CN112023940B - Preparation method of electrocatalyst, application thereof and electrode - Google Patents
Preparation method of electrocatalyst, application thereof and electrode Download PDFInfo
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- CN112023940B CN112023940B CN202010926682.4A CN202010926682A CN112023940B CN 112023940 B CN112023940 B CN 112023940B CN 202010926682 A CN202010926682 A CN 202010926682A CN 112023940 B CN112023940 B CN 112023940B
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- metal salt
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- based metal
- ruthenium
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 225
- 239000002184 metal Substances 0.000 claims abstract description 225
- 150000003839 salts Chemical class 0.000 claims abstract description 202
- 239000007787 solid Substances 0.000 claims abstract description 69
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 239000003960 organic solvent Substances 0.000 claims abstract description 30
- 239000013557 residual solvent Substances 0.000 claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002739 metals Chemical class 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 79
- 239000000243 solution Substances 0.000 claims description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000002244 precipitate Substances 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 13
- 229910009112 xH2O Inorganic materials 0.000 claims description 13
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 12
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 11
- 238000002484 cyclic voltammetry Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- 229910020437 K2PtCl6 Inorganic materials 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 238000005530 etching Methods 0.000 claims description 7
- 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 6
- 229910019029 PtCl4 Inorganic materials 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000004973 liquid crystal related substance Substances 0.000 claims description 2
- 239000010949 copper Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052802 copper Inorganic materials 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 description 26
- 239000000725 suspension Substances 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 229910045601 alloy Inorganic materials 0.000 description 15
- 239000000956 alloy Substances 0.000 description 15
- 238000004140 cleaning Methods 0.000 description 14
- 239000000446 fuel Substances 0.000 description 14
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229920000557 Nafion® Polymers 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910021397 glassy carbon Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 7
- 238000010408 sweeping Methods 0.000 description 7
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000011449 brick Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(II) bromide Substances [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910002787 Ru-Ni Inorganic materials 0.000 description 2
- 229910002793 Ru–Ni Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000005469 synchrotron radiation Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- -1 Ruthenium (triacetyl pyruvate) Chemical compound 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- DMUNQEXYOBRAQK-UHFFFAOYSA-N [Pt].CC(=O)C.CC(=O)C Chemical compound [Pt].CC(=O)C.CC(=O)C DMUNQEXYOBRAQK-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000003035 anti-peroxidant effect Effects 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- HCRZXNOSPPHATK-UHFFFAOYSA-L copper;3-oxobutanoate Chemical compound [Cu+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O HCRZXNOSPPHATK-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- MNSHGRXIICSKRQ-UHFFFAOYSA-L nickel(2+);3-oxobutanoate Chemical compound [Ni+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O MNSHGRXIICSKRQ-UHFFFAOYSA-L 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B01J35/33—
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a preparation method of an electrocatalyst, application thereof and an electrode, wherein the preparation method of the electrocatalyst comprises the following steps: uniformly mixing ruthenium-based metal salt, first metal salt and second metal salt in an organic solvent to form a metal salt precursor solution; under the condition of stirring, heating the metal salt precursor solution to 180-220 ℃, and reacting at constant temperature until a solid-liquid mixture is formed; carrying out solid-liquid separation on the solid-liquid mixture to obtain a solid; removing unstable metals and residual solvents in the solid to obtain an electrocatalyst; wherein the first metal salt is a platinum-based metal salt; the second metal salt is copper-based metal salt, nickel-based metal salt or cobalt-based metal salt. The present invention aims to provide an electrocatalyst having high activity, high stability and low cost.
Description
Technical Field
The invention relates to the technical field of PEM (proton exchange membrane) electrolyzed water, in particular to a preparation method of an electrocatalyst, application thereof and an electrode.
Background
With the increasing prominence of environmental problems and energy problems, new energy automobiles become research hotspots of automobile manufacturers and research and development institutions in the world, and among the new energy automobiles, fuel cell automobiles are widely regarded as having wide development prospects with high efficiency and near zero emission. The fuel commonly used by fuel cells is hydrogen, and a method for producing hydrogen at low cost is vigorously developed in order to develop fuel cell technology on a large scale. Today, the vast majority of hydrogen production is via the process of "steam reforming of methane", but is facing the release of carbon dioxide greenhouse gas, which is not environmentally friendly. The hydrogen production process by electrolyzing water is simple, has no carbon emission pollution, and is a next-generation clean method which is expected to replace methane steam reforming and become hydrogen fuel.
The overpotential for acidic electrolyzed water is mainly derived from the anode part of Oxygen Evolution (OER), and the development of an efficient and inexpensive oxygen evolution catalyst under acidic conditions is the most difficult and challenging of all electrolyzed water technologies. A common commercial catalyst for oxygen evolution is IrO2. However, the cost of iridium (Ir) metal is extremely highAnd the earth reserves are limited, irO is used2The cost of the electrocatalyst is high, which is not favorable for the popularization of the fuel cell.
Disclosure of Invention
The invention aims to provide a preparation method of an electrocatalyst, application thereof and an electrode, and aims to provide the electrocatalyst with high activity, high stability and low cost.
In order to achieve the above object, the present invention provides a method for preparing an electrocatalyst, comprising the steps of:
uniformly mixing ruthenium-based metal salt, first metal salt and second metal salt in an organic solvent to form a metal salt precursor solution;
under the condition of stirring, heating the metal salt precursor solution to 180-220 ℃, and reacting at constant temperature until a solid-liquid mixture is formed;
carrying out solid-liquid separation on the solid-liquid mixture to obtain a solid;
removing unstable metals and residual solvents in the solid to obtain an electrocatalyst;
wherein the first metal salt is a platinum-based metal salt;
the second metal salt is copper-based metal salt, nickel-based metal salt or cobalt-based metal salt.
Optionally, in the step of uniformly mixing the ruthenium-based metal salt, the first metal salt and the second metal salt in an organic solvent to form a metal salt precursor solution, the organic solvent includes one or more of oleylamine, oleic acid, octadecene, ethanol and cyclohexane; and/or the presence of a gas in the gas,
the first metal salt comprises Pt (acac)2、H2PtCl6·6H2O、K2PtCl6·6H2O、PtCl4One or more of; and/or the presence of a gas in the gas,
the ruthenium-based metal salt includes Ru (acac)3、RuCl3·xH2O、Ru(CO)6One or more of (a).
Optionally, when the second metal salt is a copper-based metal saltSaid copper-based metal salt comprises Cu (acac)2、CuCl2·2H2O、Cu(NO3)2·3H2O、CuBr2One or more of (a); alternatively, the first and second electrodes may be,
when the second metal salt is a nickel-based metal salt, the nickel-based metal salt includes Ni (acac)2、NiCl2·2H2O、Ni(NO3)2·3H2O、NiSO4One or more of; alternatively, the first and second liquid crystal display panels may be,
when the second metal salt is a cobalt-based metal salt, the cobalt-based metal salt includes Co (acac)2、CoCl2·2H2O、Co(NO3)2·3H2O、CoSO4One or more of (a).
Optionally, in the step of uniformly mixing the ruthenium-based metal salt, the first metal salt and the second metal salt in an organic solvent to form a metal salt precursor solution, the weight ratio of the organic solvent to the ruthenium-based metal salt to the first metal salt to the second metal salt is 1.
Optionally, the metal salt precursor solution is heated to 180-220 ℃, and the heating time is not more than 25min in the step of reacting at constant temperature to obtain a solid-liquid mixture.
Optionally, heating the metal salt precursor solution to 180-220 ℃, and reacting at constant temperature for 6-12 h until a solid-liquid mixture is obtained.
Optionally, the step of performing solid-liquid separation on the solid-liquid mixture to obtain a solid substance includes:
centrifuging the solid-liquid mixture, and collecting precipitates;
washing the precipitate by using a mixed solution of ethanol and n-hexane;
and (3) placing the cleaned precipitate at the temperature of 60-90 ℃ for vacuum drying to obtain a solid.
Optionally, the step of removing unstable metals and residual solvent from the solid to obtain the electrocatalyst comprises:
immersing the solid in an acid solution to initially etch away unstable metals in the solid;
washing the solid after acid etching, and then drying in vacuum;
loading the solid dried in vacuum on activated carbon, and carrying out annealing treatment at 380-450 ℃ in a nitrogen atmosphere to remove residual solvent in the solid;
and carrying out secondary etching treatment on the unstable metal in the solid by using an electrochemical cyclic voltammetry to obtain the electrocatalyst.
Furthermore, the invention also proposes an electrode for use in an electrolytic cell, said electrode comprising an electrocatalyst prepared by the method for preparing an electrocatalyst as described above.
In addition, the invention also provides the application of the electrocatalyst prepared by the preparation method of the electrocatalyst in PEM electrolyzed water.
According to the technical scheme provided by the invention, the stable monatomic alloy catalyst is prepared by selecting the first metal salt and the second metal salt of the alloy with strong oxidation resistance and dissolution resistance as carriers, taking ruthenium as a core and adopting a solvothermal method; meanwhile, the ruthenium (Ru) monatomic catalyst with low price and rich earth reserves is selected to prepare the ruthenium monatomic catalyst, and the electrocatalyst has excellent catalytic performance in the anode oxygen precipitation reaction of PEM electrolyzed water, so that the activity of the electrocatalyst is ensured, and the cost of the electrocatalyst is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic flow diagram of one embodiment of a method for preparing an electrocatalyst according to the present invention;
FIG. 2 is a synchrotron radiation spectrum of the electrocatalyst prepared in example 1;
FIG. 3 is an electron micrograph of an electrocatalyst prepared in example 1;
FIG. 4 is an electron micrograph of an electrocatalyst prepared according to example 2;
FIG. 5 is an electron micrograph of an electrocatalyst prepared according to example 3;
FIG. 6 is a graph comparing the catalytic performance of the electrocatalysts of examples 1 to 3 and comparative examples 1 and 2;
fig. 7 is a graph comparing the oxygen evolution stability of the electrocatalysts of examples 1 to 3 and comparative example 1.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments.
It should be noted that those whose specific conditions are not specified in the examples were performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B", including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
With the increasing prominence of environmental problems and energy problems, new energy automobiles become research hotspots of automobile manufacturers and research and development institutions in the world, and among the new energy automobiles, fuel cell automobiles are widely regarded as having wide development prospects with high efficiency and near zero emission. The fuel commonly used in fuel cells is hydrogen, and to develop fuel cell technologies on a large scale, methods for producing hydrogen at low cost have been vigorously developed. Today, the vast majority of hydrogen production is via the process of "steam reforming of methane", but is facing the release of carbon dioxide greenhouse gas, which is not environmentally friendly. The hydrogen production process by electrolyzing water is simple, has no carbon emission pollution, and is a next-generation clean method which is expected to replace methane steam reforming and become hydrogen fuel.
The overpotential for acidic electrolyzed water is mainly derived from the anode part of Oxygen Evolution (OER), and the development of an efficient and inexpensive oxygen evolution catalyst under acidic conditions is the most difficult and challenging of all electrolyzed water technologies. A common commercial catalyst for oxygen evolution is IrO2. However, iridium (Ir) metal is extremely expensive and has a limited earth reserve, and IrO is used2The cost of the electrocatalyst is high, which is not favorable for the popularization of the fuel cell.
In view of this, the present invention provides a method for preparing an electrocatalyst, by which an electrocatalyst having high activity, high stability and low price can be prepared. Fig. 1 shows an embodiment of the preparation method of the electrocatalyst according to the present invention.
Referring to fig. 1, the preparation method of the electrocatalyst includes the steps of:
step S10, ruthenium-based metal salt, first metal salt and second metal salt are uniformly mixed in an organic solvent to form a metal salt precursor solution.
Wherein the first metal salt is a platinum-based metal salt; the second metal salt is copper-based metal salt, nickel-based metal salt or cobalt-based metal salt.
Ruthenium has higher electrocatalytic activity, and compared with iridium (Ir) (240-250 yuan/g), ruthenium (Ru) (19.5-20.5 yuan/g) has richer earth reserves and cheaper price, and ruthenium is selected as a core, so that the activity of the electrocatalyst is ensured, and the cost of the electrocatalyst is reduced.
Considering RuO in a strongly acidic, strongly oxidizing environment2Is easily oxidized into RuO under high working potential4The invention selects the first metal salt and the second metal salt with stronger oxidation resistance and dissolution resistance as alloy carriers, and the monoatomic ruthenium is embedded into the stable alloy carrier to form the ruthenium monoatomic alloy catalyst with stable property, so that the structure stability of the ruthenium monoatomic alloy catalyst is maintained while the high catalytic activity of the ruthenium is kept, the participation of catalyst lattice oxygen in the OER reaction process is avoided, and the catalyst inactivation is further avoided.
Specifically, the organic solvent may be any one of oleylamine, oleic acid, octadecene, ethanol, and cyclohexane, or a mixed solution of at least two solvents of oleylamine, oleic acid, octadecene, ethanol, and cyclohexane, for example, a mixed solution in which ethanol, oleylamine, and octadecene are mixed in a volume ratio of 1:2 by volume.
The first metal salt comprises Pt (acac)2(platinum diacetone), H2PtCl6·6H2O (chloroplatinic acid), K2PtCl6·6H2O (potassium chloroplatinate), ptCl4(platinum chloride). For example, the first metal salt may be Pt (acac)2、H2PtCl6·6H2O、K2PtCl6·6H2O、PtCl4Any one of the above; or may be Pt (acac)2And H2PtCl6·6H2Mixture of O, H2PtCl6·6H2O、K2PtCl6·6H2O、PtCl4Of (2) or H2PtCl6·6H2O and K2PtCl6·6H2A mixture of O.
The ruthenium-based metal salt includes Ru (acac)3Ruthenium (triacetyl pyruvate), ruCl3·xH2O (ruthenium chloride), ru (CO)6One or more of (ruthenium hexa-carbonyl). For example, the ruthenium-based metal salt may be Ru (acac)3、RuCl3·xH2O、Ru(CO)6Can also be Ru (acac)3、RuCl3·xH2O、Ru(CO)6A mixture of any two of, and may also be Ru (acac)3、RuCl3·xH2O and Ru (CO)6The mixture of (1).
The second metal salt can be copper-based metal salt, nickel-based metal salt or cobalt-based metal salt, and compared with other metal salts, when the three metal salts are used as the alloy carrier, ruthenium single atoms can be combined to form the high-stability single-atom alloy catalyst. And because Ni and Co can provide a large amount of electrons for Ru, the Ru is prevented from being inactivated due to electron loss, and the monoatomic Ru is kept in a stable state, compared with a copper-based metal salt, the stability of the monoatomic alloy catalyst can be further improved when the second metal salt is a nickel-based metal salt or a cobalt-based metal salt, and therefore, the second metal salt is preferably the nickel-based metal salt or the cobalt-based metal salt.
Wherein, when the second metal salt is configured as a copper-based metal salt, the copper-based metal salt includes Cu (acac)2(copper diacetoacetate), cuCl2·2H2O (cupric chloride), cu (NO)3)2·3H2O (cupric nitrate), cuBr2One or more of (copper bromide); when the second metal salt is configured as a nickel-based metal salt, the nickel-based metal salt includes Ni (acac)2(Nickel diacetoacetate), niCl2·2H2O (Nickel chloride) and Ni (NO)3)2·3H2O (nickel nitrate), niSO4One or more of (nickel sulfate); when the second metal salt is configured as a cobalt-based metal salt, the cobalt-based metal salt includes Co (acac)2(cobalt diacetoacetonate), coCl2·2H2O (cobalt chloride), co (NO)3)2·3H2O (cobalt nitrate), coSO4One or more of (cobalt sulfate).
Further, the first metal salt, the second metal salt, and the ruthenium-based metal salt are mixed in a weight ratio of 1.9 to 2.3. In practical use, the organic solvent, the ruthenium-based metal salt, the first metal salt and the second metal salt are weighed in such proportions that 200g of the first metal salt, 100g of the ruthenium-based metal salt and 375g of the second metal salt are added per 100g of the organic solvent. Preferably, the weight ratio of the organic solvent, the ruthenium-based metal salt, the first metal salt, and the second metal salt is 1:1.07:2.23:4.29.
And S20, heating the metal salt precursor solution to 180-220 ℃ under the stirring condition, and reacting at constant temperature until a solid-liquid mixture is formed.
In this embodiment, after mixing the organic solvent, the ruthenium-based metal salt, the first metal salt, and the second metal salt, the metal salt precursor solution is heated while stirring until the temperature of the solution rises to 180 to 220 ℃, and then the solution is maintained at the temperature for a certain time to facilitate the reaction. It should be noted that, after the reaction starts, the color of the solution will obviously change, and a solid product is generated, and in the actual operation, the color change of the solution or whether a solid-liquid mixture is formed can be used as the basis for judgment. In addition, during actual operation, a part of solvent can be taken firstly for dissolving each metal salt, then the rest solvent is preheated, after the temperature is preheated to 60-120 ℃, the metal salt precursor solution is mixed with the preheated solvent, and then the temperature is heated to 180-220 ℃; or all the solvents and all the metal salts can be mixed to form a metal salt precursor solution, and then the temperature is rapidly raised to 180-220 ℃.
As a preferred embodiment, in this embodiment, after all the solvents are mixed with each metal salt to form a metal salt precursor solution, the temperature is rapidly raised to 180 ℃ to 220 ℃ for no more than 25min, preferably no more than 10 to 20min, so that the metal salt precursor solution can be prevented from reacting at a temperature lower than 180 ℃ to 220 ℃ to generate a byproduct.
In addition, in the embodiment, the reaction time is 6 to 12 hours under the temperature condition of 180 to 220 ℃, thereby ensuring the sufficient reaction.
And S30, carrying out solid-liquid separation on the solid-liquid mixture to obtain a solid.
In a specific implementation, step S30 may include:
step S31, carrying out centrifugal treatment on the solid-liquid mixture, and collecting precipitates;
step S32, cleaning the precipitate by using a mixed solution of ethanol and n-hexane (the volume ratio is 1;
and S33, placing the cleaned precipitate at the temperature of 60-90 ℃ for vacuum drying to obtain a solid.
And S40, removing unstable metals and residual solvents in the solid to obtain the electrocatalyst.
In a specific implementation, step S40 may be implemented as follows:
step S41, immersing the solid in an acid solution to primarily etch off unstable metals in the solid.
In this embodiment, the solid obtained in step S30 is dissolved in an acid solution, so that the acid-soluble metal in the solid is sufficiently etched. The acid solution may be any one of a hydrochloric acid solution, a nitric acid solution, and the like, and the standing time in the acid is determined according to the etching effect, for example, the acid solution may be left standing in concentrated nitric acid for 30min.
And S42, washing the solid after acid etching, and drying in vacuum.
In this embodiment, the solid processed in step S41 is cleaned with ethanol, and then dried in a vacuum drying oven at 60 to 90 ℃ overnight.
And S43, loading the solid after vacuum drying on activated carbon, and carrying out annealing treatment at 380-450 ℃ in a nitrogen atmosphere to remove residual solvent in the solid.
In the embodiment, the solid processed in step S43 is loaded on activated carbon, and then placed in a nitrogen atmosphere to be annealed at 380 to 450 ℃ for 10 to 14 hours to remove the residual solvent in the solid.
And S44, carrying out secondary etching treatment on the unstable metal in the solid by using an electrochemical cyclic voltammetry to obtain the electrocatalyst.
In this embodiment, the solid processed in step S43 is dispersed in ethanol and Nafion solution, and ultrasonically stirred for 60min to obtain a mixed and uniformly mixed suspension. Then 10 mul of suspension is transferred and coated on a glassy carbon electrode, and unstable metal Ni is further removed after sweeping 40 cycles of cyclic voltammetry in 0.1M perchloric acid solution. And finally, cleaning the solid subjected to the electrochemical cyclic voltammetry treatment by using ethanol, and drying the solid in a vacuum drying oven at 60-90 ℃ overnight to obtain the electrocatalyst.
According to the technical scheme provided by the invention, the monatomic alloy catalyst with strong stability is prepared by selecting the first metal salt and the second metal salt of the alloy with strong oxidation resistance and dissolution resistance as carriers and adopting a solvothermal method; meanwhile, ruthenium (Ru) with low price and rich earth reserves is selected to prepare the ruthenium monatomic catalyst, the electrocatalyst has excellent catalytic performance in the anode oxygen precipitation reaction of PEM electrolyzed water, and the cost of the electrocatalyst is reduced while the activity of the electrocatalyst is ensured.
Furthermore, the invention also proposes an electrode which can be used in an electrolysis cell. The preparation method comprises the following steps of selecting alloy first metal salt and alloy second metal salt with strong oxidation resistance and dissolution resistance as carriers, taking ruthenium as a core, and preparing the monatomic alloy catalyst with strong stability by a solvothermal method; meanwhile, ruthenium (Ru) with low price and rich earth reserves is selected to prepare the ruthenium monatomic catalyst, the electrocatalyst has excellent catalytic performance in the anode oxygen precipitation reaction of PEM electrolyzed water, the activity of the electrocatalyst is ensured, the cost of the electrocatalyst is reduced, and the cost of an electrode is further reduced.
The invention also relates to the use of an electrocatalyst as described above in the PEM electrolysis of water. In particular, it can be used for making anode electrodes, the anode electrodes made of the catalyst of the invention have better characteristics in acidic electrolyzed waterThe electrocatalytic activity is good, the anti-peroxidation and anti-dissolution capability is good, the activity is less degraded in a stability test lasting for 75 hours, and the stability is far better than that of commercial RuO2. Moreover, because the ruthenium (Ru) with low price and rich earth reserves is selected as the raw material, the cost of the electrocatalyst is reduced, thereby reducing the cost of hydrogen production, being beneficial to improving the popularization rate of fuel cells and being beneficial to realizing that the fuel cells replace internal combustion engines.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
Raw materials: the first metal salt is Pt (acac)2(ii) a The second metal salt is NiCl2·2H2O; the ruthenium-based metal salt being RuCl3·xH2O; the organic solvent is a mixed solvent formed by mixing oleylamine, ethanol and octadecene according to the volume ratio of 5.
22.3mg of ruthenium-based metal salt, 42.9mg of second metal salt and 10.7mg of first metal salt are respectively measured and dissolved in 10mg of organic solvent, and the solution is ultrasonically stirred for 30min to form a blue-green and clear metal salt precursor solution.
Placing the metal salt precursor solution in an oil bath pot, rapidly increasing the temperature from room temperature (25 ℃) to 180 ℃ (the temperature rise time is not more than 20 min), and keeping the temperature at 180 ℃ for 8h to obtain a solid-liquid mixture;
and centrifuging the solid-liquid mixture, collecting precipitate, cleaning the precipitate with a mixed solution of ethanol, isopropanol, acetone and n-hexane, and drying the precipitate overnight in a vacuum drying oven at the temperature of 80 ℃ to obtain a solid.
Dispersing the sample 1 in 15ml of concentrated nitric acid, standing for 30min, taking out, cleaning with ethanol, placing in a vacuum drying oven at 80 ℃ for drying overnight to obtain solid powder, loading the solid powder on activated carbon, placing in a nitrogen atmosphere, and annealing at 400 ℃ for 12h to remove residual solvent.
8mg of solid with residual solvent removed is weighed and dispersed in 960. Mu.L ethanol and 40. Mu.L Nafion solution, and stirred ultrasonically for 60min to obtain a mixed and evenly mixed suspension. And (3) transferring 10 mu L of suspension by using a liquid transfer gun, coating the suspension on a glassy carbon electrode, and further removing unstable metal Ni after sweeping 40 cycles of cyclic voltammetry in 0.1M perchloric acid solution to obtain the electrocatalyst.
Example 2
Raw materials: the first metal salt is Pt (acac)2(ii) a The second metal salt is CoCl2·2H2O; the ruthenium-based metal salt being RuCl3·xH2O; the organic solvent is a mixed solvent formed by mixing oleylamine, ethanol and octadecene according to the volume ratio of 5.
22.3mg of ruthenium-based metal salt, 42.9mg of second metal salt and 10.7mg of first metal salt are respectively measured and dissolved in 10mg of organic solvent, and the mixture is ultrasonically stirred for 30min to form brick red and clear metal salt precursor solution.
And (3) placing the metal salt precursor solution in an oil bath pot, rapidly increasing the temperature from room temperature (25 ℃) to 180 ℃ (the temperature rise time is not more than 20 min), and keeping the temperature at 180 ℃ for 8h to obtain a solid-liquid mixture.
And centrifuging the solid-liquid mixture, collecting precipitate, cleaning the precipitate with a mixed solution of ethanol, isopropanol, acetone and n-hexane, and drying the precipitate overnight in a vacuum drying oven at the temperature of 80 ℃ to obtain a solid.
Dispersing the solid in 15ml of concentrated nitric acid, standing for 30min, taking out, cleaning with ethanol, placing in a vacuum drying oven at 80 ℃ for drying overnight to obtain solid powder, loading the solid powder on activated carbon, placing in a nitrogen atmosphere, and annealing at 400 ℃ for 12h to remove residual solvent.
8mg of solid with residual solvent removed is weighed and dispersed in 960. Mu.L ethanol and 40. Mu.L Nafion solution, and stirred ultrasonically for 60min to obtain a mixed and evenly mixed suspension. And (3) transferring 10 mu L of suspension by using a liquid transfer gun, coating the suspension on a glassy carbon electrode, and further removing unstable metal Ni after sweeping 40 cycles of cyclic voltammetry in 0.1M perchloric acid solution to obtain the electrocatalyst.
Example 3
Raw materials: the first metal salt is Pt (acac)2(ii) a The second metal salt is CuCl2·2H2O; the ruthenium-based metal salt being RuCl3·xH2O; the organic solvent is a mixed solvent formed by mixing oleylamine, ethanol and octadecene according to the volume ratio of 5.
22.3mg of ruthenium-based metal salt, 42.9mg of second metal salt and 10.7mg of first metal salt are respectively measured and dissolved in 10mg of organic solvent, and the solution is ultrasonically stirred for 30min to form a blue-green and clear metal salt precursor solution.
And (3) placing the metal salt precursor solution in an oil bath pot, rapidly increasing the temperature from room temperature (25 ℃) to 180 ℃ (the temperature rise time is not more than 20 min), and keeping the temperature at 180 ℃ for 8h to obtain a solid-liquid mixture.
And centrifuging the solid-liquid mixture, collecting precipitate, cleaning with a mixed solution of ethanol, isopropanol, acetone and n-hexane, and drying in a vacuum drying oven at 80 ℃ overnight to obtain a solid.
Dispersing the solid in 15ml of concentrated nitric acid, standing for 30min, taking out, cleaning with ethanol, placing in a vacuum drying oven at 80 ℃ for drying overnight to obtain solid powder, loading the solid powder on activated carbon, placing in a nitrogen atmosphere, and annealing at 400 ℃ for 12h to remove residual solvent.
8mg of solid with residual solvent removed is weighed and dispersed in 960. Mu.L ethanol and 40. Mu.L Nafion solution, and stirred ultrasonically for 60min to obtain a mixed and evenly mixed suspension. And (3) transferring 10 mu L of suspension by using a liquid transfer gun, coating the suspension on a glassy carbon electrode, sweeping 40 circles of cyclic voltammetry in 0.1M perchloric acid solution, and further removing unstable metal Ni to obtain the electrocatalyst.
Example 4
Raw materials: the first metal salt is Pt (acac)2(ii) a The second metal salt is Ni (acac)2(ii) a The ruthenium-based metal salt being RuCl3·xH2O; the organic solvent is oleylamine.
20mg of ruthenium-based metal salt, 37.5mg of second metal salt and 10mg of first metal salt are respectively measured and dissolved in 10mg of organic solvent, and the mixture is ultrasonically stirred for 30min to form brick red and clear metal salt precursor solution.
And (3) placing the metal salt precursor solution in an oil bath kettle, rapidly increasing the temperature from room temperature (25 ℃) to 180 ℃ (the temperature rise time is not more than 20 min), and keeping the temperature at 180 ℃ for 8h to obtain a solid-liquid mixture.
And centrifuging the solid-liquid mixture, collecting precipitate, cleaning with a mixed solution of ethanol, isopropanol, acetone and n-hexane, and drying in a vacuum drying oven at 90 ℃ overnight to obtain a solid.
Dispersing the sample 1 in 15ml of concentrated nitric acid, standing for 30min, taking out, cleaning with ethanol, placing in a vacuum drying oven at 60-90 ℃ for drying overnight to obtain solid powder, loading the solid powder on activated carbon, placing in a nitrogen atmosphere, and annealing at 400 ℃ for 12h to remove residual solvent.
8mg of solid with residual solvent removed is weighed and dispersed in 960. Mu.L ethanol and 40. Mu.L Nafion solution, and stirred ultrasonically for 60min to obtain a mixed and evenly mixed suspension. And (3) transferring 10 mu L of suspension by using a liquid transfer gun, coating the suspension on a glassy carbon electrode, sweeping 40 circles of cyclic voltammetry in 0.1M perchloric acid solution, and further removing unstable metal Ni to obtain the electrocatalyst.
Example 5
Raw materials: the first metal salt is Pt (acac)2(ii) a The second metal salt is Ni (NO)3)2·3H2O; the ruthenium-based metal salt being RuCl3·xH2O; the organic solvent is a mixed solvent formed by mixing oleic acid and oleylamine according to the volume ratio of 2.
Respectively measuring 19mg of ruthenium-based metal salt, 37mg of second metal salt and 8mg of first metal salt, dissolving in 10mg of organic solvent, and ultrasonically stirring for 30min to form a brick red and clear metal salt precursor solution;
and (3) placing the metal salt precursor solution in an oil bath kettle, rapidly increasing the temperature from room temperature (25 ℃) to 180 ℃ (the temperature rise time is not more than 10 min), and keeping the temperature at 200 ℃ for 12h to obtain a solid-liquid mixture.
And centrifuging the solid-liquid mixture, collecting precipitate, cleaning with a mixed solution of ethanol, isopropanol, acetone and n-hexane, and drying in a vacuum drying oven at 80 ℃ overnight to obtain a solid.
Dispersing the solid in 15ml of concentrated nitric acid, standing for 30min, taking out, cleaning with ethanol, placing in a vacuum drying oven at 60-90 ℃ for drying overnight to obtain solid powder, loading the solid powder on activated carbon, placing in a nitrogen atmosphere, and annealing at 380 ℃ for 12h to remove residual solvent.
8mg of the solid obtained after removing the residual solvent was weighed and dispersed in 960. Mu.L of ethanol and 40. Mu.L of Nafion solution, and stirred ultrasonically for 60min to obtain a mixed and well-mixed suspension. And (3) transferring 10 mu L of suspension by using a liquid transfer gun, coating the suspension on a glassy carbon electrode, and further removing unstable metal Ni after sweeping 40 cycles of cyclic voltammetry in 0.1M perchloric acid solution to obtain the electrocatalyst.
Example 6
Raw materials: the first metal salt is Pt (acac)2(ii) a The second metal salt is NiSO4(ii) a The ruthenium-based metal salt being RuCl3·xH2O; the organic solvent is a mixed solvent formed by mixing oleylamine, ethanol and octadecene according to a volume ratio of 5.
Respectively measuring 23mg of ruthenium-based metal salt, 45mg of second metal salt and 11mg of first metal salt, dissolving in 10mg of organic solvent, and ultrasonically stirring for 30min to form a brick red and clear metal salt precursor solution;
placing the metal salt precursor solution in an oil bath pan, rapidly increasing the temperature from room temperature (25 ℃) to 180 ℃ (the temperature rise time is not more than 25 min), and keeping the temperature at 220 ℃ for 6h to obtain a solid-liquid mixture;
centrifuging the solid-liquid mixture, collecting precipitate, cleaning the precipitate by using a mixed solution of ethanol, isopropanol, acetone and n-hexane, and drying the precipitate overnight in a vacuum drying oven at the temperature of 60-90 ℃ to obtain a solid substance;
dispersing the solid in 15ml of concentrated nitric acid, standing for 30min, taking out, cleaning with ethanol, placing in a vacuum drying oven at 60-90 ℃ for drying overnight to obtain solid powder, loading the solid powder on activated carbon, placing in a nitrogen atmosphere, and annealing at 450 ℃ for 12h to remove residual solvent.
8mg of solid with residual solvent removed is weighed and dispersed in 960. Mu.L ethanol and 40. Mu.L Nafion solution, and stirred ultrasonically for 60min to obtain a mixed and evenly mixed suspension. And (3) transferring 10 mu L of suspension by using a liquid transfer gun, coating the suspension on a glassy carbon electrode, and further removing unstable metal Ni after sweeping 40 cycles of cyclic voltammetry in 0.1M perchloric acid solution to obtain the electrocatalyst.
Example 7
Compared with example 1, the procedure was the same except that the organic solvent was changed to ethanol.
Example 8
Compared with example 1, the steps are the same except that the organic solvent is changed into octadecene.
Example 9
The procedure was the same as in example 1 except that the organic solvent was cyclohexane.
Example 10
Compared with example 2 except that the second metal salt is changed to Co (acac)2Otherwise, the other steps are the same.
Example 11
Compared with example 2 except that the second metal salt is changed to Co (NO)3)2·3H2Except for O, the other steps are the same.
Example 12
Compared with example 2 except that the second metal salt is changed to CoSO4Otherwise, the other steps are the same.
Example 13
Compared with example 2 except that the second metal salt is changed to Co (acac)2And CoSO4Otherwise, the other steps are the same.
Example 14
Compared with example 1 except that the second metal salt was changed to Ni (acac)2、NiCl2·2H2O and Ni (NO)3)2·3H2Except for O, the other steps are the same.
Example 15
Compared with example 2 except that the second metal salt is changed to Co (NO)3)2·3H2O、CoSO4And CoCl2·2H2In addition to O, other steps are allThe same is true.
Example 16
Compared with example 3, except that the second metal salt is changed into CuBr2、Cu(acac)2And Cu (NO)3)2·3H2Except for O, the other steps are the same.
Example 17
Compared with example 1, except that the first metal salt is changed to H2PtCl6·6H2Except for O, the other steps are the same.
Example 18
Compared with example 1, except that the first metal salt is changed to K2PtCl6·6H2Except for O, the other steps are the same.
Example 19
Compared with example 1, except that the first metal salt is changed to PtCl4Otherwise, the other steps are the same.
Example 20
Compared with example 1, except that the first metal salt is changed to H2PtCl6·6H2O、K2PtCl6·6H2O and PtCl4Otherwise, the other steps are the same.
Example 21
Compared with example 1, except that the ruthenium-based metal salt was changed to Ru (acac)3Otherwise, the other steps are the same.
Example 22
Compared with example 1, except that the ruthenium-based metal salt was changed to Ru (CO)6Otherwise, the other steps are the same.
Example 23
Compared with example 1, except that the ruthenium-based metal salt was changed to Ru (acac)3、RuCl3·xH2O and Ru (CO)6Otherwise, the other steps are the same.
Comparative example 1 commercial RuO2Catalyst and process for preparing same
Comparative example 2 commercial IrO2Catalyst and process for producing the same
The electrocatalyst prepared in example 1 and comparative example 1 were scanned using a synchrotron radiation device, and the scanning results are shown in fig. 2.
Referring to fig. 2, it is apparent that no Ru — Ru peak is evident in the spectrum of the electrocatalyst prepared in example 1, indicating that ruthenium is present in a monoatomic state in the electrocatalyst prepared according to the present invention.
Referring to FIGS. 3 to 5, the spherical aberration electron micrographs of the electrocatalysts obtained in examples 1 to 3 are shown, from which it can be seen that the ruthenium is distributed in the form of a single atom in the alloy support.
The electrocatalysts of examples 1 to 3 and comparative examples 1 and 2 were taken for comparison of oxygen evolution performance:
adding 4mg of catalyst into 40ul of 5% Nafion and 960ul of absolute ethanol solution, and performing ultrasonic dispersion for 30min to obtain a solution; and (3) dripping 10 mu L of solution on the rotating disc electrode, and airing at room temperature to obtain the film electrode. Then, a three-electrode system is established by taking an Ag/AgCl electrode as a reference electrode and a Pt wire as a counter electrode, and finally, the three-electrode system is subjected to oxygen saturation in 0.1M HClO4In the solution, a linear voltammetric measurement was carried out using a rotating disk electrode at 1600rpm and a scanning speed of 10mV/s.
As shown in FIG. 6, the performance curves in FIG. 6 correspond to the electrocatalyst according to example 3, the electrocatalyst according to example 1, the electrocatalyst according to example 2, the electrocatalyst according to comparative example 1 and the electrocatalyst according to comparative example 2, from the top down. It can be seen from FIG. 6 that the ruthenium monatomic alloy catalysts obtained in examples 1 to 3 were at 0.1mol/L HClO4The electrolyte shows excellent oxygen precipitation activity and stability which are far superior to that of commercial RuO2Catalyst and commercial IrO2Catalyst: the current densities of the Pt-Ru-Ni electrocatalyst prepared in example 1 and the Pt-Ru-Co electrocatalyst prepared in example 2 reached 10mA/cm2Requires an overpotential of only 230mV, compared to commercial RuO2The overpotential is reduced by about 35%; the current density of the Pt-Ru-Cu electrocatalyst prepared in example 3 reaches 10mA/cm2Requires only 220mV overpotential compared to commercial RuO2The overpotential is reduced by about 40%.
Further, 0.1M HClO saturated with oxygen was tested with the electrocatalysts of examples 1 to 3 and comparative example 14Oxygen precipitation stability in solution by using rotary disk electrodeQualitative testing, the test results are shown in fig. 7.
As can be seen from FIG. 7, the ruthenium monatomic catalyst obtained in each example showed little deterioration in activity for at least 28 hours of operation, i.e., the electrocatalyst obtained by the process of the invention had a stability (not less than 28 hours) much higher than that of the commercial RuO2The stability of the catalyst (2 h) has better commercial development prospect in an acid electrolytic tank; meanwhile, both the Pt-Ru-Ni electrocatalyst (75 h) prepared in example 1 and the Pt-Ru-Co electrocatalyst (75 h) prepared in example 2 were higher than the Pt-Ru-Cu electrocatalyst (28 h) prepared in example 3.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (7)
1. Use of an electrocatalyst for PEM electrolysis of water, the preparation method of the electrocatalyst comprising the steps of:
uniformly mixing ruthenium-based metal salt, first metal salt and second metal salt in an organic solvent to form a metal salt precursor solution; wherein the weight ratio of the organic solvent to the ruthenium-based metal salt to the first metal salt to the second metal salt is 1.9 to 2.3;
under the condition of stirring, heating the metal salt precursor solution to 180-220 ℃, and reacting at constant temperature until a solid-liquid mixture is formed;
carrying out solid-liquid separation on the solid-liquid mixture to obtain a solid;
removing unstable metals and residual solvents in the solid to obtain an electrocatalyst;
wherein the first metal salt is a platinum-based metal salt;
the second metal salt is nickel-based metal salt or cobalt-based metal salt.
2. The use of an electrocatalyst in PEM electrolyzed water according to claim 1, wherein the step of uniformly mixing ruthenium-based metal salt, first metal salt, and second metal salt in an organic solvent to form a metal salt precursor solution comprises one or more of oleylamine, oleic acid, octadecene, ethanol, and cyclohexane;
the first metal salt comprises Pt (acac)2、H2PtCl6·6H2O、K2PtCl6·6H2O、PtCl4One or more of;
the ruthenium-based metal salt includes Ru (acac)3、RuCl3·xH2O、Ru(CO)6One or more of (a).
3. Use of an electrocatalyst according to claim 1 or 2 in PEM electrolysis of water,
when the second metal salt is a nickel-based metal salt, the nickel-based metal salt includes Ni (acac)2、NiCl2·2H2O、Ni(NO3)2·3H2O、NiSO4One or more of; alternatively, the first and second liquid crystal display panels may be,
when the second metal salt is a cobalt-based metal salt, the cobalt-based metal salt includes Co (acac)2、CoCl2·2H2O、Co(NO3)2·3H2O、CoSO4One or more of (a).
4. The use of the electrocatalyst in PEM electrolysis water according to claim 1, wherein the temperature of the metal salt precursor solution is raised to 180 ℃ to 220 ℃, and the temperature raising time is not more than 25min in the step of reacting at constant temperature to obtain a solid-liquid mixture.
5. The application of the electrocatalyst in PEM electrolyzed water according to claim 1, wherein the metal salt precursor solution is heated to 180-220 ℃ and reacts at constant temperature for 6-12h until a solid-liquid mixture is obtained.
6. Use of an electrocatalyst according to claim 1 in PEM electrolysis of water, wherein the step of solid-liquid separation of the solid-liquid mixture to obtain solids comprises:
centrifuging the solid-liquid mixture, and collecting precipitate;
washing the precipitate by using a mixed solution of ethanol and n-hexane;
and (3) placing the cleaned precipitate at the temperature of 60-90 ℃ for vacuum drying to obtain a solid.
7. Use of an electrocatalyst according to claim 1 in PEM electrolysis of water, wherein the step of removing unstable metals and residual solvent from the solids to obtain an electrocatalyst comprises:
immersing the solid in an acid solution to initially etch away unstable metals in the solid;
washing the solid after acid etching, and then drying in vacuum;
loading the solid subjected to vacuum drying on activated carbon, and annealing at 380-450 ℃ in a nitrogen atmosphere to remove residual solvent in the solid;
and carrying out secondary etching treatment on the unstable metal in the solid by using an electrochemical cyclic voltammetry to obtain the electrocatalyst.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2238123A1 (en) * | 1997-05-21 | 1998-11-21 | Degussa Aktiengesellschaft | A carbon monoxide tolerant anode catalyst for polymer electrolyte membrane fuel cells and a process for its preparation |
| CN106914237A (en) * | 2017-02-28 | 2017-07-04 | 清华大学 | A kind of monoatomic preparation method of metal |
| CN111545250A (en) * | 2020-05-21 | 2020-08-18 | 浙江工业大学 | Ruthenium catalyst with efficient electrocatalytic full-hydrolytic performance and application thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| KR101100297B1 (en) * | 2009-01-09 | 2011-12-28 | 한국과학기술연구원 | Method for preparing metal compound powders |
| CN103413951A (en) * | 2013-08-28 | 2013-11-27 | 武汉科技大学 | Nitrogen-doped graphene-loaded Pt-based alloy nanometre electrocatalyst and preparation method thereof |
| CN104923254B (en) * | 2015-05-28 | 2017-03-01 | 中国科学技术大学 | A kind of cuprio noble metal catalyst, its preparation method and application |
| CN108514877B (en) * | 2018-04-11 | 2020-02-21 | 河南郑大催化技术研究院有限公司 | Ruthenium/carbon double-shell layer water electrolysis catalyst and preparation method thereof |
| CN109225257B (en) * | 2018-10-16 | 2021-07-27 | 中国科学技术大学先进技术研究院 | Supported monatomic catalyst and preparation method thereof |
| CN110252335B (en) * | 2019-05-31 | 2022-03-29 | 苏州大学 | Carbon-coated nickel-ruthenium nano material and preparation method and application thereof |
| CN111111690B (en) * | 2019-12-27 | 2021-01-15 | 大连理工大学 | Carbon-supported platinum-cobalt-rhodium nanorod catalyst for acidic hydrogen evolution reaction and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2238123A1 (en) * | 1997-05-21 | 1998-11-21 | Degussa Aktiengesellschaft | A carbon monoxide tolerant anode catalyst for polymer electrolyte membrane fuel cells and a process for its preparation |
| CN106914237A (en) * | 2017-02-28 | 2017-07-04 | 清华大学 | A kind of monoatomic preparation method of metal |
| CN111545250A (en) * | 2020-05-21 | 2020-08-18 | 浙江工业大学 | Ruthenium catalyst with efficient electrocatalytic full-hydrolytic performance and application thereof |
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