtained in the step 4) with Ru (acac)3And (2) fully grinding the mixture in a mortar according to the mass ratio of 5:2, placing the ground mixture powder in a quartz boat, heating the quartz boat for 3 hours at the temperature of 300 ℃ in a nitrogen atmosphere, and finally naturally cooling the quartz boat to room temperature to obtain the ruthenium-loaded two-dimensional metal organic framework catalyst.
Example 4 electrode preparation and electrode testing process conditions the same as in example 1, the linear sweep voltammogram of the ruthenium doped nickel-cobalt two-dimensional metal organic framework catalyst of example 4 for OER reaction is shown in fig. 4, and the linear sweep voltammogram of the ruthenium supported two-dimensional metal organic framework catalyst of example 4 for HER reaction is shown in fig. 5.
Example 5:
with RuO2The performance test method of the comparative sample with/C as OER reaction is as follows: weighing 4 mg of RuO2Adding the catalyst/C into a 4mL centrifuge tube, adding 900 mu L ethanol and 100 mu L Nafion solution (the mass fraction of the Nafion solution is 5%), performing ultrasonic treatment for 0.5 hour, completely dispersing the catalyst in the ethanol to obtain uniform catalyst slurry, and cutting a carbon cloth to about 1 × 1 cm2And (3) dripping 0.2 mu L of dispersed catalyst slurry on carbon cloth, naturally drying, and directly using as a working electrode, a platinum sheet as a counter electrode, and an Ag/AgCl electrode as a reference electrode. The electrocatalytic performance test was performed at room temperature using the CHI760E three-electrode electrolytic cell system of shanghai chenghua; the electrolyte is 1mol/L KOH aqueous solution, oxygen is firstly introduced for 0.5h before OER test is carried out, so that the hydrogen in the solution is saturated, and the scanning rate of the linear scanning voltammetry is 5 mV/s.
Taking Pt/C (Pt load is 20%) as a comparative sample of HER reaction, the performance test method comprises the steps of weighing 4 mgPt/C, adding the weighed Pt/C into a 4mL centrifuge tube, adding 900 mu L ethanol and 100 mu L Nafion solution (the mass fraction of the Nafion solution is 5%), carrying out ultrasonic treatment for 0.5 hour, completely dispersing the catalyst into the ethanol to obtain uniform catalyst slurry, cutting the carbon cloth to about 1 × 1 cm2And (3) dripping 0.2 mu L of dispersed catalyst slurry on carbon cloth, naturally drying, and directly using as a working electrode, a carbon rod as a counter electrode, and an Ag/AgCl electrode as a reference electrode. The electrocatalytic performance test was performed at room temperature using the CHI760E three-electrode electrolytic cell system of shanghai chenghua; the electrolyte is 1mol/L KOH aqueous solution, hydrogen is firstly introduced for 0.5h before HER test is carried out, so that the hydrogen in the solution is saturated, and the scanning rate of linear scanning voltammetry is 5 mV/s.
Nickel-cobalt two-dimensional metal organic framework catalyst of example 2, ruthenium doped nickel-cobalt two-dimensional metal organic framework catalysts of examples 1, 3 and 4, and RuO of example 52The linear sweep voltammogram of the OER for the/C catalyst is shown in FIG. 4, from which it can be seen that: example 2 ruthenium-free doped nickel-cobalt two-dimensional metal organic framework catalyst, its OER PropertiesEnergy lower than RuO2a/C catalyst; and RuO2The OER performance of the/C catalyst was lower than the ruthenium doped nickel-cobalt two-dimensional metal organic framework catalysts of examples 1, 3 and 4. The reason for this is that: in the process of OER reaction, Co-Ni-MOL two-dimensional MOF takes Co as an active site of the reaction, and the introduction of trace ruthenium element generates Co-Ru bond, which reduces the free energy delta of the rate-determining step (generation of OOH) of the OER reactionGThereby leading to obvious improvement of the performance of the Co-Ni-MOL without introducing ruthenium.
The linear sweep voltammograms of the HER of the Pt/C supported two-dimensional metal organic framework catalysts of examples 1-4 and example 5 are shown in FIG. 5. from FIG. 5, it can be seen that "the test result curve of example 1 almost completely coincides with that of example 5, indicating that both performances are similar". The ruthenium-supported two-dimensional metal organic framework catalyst prepared by the invention has good HER performance, and the reasons are as follows: in the preparation process of the catalyst, trace ruthenium is doped into the nickel-cobalt two-dimensional metal organic framework material, and electrons which are not coordinated by trivalent ruthenium in the nickel-cobalt two-dimensional metal organic framework material provide anchor sites for subsequent loading of ruthenium clusters, so that the uniform dispersion loading of ruthenium active ingredients on the nickel-cobalt two-dimensional metal organic framework material is facilitated, and the ruthenium nanoparticles with small particle size are better active sites for cathode reaction HER.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (8)
1. The ruthenium catalyst with high-efficiency electrocatalytic full-hydrolytic performance is characterized by comprising a ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst, and the preparation method comprises the following steps:
1) dissolving cobalt metal salt, nickel metal salt and ruthenium metal salt in ultrapure water, dissolving aromatic carboxylic acid in an organic solvent, adding the two solutions into a reaction kettle, uniformly mixing, heating for reaction, and cooling to room temperature after the reaction is finished;
2) carrying out suction filtration on the reaction liquid cooled in the step 1), washing filter residues with water, and finally carrying out vacuum drying;
3) and (3) transferring the solid obtained by drying in the step 2) into a quartz boat, then placing the quartz boat into a tube furnace, carrying out high-temperature calcination in an ammonia atmosphere, and then naturally cooling to room temperature to obtain the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst.
2. The ruthenium catalyst with high-efficiency electrocatalytic full-hydrolytic capacity as claimed in claim 1, wherein in step 1), the cobalt metal salt is cobalt acetate, cobalt nitrate or cobalt chloride; the nickel metal salt is nickel acetate, nickel nitrate or nickel chloride; the ruthenium metal salt is ruthenium trichloride, nitrosyl ruthenium nitrate or acetylacetone ruthenium; the aromatic carboxylic acid is terephthalic acid; the organic solvent is N, N-dimethylacetamide, chloroform, dichloromethane, methanol or ethanol.
3. The ruthenium catalyst with high-efficiency electrocatalytic full-hydrolytic capacity as claimed in claim 1, wherein in the step 1), the temperature of the heating reaction is 100-200 ℃, preferably 150 ℃; the heating reaction time is 1-5 h, preferably 3 h.
4. The ruthenium catalyst with high-efficiency electrocatalytic full-hydrolytic capacity as claimed in claim 1, wherein in the step 1), the molar ratio of the cobalt metal salt, the nickel metal salt, the ruthenium metal salt and the aromatic carboxylic acid is 1: 0.5-1.5: 8-12, preferably 1: 1: 1: 10.
5. The ruthenium catalyst with high-efficiency electrocatalytic full-hydrolytic capacity as claimed in claim 1, wherein in the step 3), the high-temperature calcination temperature is 550-650 ℃, preferably 600 ℃; the calcination time is 1-5 h, preferably 3 h.
6. The ruthenium catalyst with high-efficiency electrocatalytic full-water splitting performance as claimed in claim 1, wherein the ruthenium catalyst further comprises a ruthenium-supported two-dimensional metal organic framework catalyst, and the preparation method of the ruthenium-supported two-dimensional metal organic framework catalyst comprises the following steps:
s1: mixing the ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst and Ru (acac)3Putting the mixture into a mortar and fully grinding;
s2: and (4) transferring the mixture obtained by grinding in the step (S1) to a quartz boat, then placing the quartz boat in a tube furnace, carrying out high-temperature calcination in a nitrogen atmosphere, and finally naturally cooling to room temperature to obtain the ruthenium-loaded two-dimensional metal organic framework catalyst.
7. The ruthenium catalyst with high-efficiency electro-catalytic full-hydrolytic capacity as claimed in claim 6, wherein in step S1, the ruthenium doped nickel-cobalt two-dimensional metal organic framework catalyst and Ru (acac)3The mass ratio of (A) to (B) is 1-5: 1, preferably 2.5: 1; in the step S2, the high-temperature calcination temperature is 250-350 ℃, and preferably 300 ℃; the high-temperature calcination time is 2-5 h, preferably 3 h.
8. The application of the ruthenium catalyst with high-efficiency electrocatalytic total water splitting performance in electrocatalytic total water splitting reaction as claimed in claim 6, characterized in that the total water splitting reaction is carried out by taking a ruthenium-doped nickel-cobalt two-dimensional metal organic framework catalyst as a cathode catalyst, taking a ruthenium-loaded two-dimensional metal organic framework catalyst as an anode catalyst and taking an inorganic alkaline aqueous solution as an electrolyte.
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