CN106984305B - A kind of high-efficient electrolytic water catalyst HRu4O8Micron bar and preparation method thereof - Google Patents
A kind of high-efficient electrolytic water catalyst HRu4O8Micron bar and preparation method thereof Download PDFInfo
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- CN106984305B CN106984305B CN201710311836.7A CN201710311836A CN106984305B CN 106984305 B CN106984305 B CN 106984305B CN 201710311836 A CN201710311836 A CN 201710311836A CN 106984305 B CN106984305 B CN 106984305B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002105 nanoparticle Substances 0.000 claims abstract description 21
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 239000008246 gaseous mixture Substances 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000001307 helium Substances 0.000 claims description 8
- 229910052734 helium Inorganic materials 0.000 claims description 8
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 5
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 4
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 2
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000003 Lead carbonate Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H aluminium carbonate Inorganic materials [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Inorganic materials [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000025 caesium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Inorganic materials [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 claims description 2
- OVFCVRIJCCDFNQ-UHFFFAOYSA-N carbonic acid;copper Chemical compound [Cu].OC(O)=O OVFCVRIJCCDFNQ-UHFFFAOYSA-N 0.000 claims description 2
- ONIOAEVPMYCHKX-UHFFFAOYSA-N carbonic acid;zinc Chemical compound [Zn].OC(O)=O ONIOAEVPMYCHKX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000009 copper(II) carbonate Inorganic materials 0.000 claims description 2
- 239000011646 cupric carbonate Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910000015 iron(II) carbonate Inorganic materials 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 claims description 2
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 2
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Inorganic materials [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 19
- 239000003792 electrolyte Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 3
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
-
- 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
A kind of high-efficient electrolytic water catalyst HRu4O8Micron bar, it is related to a kind of high-efficient electrolytic water catalyst HRu4O8Micron bar and preparation method thereof.The purpose of the present invention is to solve existing elctro-catalysts can not be simultaneously the problem of showing excellent catalytic performance and stability on HER and OER.HRu of the present invention4O8The atomic ratio of H:Ru:O is 1:4:8, HRu in micron bar4O8The diameter of micron bar is 1~10 μm, and length is 5~100 μm.The preparation method comprises the following steps: one, preparation RuO2Nanoparticle；Two, ruthenate micron bar is prepared；Three, HRu is prepared4O8Micron bar.HRu prepared by the present invention4O8Micron bar can be applied to HER, OER, and performance and stability are excellent.The present invention is applied to electro-catalysis field.
Description
Technical field
The present invention relates to a kind of high-efficient electrolytic water catalyst HRu4O8Micron bar and preparation method thereof.
Background technique
Hydrogen has many advantages, such as that abundance, calorific value are high and pollution-free, it is considered to be substitution can not be again as energy carrier
The ideal chose of raw fossil fuel.Electrolyzed alkaline water is due to its is environmental-friendly, low for equipment requirements, output stablizes, is highly-safe
Widely paid close attention to.Electrolysis water includes to produce hydrogen (HER) and produce oxygen (OER) two half-reactions, and Pt is considered as best HER
Catalyst, but Pt is expensive, and the activity in alkaline solution is poor with stability, seriously limits its extensive use；
RuO2It is considered as best one of OER catalyst, however its performance degradation is serious, and OER is four electronic processes, dynamics is slow
Slowly, overpotential is higher, so that the virtual voltage of electrolysis water is much higher than its theoretical value (1.23V), high energy consumption limitation resulting from
Its extensive use.
In order to reduce the overpotential of HER and OER, a series of HER and OER catalyst phases with greater activity and stability
After being reported.However, two distinct types of catalyst usually works under different pH environment, working environment it is incompatible
Property and prepare different catalyst and the high cost of bring limits its application in complete solution water.Therefore, it develops in alkalinity
In electrolyte simultaneously have the elctro-catalyst of excellent HER and OER Activity and stabill for reduce electrolysis water equipment manufacturing costs,
Simplify operation, energy saving have great importance.
Summary of the invention
The purpose of the present invention is to solve existing elctro-catalyst can not show on HER and OER simultaneously it is excellent
The problem of catalytic performance and stability, provides a kind of high-efficient electrolytic water catalyst HRu4O8Micron bar and preparation method thereof.
A kind of high-efficient electrolytic water catalyst HRu of the present invention4O8The atomic ratio of H:Ru:O is 1:4:8, HRu in micron bar4O8It is micro-
The diameter of rice stick is 1~10 μm, and length is 5~100 μm.A kind of high-efficient electrolytic water catalyst HRu of the present invention4O8The system of micron bar
Preparation Method carries out according to the following steps:
One, RuO2The preparation of nanoparticle: with molar ratio being 1:(1~20 by ruthenium presoma and nitrate) ratio be dissolved in
In water, stirring obtains mixed solution to being uniformly mixed, and the concentration of ruthenium presoma is 1~100g/L in mixed solution, will mix molten
Liquid drying, obtains solid, then solid is put into container, then 0.5~10h is kept the temperature at inert atmosphere, 200~400 DEG C, then
1~10h is kept the temperature at 400~700 DEG C, is taken out after cooling, is washed 3~10 times, and drying obtains RuO2Nanoparticle；
Two, the preparation of ruthenate micron bar: by RuO2Nanoparticle and carbonate or bicarbonate in molar ratio (0.5~
10): 1 ratio mixing is then placed in container, then keep the temperature 2~30h at inert atmosphere, 300~1200 DEG C, takes after cooling
Out, it washs 3~10 times, drying obtains ruthenate micron bar；
Three, HRu4O8The preparation of micron bar: ruthenate micron bar is added in the acid solution that concentration is 0.1M~5M, 30
1~7d is stirred at~150 DEG C, is washed 3~10 times, drying；Again 150~1000 DEG C of 1~30h of heat preservation to get arrive HRu4O8Micron
Stick；Wherein the ratio of ruthenate micron bar and acid solution is 1g:(50~500) mL.
Beneficial effects of the present invention:
One, HRu of the invention4O8Micron bar is applied to HER, OER, and has excellent performance, and obtains one kind in alkaline electrolysis
HER and OER shows the bifunctional electrocatalyst of excellent catalytic activity under liquid system, can high-efficient electrolytic water；
Two, HRu of the invention4O8The HER of micron bar, business Pt/C in 1M KOH is in 10mA/cm2Under overpotential point
Not Wei 50mV, 108mV (not carrying out IR correction), performance is much better than business Pt/C.HRu4O8Micron bar, business RuO2In 1M
OER in KOH is in 10mA/cm2Under overpotential be only 300mV, 323mV (not carrying out IR correction), performance is better than business
RuO2；
Three, the catalyst prepared by the present invention shows excellent stability, HRu after i-t 8h in HER4O8Micron bar,
The current density of business Pt/C is respectively the 104.66% of its corresponding initial value, 10.69%, it is seen that prepared HRu4O8It is micro-
Rice stick stability is much better than business Pt/C；HRu after i-t 8h in OER4O8Micron bar, business RuO2Current density be respectively
96.65%, the 61.07% of its corresponding initial value, it is seen that prepared HRu4O8Micron bar stability is much better than business RuO2。
Detailed description of the invention
Fig. 1 is HRu prepared by embodiment 14O8The XRD diagram of micron bar；
Fig. 2 is HRu prepared by embodiment 14O8Micron bar SEM figure；
Fig. 3 is HRu prepared by embodiment 14O8The HER performance map of micron bar and business Pt/C, electrolyte are 1M KOH, are swept
Speed is 10mV/s, and revolving speed 1600rpm, potential range is 0.05~-0.3V vs RHE；Wherein a is business Pt/C, and b is
HRu4O8Micron bar；
Fig. 4 is HRu prepared by embodiment 14O8Micron bar and business RuO2OER performance map, electrolyte be 1M KOH, sweep
Speed is 10mV/s, and revolving speed 1600rpm, potential range is 1.0~1.8V vs RHE；Wherein a is business RuO2, b HRu4O8
Micron bar；
Fig. 5 is HRu prepared by embodiment 14O8Micron bar is 10mA/cm in HER current density with business Pt/C2Current potential
Under i-t curve, electrolyte be 1M KOH, revolving speed 1600rpm；Wherein a is business Pt/C, b HRu4O8Micron bar；
Fig. 6 is HRu prepared by embodiment 14O8Micron bar and business RuO2It is 10mA/cm in OER current density2Current potential
Under i-t curve, electrolyte be 1M KOH, revolving speed 1600rpm；Wherein a is business RuO2, b HRu4O8Micron bar.
Specific embodiment
Specific embodiment 1: a kind of high-efficient electrolytic water catalyst HRu of present embodiment4O8The original of H:Ru:O in micron bar
Son is than being 1:4:8, HRu4O8The diameter of micron bar is 1~10 μm, and length is 5~100 μm.
Present embodiment the utility model has the advantages that
One, the HRu of present embodiment4O8Micron bar is applied to HER, OER, and has excellent performance, and obtains one kind in alkalinity
HER and OER shows the bifunctional electrocatalyst of excellent catalytic activity under electrolyte system, can high-efficient electrolytic water；
Two, the HRu of present embodiment4O8The HER of micron bar, business Pt/C in 1M KOH is in 10mA/cm2Under it is excessively electric
Position is respectively 50mV, 108mV (not carrying out IR correction), and performance is much better than business Pt/C.HRu4O8Micron bar, business RuO2In 1M
OER in KOH is in 10mA/cm2Under overpotential be only 300mV, 323mV (not carrying out IR correction), performance is better than business
RuO2；
Three, catalyst prepared by present embodiment shows excellent stability, HRu after i-t 8h in HER4O8It is micro-
Rice stick, business Pt/C current density be respectively the 104.66% of its corresponding initial value, 10.69%, it is seen that it is prepared
HRu4O8Micron bar stability is much better than business Pt/C；HRu after i-t 8h in OER4O8Micron bar, business RuO2Current density
Respectively 96.65%, the 61.07% of its corresponding initial value, it is seen that prepared HRu4O8Micron bar stability is much better than business
RuO2。
Specific embodiment 2: a kind of high-efficient electrolytic water catalyst HRu of present embodiment4O8The preparation method of micron bar is
It carries out according to the following steps:
One, RuO2The preparation of nanoparticle: with molar ratio being 1:(1~20 by ruthenium presoma and nitrate) ratio be dissolved in
In water, stirring obtains mixed solution to being uniformly mixed, and the concentration of ruthenium presoma is 1~100g/L in mixed solution, will mix molten
Liquid drying, obtains solid, then solid is put into container, then 0.5~10h is kept the temperature at inert atmosphere, 200~400 DEG C, then
1~10h is kept the temperature at 400~700 DEG C, is taken out after cooling, is washed 3~10 times, and drying obtains RuO2Nanoparticle；
Two, the preparation of ruthenate micron bar: by RuO2Nanoparticle and carbonate or bicarbonate in molar ratio (0.5~
10): 1 ratio mixing is then placed in container, then keep the temperature 2~30h at inert atmosphere, 300~1200 DEG C, takes after cooling
Out, it washs 3~10 times, drying obtains ruthenate micron bar；
Three, HRu4O8The preparation of micron bar: ruthenate micron bar is added in the acid solution that concentration is 0.1M~5M, 30
1~7d is stirred at~150 DEG C, is washed 3~10 times, drying；Again 150~1000 DEG C of 1~30h of heat preservation to get arrive HRu4O8Micron
Stick；Wherein the ratio of ruthenate micron bar and acid solution is 1g:(50~500mL).
Specific embodiment 3: present embodiment is unlike specific embodiment two: ruthenium presoma is in step 1
RuCl3·nH2O、Ru(acac)3、Ru2(CO)6Cl4、K2RuCl5·nH2In three (2,2- bipyridyl) ruthenic chlorides of hydration of O and six
One or more are mixed by any ratio.It is other to be identical with embodiment two.
Specific embodiment 4: present embodiment is unlike specific embodiment two or three: nitrate NaNO3、
KNO3、LiNO3、RbNO3、Sr(NO3)2、Ba(NO3)2、Mg(NO3)2、Fe(NO3)2、Fe(NO3)3、CuNO3、 Cu(NO3)2、Zn
(NO3)2、Pb(NO3)2、Mn(NO3)2、Bi(NO3)3、CsNO3、Ca(NO3)2、Ni(NO3)2、Co(NO3)2With Al (NO3)3In one
Kind or several be mixed by any ratio.It is other identical as specific embodiment two or three.
Specific embodiment 5: unlike one of present embodiment and specific embodiment two to four: in step 2
Carbonate or bicarbonate are Na2CO3、K2CO3、Li2CO3、Rb2CO3、SrCO3、BaCO3、MgCO3、FeCO3、 Fe2(CO3)3、
CuCO3、Cu2CO3、ZnCO3、PbCO3、MnCO3、Bi2(CO3)3、Cs2CO3、CaCO3、 NiCO3、CoCO3、Al2(CO3)3、
NaHCO3、KHCO3、LiHCO3、RbHCO3、Sr(HCO3)2、 Ba(HCO3)2、Mg(HCO3)2、Fe(HCO3)2、Fe(HCO3)3、Cu
(HCO3)2、Zn(HCO3)2、Pb(HCO3)2、 Mn(HCO3)2、Bi(HCO3)3、CsHCO3、Ca(HCO3)2、Ni(HCO3)2And Co
(HCO3)2One or more of be mixed by any ratio.It is other identical as one of specific embodiment two to four.
Specific embodiment 6: unlike one of present embodiment and specific embodiment two to five: step 1 and two
In inert atmosphere be nitrogen, argon gas or helium.It is other identical as one of specific embodiment two to five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment two to six: described in step 3
Acid solution be H2SO4、HNO3、HCl、H3PO4、HClO4、CH3CH(OH)COOH、C6H8O7、HOOCCOOH、 HCOOH、CH3COOH
And CH3CH2One or more of COOH is mixed by any ratio.It is other identical as one of specific embodiment two to six.
Specific embodiment 8: unlike one of present embodiment and specific embodiment two to seven: Step 1: two and
The rate to heat up in three is 1~50 DEG C/min.It is other identical as one of specific embodiment two to seven.
Specific embodiment 9: unlike one of present embodiment and specific embodiment two to eight: step 1 and three
In stirring be mechanical stirring, magnetic agitation or ultrasonic agitation.It is other identical as one of specific embodiment two to eight.
Specific embodiment 10: unlike one of present embodiment and specific embodiment two to nine: in step 3
150~1000 DEG C of 1~30h of heat preservation are kept the temperature under atmosphere protection, wherein atmosphere be air, oxygen, hydrogen, nitrogen, argon gas,
Gaseous mixture, carbon monoxide, ammonia or the vacuum of the gaseous mixture of hydrogen and nitrogen, the gaseous mixture of hydrogen and argon gas, hydrogen and helium.
It is other identical as one of specific embodiment two to nine.
Specific embodiment 11: unlike one of present embodiment and specific embodiment two to ten: hydrogen and nitrogen
The gaseous mixture of gas, the gaseous mixture of hydrogen and argon gas, hydrogen and helium gaseous mixture in the volume content of hydrogen be 1~20%.Its
It is identical as one of specific embodiment two to ten.
A kind of high-efficient electrolytic water catalyst HRu of embodiment 1, the present embodiment4O8The preparation method of micron bar is according to the following steps
It carries out:
One, RuO2The preparation of nanoparticle: by RuCl3·nH2O and NaNO3It is soluble in water for the ratio of 1:8 with molar ratio,
Stirring obtains mixed solution, RuCl in mixed solution to being uniformly mixed3·nH2The concentration of O is 15g/L, and mixed solution is dried,
Solid is obtained, then solid is put into container, rises to 400 DEG C in a nitrogen atmosphere with the heating rate of 10 DEG C/min, heat preservation
0.5h, then 500 DEG C are risen to the heating rate of 5 DEG C/min, 1h is then kept the temperature, is taken out after cooling, is washed 7 times, drying obtains
RuO2Nanoparticle；
Two, the preparation of ruthenate micron bar: by RuO2Nanoparticle and K2CO3The ratio mixing of 8:5 in molar ratio, then
It is put into container, in a nitrogen atmosphere, is risen at 850 DEG C with the heating rate of 5 DEG C/min and keep the temperature 12h, taken out after cooling, wash
7 times, drying obtains KRu4O8Micron bar；
Three, HRu4O8The preparation of micron bar: by KRu4O8Micron bar is added in the HCl that concentration is 1M, is stirred at 60 DEG C
3d is washed 7 times, drying；Again under air with the heating rate of 5 DEG C/min, 300 DEG C of heat preservation 2h to get arrive HRu4O8Micron bar；Its
Middle KRu4O8The ratio of micron bar and acid solution is 1g:100mL.
Fig. 1 is HRu manufactured in the present embodiment4O8The XRD diagram of micron bar, it can be seen that it is hollandite type knot from XRD
Structure determines that group is divided into HRu4O8, because being in itself KRu4O8It is obtained after acid exchange completely, it is exactly HRu that K, which is exchanged into H,4O8；
Fig. 2 is HRu manufactured in the present embodiment4O8The SEM of micron bar schemes, and as can be seen from Figure 2 a diameter of 1~4 μm, length is 3~
15μm。
Catalyst is dispersed by uniform sizing material using ethyl alcohol when the present embodiment electro-chemical test, the rotation in platinum carbon material is added dropwise
The carrying capacity for turning to control catalyst on disk electrode (RDE) is 0.2mg/cm2, and be 20 μ L/cm by dripping quantity2Mass fraction is added dropwise
For 0.05% Nafion ethanol solution, it is dipped in after dry in the 1M KOH solution of argon gas saturation.
It is tested when test using electrochemical workstation, using the RED of dropwise addition catalyst as working electrode, Hg/HgO
As reference electrode, Pt piece is used as to electrode.
HRu manufactured in the present embodiment4O8The HER of micron bar, business Pt/C in 1M KOH is in 10mA/cm2Under overpotential
Respectively 50mV, 108mV (not carrying out IR correction), performance is much better than business Pt/C, as shown in Figure 3.HRu4O8Micron bar, quotient
Industry RuO2OER in 1M KOH is in 10mA/cm2Under overpotential be only 300mV, 323mV (not carrying out IR correction), performance
Better than business RuO2, as shown in Figure 4.Catalyst prepared by the present embodiment shows excellent stability, as in Fig. 5 in HER
HRu after i-t 8h4O8Micron bar, business Pt/C current density be respectively its corresponding initial value 104.66%,
10.69%, it is seen that prepared HRu4O8Micron bar stability is much better than business Pt/C.As in Fig. 6 in OER after i-t 8h
HRu4O8Micron bar, business RuO2Current density be respectively the 96.65% of its corresponding initial value, 61.07%, it is seen that it is made
Standby HRu4O8Micron bar stability is much better than business RuO2。
A kind of high-efficient electrolytic water catalyst HRu of embodiment 2, the present embodiment4O8The preparation method of micron bar is according to the following steps
It carries out:
One, RuO2The preparation of nanoparticle: by Ru (acac)3And KNO3It is soluble in water for the ratio of 1:4 with molar ratio, it stirs
It mixes to being uniformly mixed, obtains mixed solution, Ru (acac) in mixed solution3Concentration be 20g/L, mixed solution is dried, is obtained
To solid, then solid is put into container, rises to 300 DEG C under an argon atmosphere with the heating rate of 10 DEG C/min, keeps the temperature 1h,
450 DEG C are risen to the heating rate of 10 DEG C/min again, 2h is then kept the temperature, is taken out after cooling, is washed 7 times, drying obtains RuO2It receives
Rice corpuscles；
Two, the preparation of ruthenate micron bar: by RuO2Nanoparticle and Na2CO3The ratio mixing of 2:1 in molar ratio, then
It is put into container, under helium atmosphere, is risen at 750 DEG C with the heating rate of 10 DEG C/min and keep the temperature 10h, taken out, wash after cooling
It washs 7 times, dries, obtain NaRu4O8Micron bar；
Three, HRu4O8The preparation of micron bar: by NaRu4O8Micron bar is added to the HNO that concentration is 0.5M3In, it is stirred at 30 DEG C
5d is mixed, is washed 7 times, drying；Again under a nitrogen with the heating rate of 10 DEG C/min, 400 DEG C of heat preservation 3h to get arrive HRu4O8Micron
Stick；Wherein NaRu4O8The ratio of micron bar and acid solution is 1g:150mL.
A kind of high-efficient electrolytic water catalyst HRu of embodiment 3, the present embodiment4O8The preparation method of micron bar is according to the following steps
It carries out:
One, RuO2The preparation of nanoparticle: by Ru2(CO)6Cl4And LiNO3It is soluble in water for the ratio of 1:5 with molar ratio,
Stirring obtains mixed solution, Ru in mixed solution to being uniformly mixed2(CO)6Cl4Concentration be 25g/L, mixed solution is dried,
Solid is obtained, then solid is put into container, rises to 350 DEG C under helium atmosphere with the heating rate of 5 DEG C/min, heat preservation
1h, then 450 DEG C are risen to the heating rate of 5 DEG C/min, 3h is then kept the temperature, is taken out after cooling, is washed 6 times, drying obtains RuO2
Nanoparticle；
Two, the preparation of ruthenate micron bar: by RuO2Nanoparticle and KHCO3The ratio mixing of 3:1 in molar ratio, then
It is put into container, under an argon atmosphere, is risen at 800 DEG C with the heating rate of 8 DEG C/min and keep the temperature 5h, taken out after cooling, washing 8
Secondary, drying obtains KRu4O8Micron bar；
Three, HRu4O8The preparation of micron bar: by KRu4O8Micron bar is added to the H that concentration is 0.2M2SO4In, it is stirred at 40 DEG C
2d is mixed, is washed 8 times, drying；Again under oxygen with the heating rate of 2 DEG C/min, 350 DEG C of heat preservation 4h to get arrive HRu4O8Micron
Stick；Wherein KRu4O8The ratio of micron bar and acid solution is 1g:200mL.
A kind of high-efficient electrolytic water catalyst HRu of embodiment 4, the present embodiment4O8The preparation method of micron bar is according to the following steps
It carries out:
One, RuO2The preparation of nanoparticle: by K2RuCl5·nH2O and Sr (NO3)2It is dissolved in molar ratio for the ratio of 1:3
In water, stirring obtains mixed solution, K in mixed solution to being uniformly mixed2RuCl5·nH2The concentration of O is 35g/L, will be mixed molten
Liquid drying, obtains solid, then solid is put into container, rise to 300 in a nitrogen atmosphere with the heating rate of 5 DEG C/min
DEG C, 2h is kept the temperature, then rise to 500 DEG C with the heating rate of 10 DEG C/min, then keep the temperature 1h, taken out after cooling, washed 7 times, drying,
Obtain RuO2Nanoparticle；
Two, the preparation of ruthenate micron bar: by RuO2Nanoparticle and Rb2CO3The ratio mixing of 4:1 in molar ratio, then
It is put into container, under helium atmosphere, is risen at 600 DEG C with the heating rate of 3 DEG C/min and keep the temperature 20h, taken out after cooling, wash
6 times, drying obtains RbRu4O8Micron bar；
Three, HRu4O8The preparation of micron bar: by RbRu4O8Micron bar is added to the CH that concentration is 0.5M3In COOH, 50 DEG C
Lower stirring 2d is washed 6 times, drying；Again in H2With the heating rate of 3 DEG C/min, 350 DEG C of heat preservation 5h under/Ar=5/95 atmosphere, i.e.,
Obtain HRu4O8Micron bar；Wherein RbRu4O8The ratio of micron bar and acid solution is 1g:300mL.
The HRu of Examples 1 to 4 preparation4O8Micron bar can be applied to HER, OER, and have excellent performance, and obtains one kind and exists
HER and OER shows the bifunctional electrocatalyst of excellent catalytic performance and stability under alkaline electrolysis liquid system, can efficient electric
Xie Shui.
Claims (5)
1. a kind of high-efficient electrolytic water catalyst HRu4O8Micron bar, it is characterised in that the HRu4O8The original of H:Ru:O in micron bar
Son is than being 1:4:8, HRu4O8The diameter of micron bar is 1~10 μm, and length is 5~100 μm；Wherein high-efficient electrolytic water catalyst
HRu4O8The preparation method of micron bar carries out according to the following steps:
One, RuO2The preparation of nanoparticle: with molar ratio being 1:(1~20 by ruthenium presoma and nitrate) ratio it is soluble in water,
Stirring obtains mixed solution to being uniformly mixed, and the concentration of ruthenium presoma is 1~100g/L in mixed solution, and mixed solution is dried
It is dry, solid is obtained, then solid is put into container, then keeps the temperature 0.5~10h at inert atmosphere, 200~400 DEG C, then
1~10h is kept the temperature at 400~700 DEG C, is taken out after cooling, is washed 3~10 times, and drying obtains RuO2Nanoparticle；
Two, the preparation of ruthenate micron bar: by RuO2Nanoparticle and carbonate or bicarbonate be in molar ratio (0.5~10): 1
Ratio mixing, be then placed in container, then at inert atmosphere, 300~1200 DEG C keep the temperature 2~30h, take out, wash after cooling
It washs 3~10 times, dries, obtain ruthenate micron bar；
Three, HRu4O8The preparation of micron bar: ruthenate micron bar is added in the acid solution that concentration is 0.1M~5M, 30~150
1~7d is stirred at DEG C, is washed 3~10 times, drying；Again 150~1000 DEG C of 1~30h of heat preservation to get arrive HRu4O8Micron bar；Its
The ratio of middle ruthenate micron bar and acid solution is 1g:(50~500) mL；
Wherein ruthenium presoma is RuCl in step 13·nH2O、Ru(acac)3、Ru2(CO)6Cl4、K2RuCl5·nH2O and six water
One or more of three (2,2- bipyridyl) ruthenic chlorides are closed to be mixed by any ratio；
Nitrate is NaNO in step 13、KNO3、LiNO3、RbNO3、Sr(NO3)2、Ba(NO3)2、Mg(NO3)2、Fe(NO3)2、Fe
(NO3)3、CuNO3、Cu(NO3)2、Zn(NO3)2、Pb(NO3)2、Mn(NO3)2、Bi(NO3)3、CsNO3、Ca(NO3)2、Ni(NO3)2、
Co(NO3)2With Al (NO3)3One or more of be mixed by any ratio；
Carbonate or bicarbonate in step 2 are Na2CO3、K2CO3、Li2CO3、Rb2CO3、SrCO3、BaCO3、MgCO3、
FeCO3、Fe2(CO3)3、CuCO3、Cu2CO3、ZnCO3、PbCO3、MnCO3、Bi2(CO3)3、Cs2CO3、CaCO3、NiCO3、CoCO3、
Al2(CO3)3、NaHCO3、KHCO3、LiHCO3、RbHCO3、Sr(HCO3)2、Ba(HCO3)2、Mg(HCO3)2、Fe(HCO3)2、Fe
(HCO3)3、Cu(HCO3)2、CuHCO3、Zn(HCO3)2、Pb(HCO3)2、Mn(HCO3)2、Bi(HCO3)3、CsHCO3、Ca(HCO3)2、
Ni(HCO3)2With Co (HCO3)2One or more of be mixed by any ratio；
Acid solution described in step 3 is H2SO4、HNO3、HCl、H3PO4、HClO4、CH3CH(OH)COOH、C6H8O7、HOOCCOOH、
HCOOH、CH3COOH and CH3CH2One or more of COOH is mixed by any ratio.
2. a kind of high-efficient electrolytic water catalyst HRu according to claim 14O8Micron bar, it is characterised in that step 1 and two
In inert atmosphere be nitrogen, argon gas or helium.
3. a kind of high-efficient electrolytic water catalyst HRu according to claim 14O8Micron bar, it is characterised in that Step 1: two
It is 1~50 DEG C/min with the heating rate in three.
4. a kind of high-efficient electrolytic water catalyst HRu according to claim 14O8Micron bar, it is characterised in that step 1 and three
In stirring be mechanical stirring, magnetic agitation or ultrasonic agitation.
5. a kind of high-efficient electrolytic water catalyst HRu according to claim 14O8Micron bar, it is characterised in that in step 3
150~1000 DEG C of 1~30h of heat preservation are kept the temperature under atmosphere protection, wherein atmosphere be air, oxygen, hydrogen, nitrogen, argon gas,
Gaseous mixture, carbon monoxide, ammonia or the vacuum of the gaseous mixture of hydrogen and nitrogen, the gaseous mixture of hydrogen and argon gas, hydrogen and helium.
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