CN114525534A - Active electrolytic water electrode and preparation method and application thereof - Google Patents
Active electrolytic water electrode and preparation method and application thereof Download PDFInfo
- Publication number
- CN114525534A CN114525534A CN202011315032.2A CN202011315032A CN114525534A CN 114525534 A CN114525534 A CN 114525534A CN 202011315032 A CN202011315032 A CN 202011315032A CN 114525534 A CN114525534 A CN 114525534A
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- Prior art keywords
- alloy
- amorphous
- electroplating
- cobalt
- nickel
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title description 9
- 239000000758 substrate Substances 0.000 claims abstract description 70
- 230000003197 catalytic effect Effects 0.000 claims abstract description 51
- 239000006260 foam Substances 0.000 claims abstract description 51
- 239000000463 material Substances 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 15
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims abstract description 11
- 238000009713 electroplating Methods 0.000 claims description 77
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 57
- 239000012498 ultrapure water Substances 0.000 claims description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 52
- 229910001096 P alloy Inorganic materials 0.000 claims description 32
- 229910052759 nickel Inorganic materials 0.000 claims description 28
- 238000001291 vacuum drying Methods 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000007789 sealing Methods 0.000 claims description 21
- AXFKVYBBROZOGA-UHFFFAOYSA-N [P].[Mo].[Co] Chemical compound [P].[Mo].[Co] AXFKVYBBROZOGA-UHFFFAOYSA-N 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000007747 plating Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 229910001199 N alloy Inorganic materials 0.000 claims description 12
- 229910000796 S alloy Inorganic materials 0.000 claims description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 12
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 12
- 235000011151 potassium sulphates Nutrition 0.000 claims description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 12
- 235000011152 sodium sulphate Nutrition 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 11
- 229940044175 cobalt sulfate Drugs 0.000 claims description 11
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 9
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 9
- 235000015393 sodium molybdate Nutrition 0.000 claims description 9
- 239000011684 sodium molybdate Substances 0.000 claims description 9
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000008055 phosphate buffer solution Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- LEAHFJQFYSDGGP-UHFFFAOYSA-K trisodium;dihydrogen phosphate;hydrogen phosphate Chemical compound [Na+].[Na+].[Na+].OP(O)([O-])=O.OP([O-])([O-])=O LEAHFJQFYSDGGP-UHFFFAOYSA-K 0.000 claims description 3
- 229910000531 Co alloy Inorganic materials 0.000 claims description 2
- 229910001313 Cobalt-iron alloy Inorganic materials 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229910001309 Ferromolybdenum Inorganic materials 0.000 claims description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 2
- 241001089723 Metaphycus omega Species 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- VZXASIQUADSCEB-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[K+].S(O)(O)(=O)=O.[K+].[K+] Chemical compound P(=O)([O-])([O-])[O-].[K+].S(O)(O)(=O)=O.[K+].[K+] VZXASIQUADSCEB-UHFFFAOYSA-K 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 2
- IBRMMDRWVRHBJN-UHFFFAOYSA-N [Fe].[Mo].[P] Chemical compound [Fe].[Mo].[P] IBRMMDRWVRHBJN-UHFFFAOYSA-N 0.000 claims description 2
- SUECRJAYGFKIJH-UHFFFAOYSA-N [Hg+].[O-2].[Cr+3].[O-2] Chemical compound [Hg+].[O-2].[Cr+3].[O-2] SUECRJAYGFKIJH-UHFFFAOYSA-N 0.000 claims description 2
- RMKJDGIKQWEFFT-UHFFFAOYSA-N [N].[Co].[Ni] Chemical compound [N].[Co].[Ni] RMKJDGIKQWEFFT-UHFFFAOYSA-N 0.000 claims description 2
- MCONQMQZJCTYCP-UHFFFAOYSA-N [N].[Fe].[Co] Chemical compound [N].[Fe].[Co] MCONQMQZJCTYCP-UHFFFAOYSA-N 0.000 claims description 2
- MOEFVHGLEYAZHU-UHFFFAOYSA-N [N].[Fe].[Mo] Chemical compound [N].[Fe].[Mo] MOEFVHGLEYAZHU-UHFFFAOYSA-N 0.000 claims description 2
- JGOAJGFZMIYKDE-UHFFFAOYSA-N [N].[Mo].[Ni] Chemical compound [N].[Mo].[Ni] JGOAJGFZMIYKDE-UHFFFAOYSA-N 0.000 claims description 2
- CKQGJVKHBSPKST-UHFFFAOYSA-N [Ni].P#[Mo] Chemical compound [Ni].P#[Mo] CKQGJVKHBSPKST-UHFFFAOYSA-N 0.000 claims description 2
- IGOJDKCIHXGPTI-UHFFFAOYSA-N [P].[Co].[Ni] Chemical compound [P].[Co].[Ni] IGOJDKCIHXGPTI-UHFFFAOYSA-N 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims description 2
- LOUWOZBMDAQCRT-UHFFFAOYSA-N cobalt sulfanylideneiron Chemical compound [S].[Fe].[Co] LOUWOZBMDAQCRT-UHFFFAOYSA-N 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- -1 cobalt-molybdenum-iron-nitrogen Chemical compound 0.000 claims description 2
- INILCLIQNYSABH-UHFFFAOYSA-N cobalt;sulfanylidenemolybdenum Chemical compound [Mo].[Co]=S INILCLIQNYSABH-UHFFFAOYSA-N 0.000 claims description 2
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- KCYJMWPVYGWYAF-UHFFFAOYSA-N iron phosphanylidynecobalt Chemical compound [Fe].[Co]#P KCYJMWPVYGWYAF-UHFFFAOYSA-N 0.000 claims description 2
- LHLROOPJPUYVKD-UHFFFAOYSA-N iron phosphanylidynenickel Chemical compound [Fe].[Ni]#P LHLROOPJPUYVKD-UHFFFAOYSA-N 0.000 claims description 2
- ADULOCGXJMPDRK-UHFFFAOYSA-N iron;sulfanylidenemolybdenum Chemical compound [Fe].[Mo]=S ADULOCGXJMPDRK-UHFFFAOYSA-N 0.000 claims description 2
- ILKIXSABKPWMHU-UHFFFAOYSA-N iron;sulfanylidenenickel Chemical compound [Fe].[Ni]=S ILKIXSABKPWMHU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 2
- MRDDPVFURQTAIS-UHFFFAOYSA-N molybdenum;sulfanylidenenickel Chemical compound [Ni].[Mo]=S MRDDPVFURQTAIS-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- WNNZRIZCFPBTFZ-UHFFFAOYSA-N [N].[Fe].[Ni] Chemical compound [N].[Fe].[Ni] WNNZRIZCFPBTFZ-UHFFFAOYSA-N 0.000 claims 1
- 229910000358 iron sulfate Inorganic materials 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000004070 electrodeposition Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 20
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000004806 packaging method and process Methods 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- ZMXPKUWNBXIACW-UHFFFAOYSA-N [Fe].[Co].[Mo] Chemical compound [Fe].[Co].[Mo] ZMXPKUWNBXIACW-UHFFFAOYSA-N 0.000 description 3
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 3
- SIBIBHIFKSKVRR-UHFFFAOYSA-N phosphanylidynecobalt Chemical compound [Co]#P SIBIBHIFKSKVRR-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- RPZHFKHTXCZXQV-UHFFFAOYSA-N mercury(i) oxide Chemical compound O1[Hg][Hg]1 RPZHFKHTXCZXQV-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- HZUJFPFEXQTAEL-UHFFFAOYSA-N azanylidynenickel Chemical compound [N].[Ni] HZUJFPFEXQTAEL-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000003345 natural gas Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 1
Images
Classifications
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
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Abstract
The invention provides an amorphous alloy electrolytic water electrode catalytic material, which is characterized in that foam metal with excellent conductivity is selected as a substrate, a layer of multi-element amorphous alloy material is prepared on the surface of the foam metal, and the catalytic performance of a hydrogen evolution electrode is greatly improved through the synergistic effect of multiple elements. Meanwhile, the combination problem of the catalytic material and the substrate material is improved by an electrodeposition in-situ growth method. The prepared integral catalytic electrode realizes efficient hydrolysis hydrogen evolution catalysis, still keeps extremely high activity and stability under the working condition of high current density, and has good industrial application prospect and commercial value. Solves the problems of high cost, insufficient activity, poor conductivity, poor stability under high current density and the like of the existing electrolysis water hydrogen evolution catalyst.
Description
Technical Field
The invention belongs to the field of material science and technology, and particularly relates to a preparation method and application of an amorphous alloy integral catalytic electrode
Background
The hydrogen can be used as a clean energy source in the energy field of fuel cells and the like because of the extremely high energy density (283 kJ.mol < -1 >) and the clean combustion product (water), and is an ideal green fuel. The traditional hydrogen manufacturing industry produces by conversion of petrochemical energy sources, such as natural gas dehydrogenation, water gas and alcohol reforming technologies, but such technologies not only consume a large amount of fossil energy sources, but also are accompanied by the disadvantages of high energy consumption, high pollution, high investment, low purity and the like. The water electrolysis technology is a renewable hydrogen production strategy which is green, environment-friendly and efficient. However, efficient water electrolysis requires the use of active catalytic electrode materials to reduce the excess energy consumption in the hydrogen production process. At present, catalysts used for Hydrogen Evolution (HER) by water electrolysis are mainly platinum-based noble metal catalysts, so the high cost greatly limits the popularization of water electrolysis hydrogen production technology, and the water electrolysis hydrogen production only accounts for 4% of the hydrogen production industry in China by 2019. In addition, the activity and stability of the catalytic material under extreme working conditions such as large current are another important factor for restricting large-scale commercial use of the catalytic material. Therefore, the development of a non-noble metal-based electrolytic water catalytic cathode with high activity and stability and suitable for large-current working condition operation is of great commercial value.
The transition metal elements such as nickel, cobalt and the like are extremely suitable to be used as active hydrogen evolution cathode materials due to the unique electronic structure and abundant crustal reserves. However, the transition metal in the elemental state has low surface adsorption energy in the hydrogen evolution process, and is not beneficial to the hydrogen evolution reaction. Needs to be blended by multi-alloying to optimize the hydrogen absorption effect of the intermediate product in the adsorption state. In addition, the transition metal alloy is extremely easy to be oxidized during storage and use, which causes poisoning and deactivation of the catalytic material and affects the performance of the catalytic material, and therefore, the oxidation resistance of the material needs to be further improved, thereby ensuring the service life of the material. In addition, since the electrochemical hydrogen evolution process is a liquid-solid-gas three-phase interface participating reaction, the catalytic electrode itself needs to have good catalytic activity, and also needs to have good conductivity and a three-dimensional porous structure so as to improve the mass transfer process and the gas diffusion process of reactants and products. This characteristic is particularly important under high current conditions, requiring optimization and treatment of the overall structure and surface of the catalytic electrode. Finally, hydrogen production by water electrolysis is mainly carried out in alkaline electrolyte to improve the conductivity of the electrolyte, but strong alkaline solution corrodes an electrolytic cell, a pipeline and the like to a great extent, so that the development of a high-efficiency integral catalytic electrode suitable for a neutral or weak alkaline system is another technical problem of hydrogen production by water electrolysis.
In summary, an integral active electrode that fully satisfies the above requirements is not available, and the preparation process of the active catalytic material is complex, such as high-temperature calcination, ion sputtering, multi-step chemical synthesis, and the like, and is not suitable for large-scale commercial production.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of an amorphous multi-element transition metal alloy catalytic monolithic electrode, which takes foam metal as a conductive substrate and adopts an electrodeposition method to prepare an active plating layer, and the prepared monolithic catalytic electrode has higher catalytic activity when being applied to alkaline and neutral electrolytic water-out hydrogen reactions, and the catalyst can ensure long-term high activity under the condition of large current and has good stability.
The technical means adopted by the invention are as follows:
an electrolytic water material takes conductive porous foam metal as a substrate, and an alloy catalytic material is deposited on the surface of the substrate; the alloy catalytic material is an amorphous multi-element transition metal alloy. The alloy catalytic material grows on the surface of the conductive porous foam metal substrate by an electrodeposition (electroplating) method, is combined with the conductive substrate in a chemical bonding mode, and has strong adhesion and stability. The monolithic electrolytic water material grows in a self-supporting form on the conductive substrate without the addition of a binder.
Further, the foam metal is at least one of foam copper, foam nickel, foam titanium or foam alloy, the pore size of the foam metal is 50-700 PPI, and the thickness of the foam metal is 1-20 mm; the amorphous alloy is cobalt-based, nickel-based, molybdenum-based or iron-based.
Further, the amorphous alloy is one or more of amorphous nickel-cobalt alloy, amorphous nickel-iron alloy, amorphous nickel-molybdenum alloy, amorphous cobalt-iron alloy, amorphous cobalt-molybdenum alloy, amorphous ferromolybdenum alloy, amorphous nickel-iron-phosphorus alloy, amorphous nickel-iron-sulfur alloy, amorphous nickel-nitrogen alloy, amorphous nickel-cobalt-sulfur alloy, amorphous nickel-cobalt-phosphorus alloy, amorphous nickel-cobalt-nitrogen alloy, amorphous nickel-molybdenum-phosphorus alloy, amorphous nickel-molybdenum-sulfur alloy, amorphous nickel-molybdenum-nitrogen alloy, amorphous cobalt-iron-phosphorus alloy, amorphous cobalt-iron-sulfur alloy, amorphous cobalt-iron-nitrogen alloy, amorphous cobalt-molybdenum-phosphorus alloy, amorphous cobalt-molybdenum-sulfur alloy, amorphous cobalt-molybdenum-nitrogen alloy, amorphous molybdenum-iron-phosphorus alloy, amorphous iron-molybdenum-sulfur alloy, and amorphous molybdenum-iron-nitrogen alloy.
The invention also provides a preparation method of the water electrolysis material, which comprises the following steps:
(1) selecting porous foam metal with different parameters as an electrode substrate material; sequentially placing the foam metal substrate in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethyl alcohol and ultrapure water, respectively performing ultrasonic treatment for 10-30 min, then placing the foam metal substrate in a vacuum drying oven, drying the foam metal substrate for 1-12 h at 50-70 ℃ to obtain a substrate material with a clean surface, and sealing and storing the substrate material;
(2) dissolving the plating solution precursor in a solvent, and performing ultrasonic dispersion for 30-90 min to obtain a plating solution; the solvent is one or more of ethanol, water, dimethyl sulfoxide or tartaric acid;
(3) putting the substrate material with clean surface into electroplating solution to carry out electrodeposition (electroplating);
(4) and (3) placing the material obtained after electrodeposition in ultrapure water for ultrasonic washing for 10-30 min, then drying in vacuum at 50-70 ℃ for 1-12 h, and sealing for storage.
Further, in the step (1), the concentration of the dilute hydrochloric acid is 1-5 mol.L-1(ii) a The ultrapure water resistance was 18.2 M.OMEGA.cm.
Further, in the step (2), the precursor of the electroplating solution is cobalt sulfate, cobalt chloride, cobalt acetate, nickel sulfate, copper sulfate, nickel chloride, and ferric sulfateAt least one of sodium molybdate, ammonium molybdate, sodium citrate, sodium sulfate, potassium sulfate, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen hypophosphite, ammonia water, sodium hydroxide or dilute sulfuric acid; the total molar concentration of the electroplating liquid precursor is 0.01-20 mol.L-1。
Further, in the step (3), the electroplating system is a two-electrode system or a three-electrode system; in the two-electrode system, the working cathode is a foam metal substrate, and the counter electrode comprises one of a carbon plate, metal nickel, metal copper or metal titanium; in the three-electrode system, a working cathode is a foam metal substrate, a counter electrode comprises one of a carbon plate, metal nickel, metal copper or metal titanium, and a reference electrode comprises one of saturated calomel, mercury-chromium oxide or silver-silver chloride electrodes;
the electroplating is one of constant current electroplating, constant current pulse electroplating, constant potential electroplating or constant potential pulse electroplating; the current density applied in electroplating is 0.001-5A cm-2(ii) a The applied voltage for electroplating is 0.001-10V; the electroplating temperature is 25-100 ℃; the electroplating time is 0-720 min;
when constant current pulse plating or constant potential pulse plating is adopted, the time duty ratio is 1: 1-1: 500 (second), and the cycle period is 500-;
and magnetically stirring the electroplating solution in the electroplating process, wherein the stirring speed is 100-1200 rpm.
The invention also provides an application of the water electrolysis material as an integral active catalytic electrode in the cathode hydrogen evolution reaction of alkaline and neutral electrolysis water. The electrolyzed water material is a non-noble metal material, has a multi-element amorphous structure, can be used as an integral electrode for the cathode hydrogen evolution catalytic reaction of alkali and neutral electrolyzed water, and still maintains higher activity and stability under the condition of high current density.
Further, the alkaline hydrogen evolution electrolyte is one or more of a sodium hydroxide solution, a potassium hydroxide solution or a sodium carbonate solution; the neutral hydrogen-separating electrolyte is one or more of pure water solution, sodium sulfate solution, potassium sulfate solution, disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution or dipotassium hydrogen sulfate-potassium dihydrogen phosphate buffer solution.
Furthermore, the integral active catalytic electrode is suitable for an electrolyte system with the pH value more than or equal to 7; the current density of the electrolyzed water for hydrogen evolution is 0.001-10A cm-2Preferably, the current density is 0.001 to 5A cm-2。
Advantageous effects
1. The invention utilizes the unique synergistic effect of the amorphous multi-component alloy to adjust and optimize the catalytic activity in the hydrogen evolution process of the electrolyzed water, is applied to the hydrogen production equipment of the electrolyzed water, greatly improves the electrolysis efficiency and saves the electric power cost in the hydrogen production process.
2. The integral catalytic electrode provided by the invention takes the conductive foam metal as the substrate, has the advantages of excellent conductivity, larger specific surface area and the like, and is beneficial to the electron transfer and mass transfer process in the reaction.
3. The integral electrode provided by the invention does not need to be additionally provided with a bonding agent, and the active material and the base are combined by a firm chemical bond through an electroplating method, so that the stability and the conductivity of the catalyst on the substrate are greatly improved.
4. The integral catalytic electrode provided by the invention is suitable for an alkaline and neutral wide-pH electrolyte system, can effectively avoid the corrosion of strong alkali on hydrogen production equipment, and reduces the operation difficulty and equipment maintenance cost in the process of producing hydrogen by electrolyzing water.
5. The catalytic material does not use noble metal elements, has low production cost, simple operation and wide precursor source, can realize macro preparation and is easy to enlarge production.
Drawings
FIG. 1 is a scanning electron microscope image (SEM) of a sample of example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a foamed nickel substrate used in example 1 of the present invention;
FIG. 3 is a graph of electron diffraction analysis (SAED) of a sample of example 1 of the present invention;
FIG. 4 is a graph showing the hydrogen evolution activity of a sample in an alkaline neutral electrolyte according to example 1 of the present invention.
Detailed Description
The following examples are given to illustrate the preparation of the electrolytic water material of the present application in detail, and the raw materials used in the following examples are all conventional products commercially available.
Example 1
Preparing a foamed nickel loaded ternary amorphous cobalt-molybdenum-phosphorus alloy integral catalytic electrode:
1. placing foam nickel (4 x 2cm, 120PPI, 1mm) with certain size in a vacuum drying oven, sequentially placing the conductive foam metal substrate in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethyl alcohol and ultrapure water, respectively performing ultrasonic treatment for 10min, then placing the substrate in a vacuum drying oven, drying for 12h at 70 ℃ to obtain a substrate material with a clean surface, and sealing and storing;
2. dissolving 3mmol of sodium sulfate, 1ml of ammonia water, 2mmol of cobalt sulfate, 5mmol of sodium molybdate, 3mmol of potassium sulfate and 3mmol of sodium dihydrogen phosphate in 50ml of water to prepare electroplating solution;
3. transferring the electroplating solution obtained in the step (2) into a paper electroplating bath, packaging the substrate obtained in the step (1) by using a raw material belt and a resin adhesive, connecting a constant-current voltage-stabilized power supply after the exposed area is 2 x 2cm, and electroplating a two-electrode system, wherein the counter electrode is a carbon plate; applied current density 10mA cm-2Stirring the plastic by electroplating solution at 1200rpm for 1 min;
4. and (4) transferring the integral electrode obtained in the step (3) to ultra-pure water for ultrasonic washing for 10min, then placing the integral electrode in a vacuum drying oven for drying at 60 ℃ for 1h, and sealing and storing.
The prepared electrodes were subjected to scanning electron microscopy analysis (fig. 1), and a rough plating was observed compared to a smooth foamed nickel substrate (fig. 2); performing electron transmission microscope electron diffraction analysis (FIG. 3) to obtain halo-like diffraction pattern, and describing its amorphous alloy structure; the hydrogen evolution catalytic activity of the catalyst is represented under alkaline and neutral conditions (figure 4), and the catalyst shows extremely high hydrogen evolution efficiency.
Example 2
Preparing a foamed nickel loaded ternary amorphous cobalt-molybdenum-phosphorus alloy integral catalytic electrode:
1. placing foam nickel (4 x 2cm, 120PPI, 1mm) with certain size in a vacuum drying oven, sequentially placing the conductive foam metal substrate in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethyl alcohol and ultrapure water, respectively performing ultrasonic treatment for 10min, then placing the substrate in a vacuum drying oven, drying for 12h at 70 ℃ to obtain a substrate material with a clean surface, and sealing and storing;
2. dissolving 3mmol of sodium sulfate, 1ml of ammonia water, 2mmol of cobalt sulfate, 5mmol of sodium molybdate, 3mmol of potassium sulfate and 3mmol of sodium dihydrogen phosphate in 50ml of water to prepare electroplating solution;
3. transferring the electroplating solution obtained in the step (2) into a paper electroplating bath, packaging the substrate obtained in the step (1) by using a raw material belt and a resin adhesive, connecting a constant-current voltage-stabilized power supply after the exposed area is 2 x 2cm, and electroplating a three-electrode system, wherein the counter electrode is a titanium plate, and the reference electrode is a silver-silver chloride electrode; applying voltage of 3V, stirring plastic by electroplating solution at 1200rpm, and electroplating for 1 min;
4. and (4) transferring the integral electrode obtained in the step (3) to ultrapure water for ultrasonic washing for 10min for washing, then placing the electrode in a vacuum drying oven for drying at 60 ℃ for 1h, sealing and storing.
Example 3
Preparing a foamy copper loaded ternary amorphous cobalt-molybdenum-phosphorus alloy integral catalytic electrode:
1. placing foam copper (4 x 2cm, 120PPI, 1mm) with certain size in a vacuum drying oven, sequentially placing the conductive foam metal substrate in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethyl alcohol and ultrapure water, respectively performing ultrasonic treatment for 10min, drying for 12h at 70 ℃ to obtain a substrate material with a clean surface, and sealing and storing;
2. dissolving 3mmol of sodium sulfate, 1ml of ammonia water, 2mmol of cobalt sulfate, 5mmol of sodium molybdate, 3mmol of potassium sulfate and 3mmol of sodium dihydrogen phosphate in 50ml of water to prepare electroplating solution;
3. transferring the electroplating solution obtained in the step (2) into a paper electroplating bath, packaging the substrate obtained in the step (1) by using a raw material belt and a resin adhesive, connecting a constant-current voltage-stabilized power supply after the exposed area is 2 x 2cm, and electroplating a three-electrode system, wherein the counter electrode is a titanium plate, and the reference electrode is a silver-silver chloride electrode; applying voltage of 3V, stirring plastic by electroplating solution at 1200rpm, and electroplating for 1 min;
4. and (4) transferring the integral electrode obtained in the step (3) to ultrapure water for ultrasonic washing for 10min for washing, then placing the electrode in a vacuum drying oven for drying at 60 ℃ for 1h, sealing and storing.
Example 4
Preparing a foam nickel iron loaded ternary amorphous cobalt-molybdenum-iron alloy integral catalytic electrode:
1. 4 x 2cm, 120PPI and 1mm) of foam ferronickel with certain size, sequentially placing the conductive foam metal substrate in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethyl alcohol and ultrapure water for respectively carrying out ultrasonic treatment for 10min, then placing the substrate in a vacuum drying oven for drying at 70 ℃ for 12h to obtain a substrate material with a clean surface, and sealing and storing the substrate material;
2. 3mmol of sodium sulfate, 1ml of dilute sulfuric acid, 2mmol of cobalt sulfate, 5mmol of sodium molybdate, 3mmol of potassium sulfate and 3mmol of ferric sulfate are put in 50ml of water to prepare electroplating solution;
3. transferring the electroplating solution obtained in the step (2) into a paper electroplating bath, packaging the substrate obtained in the step (1) by using a raw material belt and a resin adhesive, connecting a constant-current voltage-stabilized power supply after the exposed area is 2 x 2cm, and electroplating a three-electrode system, wherein the counter electrode is a titanium plate, and the reference electrode is a silver-silver chloride electrode; applying voltage of 3V, stirring plastic by electroplating solution at 1200rpm, and electroplating for 1 min;
4. and (4) transferring the integral electrode obtained in the step (3) to ultrapure water for ultrasonic washing for 10min for washing, then placing the electrode in a vacuum drying oven for drying at 60 ℃ for 1h, sealing and storing.
Example 5
Preparing a foamed titanium loaded ternary amorphous cobalt-molybdenum-phosphorus alloy integral catalytic electrode:
1. placing a conductive foam metal substrate into ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethyl alcohol and ultrapure water in sequence, performing ultrasonic treatment for 10min, then placing the substrate into a vacuum drying oven, drying for 12h at 70 ℃ to obtain a substrate material with a clean surface, and sealing and storing the substrate material;
2. dissolving 3mmol of sodium sulfate, 1ml of ammonia water, 2mmol of cobalt sulfate, 5mmol of sodium molybdate, 3mmol of potassium sulfate and 3mmol of sodium dihydrogen phosphate in 50ml of water to prepare electroplating solution;
3. will step withTransferring the electroplating solution obtained in the step (2) into a paper electroplating bath, packaging the substrate obtained in the step (1) by using a raw material belt and a resin adhesive, connecting a constant-current voltage-stabilized power supply after the exposed area is 2 x 2cm, and electroplating a two-electrode system, wherein the counter electrode is a carbon plate; applying a pulse current density of 10mA cm-2The duty ratio is 1s/2s, the cycle period is 1000, and the electroplating solution stirs the plastic at 1200 rpm;
4. and (4) transferring the integral electrode obtained in the step (3) to ultrapure water for ultrasonic washing for 10min for washing, then placing the electrode in a vacuum drying oven for drying at 60 ℃ for 1h, sealing and storing.
Example 6
Preparing a foamed copper-zinc loaded ternary amorphous cobalt-molybdenum-phosphorus alloy integral catalytic electrode:
1. placing foam copper zinc (4 x 2cm, 120PPI, 1mm) with certain size in a vacuum drying oven, sequentially placing the conductive foam metal substrate in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethyl alcohol and ultrapure water, performing ultrasonic treatment for 10min, then placing the substrate in a vacuum drying oven, drying for 12h at 70 ℃ to obtain a substrate material with a clean surface, and sealing and storing;
2. dissolving 3mmol of sodium sulfate, 1ml of ammonia water, 2mmol of cobalt sulfate, 5mmol of sodium molybdate, 3mmol of potassium sulfate and 3mmol of sodium dihydrogen phosphate in 50ml of water to prepare electroplating solution;
3. transferring the electroplating solution obtained in the step (2) into a paper electroplating bath, packaging the substrate obtained in the step (1) by using a raw material belt and a resin adhesive, connecting a constant-current voltage-stabilized power supply after the exposed area is 2 x 2cm, and electroplating a three-electrode system, wherein the counter electrode is a titanium plate, and the reference electrode is a silver-silver chloride electrode; applying pulse voltage of 3V, duty ratio of 2s/4s, cycle period of 500, and stirring plastic by electroplating solution at 1200 rpm;
4. and (4) transferring the integral electrode obtained in the step (3) to ultrapure water for ultrasonic washing for 10min for washing, then placing the electrode in a vacuum drying oven for drying at 60 ℃ for 1h, sealing and storing.
Comparative example 1
Preparing a foamed nickel loaded binary amorphous cobalt-phosphorus alloy integral catalytic electrode:
1. placing foam nickel (4 x 2cm, 120PPI, 1mm) with certain size on a conductive foam metal substrate, sequentially placing the conductive foam metal substrate in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethyl alcohol and ultrapure water, performing ultrasonic treatment for 10min, then placing the substrate in a vacuum drying oven, drying the substrate for 12h at 70 ℃ to obtain a substrate material with a clean surface, and sealing and storing the substrate material;
2. dissolving 3mmol of sodium sulfate, 1ml of ammonia water, 2mmol of cobalt sulfate, 3mmol of potassium sulfate and 3mmol of sodium dihydrogen phosphate in 50ml of water to prepare electroplating solution;
3. transferring the electroplating solution obtained in the step (2) into a paper electroplating bath, packaging the substrate obtained in the step (1) by using a raw material belt and a resin adhesive, connecting a constant-current voltage-stabilized power supply after the exposed area is 2 x 2cm, and electroplating a two-electrode system, wherein the counter electrode is a carbon plate; applied current density 10mA cm-2Stirring the plastic by electroplating solution at 1200rpm for 1 min;
4. and (4) transferring the integral electrode obtained in the step (3) to ultrapure water for ultrasonic washing for 10min for washing, then placing the electrode in a vacuum drying oven for drying at 60 ℃ for 1h, sealing and storing.
Comparative example 2
The preparation of the foam nickel load binary amorphous cobalt-phosphorus alloy integral catalytic electrode by a sintering method comprises the following steps:
1. placing foam nickel (4 x 2cm, 120PPI, 1mm) with certain size on a conductive foam metal substrate, sequentially placing the conductive foam metal substrate in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethyl alcohol and ultrapure water, performing ultrasonic treatment for 10min, then placing the substrate in a vacuum drying oven, drying the substrate for 12h at 70 ℃ to obtain a substrate material with a clean surface, and sealing and storing the substrate material;
2. dissolving 3mmol of cobalt sulfate, 1mmol of ammonium fluoride and 3mol of urea in 50ml of water, placing the mixture in a hydrothermal kettle, and reacting for 6 hours at 120 ℃ to obtain the foamed nickel loaded chromium hydroxide precursor integral electrode.
3. Introducing H into the electrode transfer paper tube furnace obtained in the step (2)2(5%)/Ar (95%) mixed gas, 2g of sodium dihydrogen hypophosphite as a phosphorus source was placed at a gas flow inlet, reacted at 350 ℃ for 2 hours, and then annealed.
4. And (4) transferring the integral electrode obtained in the step (3) to ultrapure water for ultrasonic washing for 10min for washing, then placing the electrode in a vacuum drying oven for drying at 60 ℃ for 1h, sealing and storing.
5. Comparative example 2 the monolithic electrode prepared by the sintering method had low mechanical strength and could not be evaluated electrochemically.
Comparative example 3
Preparing a foamed nickel loaded ternary amorphous cobalt-molybdenum-phosphorus alloy integral catalytic electrode:
1. placing foam nickel (4 x 2cm, 120PPI, 1mm) with certain size in a vacuum drying oven, sequentially placing the conductive foam metal substrate in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethyl alcohol and ultrapure water, respectively performing ultrasonic treatment for 10min, then placing the substrate in a vacuum drying oven, drying for 12h at 70 ℃ to obtain a substrate material with a clean surface, and sealing and storing;
2. dissolving 3mmol of sodium sulfate, 1ml of ammonia water, 2mmol of cobalt sulfate, 5mmol of sodium molybdate, 3mmol of potassium sulfate and 3mmol of sodium dihydrogen phosphate in 50ml of water to prepare electroplating solution;
3. transferring the electroplating solution obtained in the step (2) into a paper electroplating bath, packaging the substrate obtained in the step (1) by using a raw material belt and a resin adhesive, connecting a constant-current voltage-stabilized power supply after the exposed area is 2 x 2cm, and electroplating a two-electrode system, wherein the counter electrode is a carbon plate; applied current density 5.1A cm-2Stirring the plastic by electroplating solution at 1200rpm for 1 min;
4. and (4) transferring the integral electrode obtained in the step (3) to ultrapure water for ultrasonic washing for 10min for washing, then placing the electrode in a vacuum drying oven for drying at 60 ℃ for 1h, sealing and storing.
5. In the electrode prepared in the comparative example 3 under the high current density, the catalyst layer is too thick, the adhesive force is insufficient, and a large amount of the catalyst layer falls off during electrochemical evaluation, so that the stability of the electrode is influenced.
Application example 1
The catalytic electrodes obtained in examples 1 to 6 and comparative examples 1 to 3 were used to evaluate the electrochemical hydrogen evolution activity under alkaline conditions.
1. Analyzing by adopting a standard three-electrode electrochemical linear voltammetry scanning method, wherein a reference electrode is a mercury-mercury oxide electrode, a counter electrode is a carbon sheet, an electrolyte is a 1M KOH solution, a working electrode is a prepared integral catalytic electrode, and the effective exposure area is 1 x 1 cm;
2. and (3) testing temperature: 25 ℃;
3. the hydrogen evolution activity sequence is as follows (table 1):
nickel-based amorphous cobalt molybdenum phosphorus alloy monolithic electrode (example 1) > nickel-based amorphous cobalt molybdenum phosphorus alloy monolithic electrode (example 2) ═ copper-based amorphous cobalt molybdenum phosphorus alloy monolithic electrode (example 3) > titanium-based amorphous cobalt molybdenum phosphorus alloy monolithic electrode (example 5) > copper-zinc-based amorphous cobalt molybdenum phosphorus alloy monolithic electrode (example 6) > nickel-iron-based amorphous cobalt molybdenum iron alloy monolithic electrode (example 4) > nickel-based amorphous cobalt phosphorus alloy monolithic electrode (comparative example 1);
the invention can regulate and control the catalytic activity by adjusting the components of the plating solution precursor and the plating process, and the catalytic activity of the ternary amorphous alloy monolithic electrode is generally superior to that of a binary component catalytic electrode.
Application example 2
The catalytic electrodes obtained in examples 1 to 6 and comparative examples 1 to 3 were used to evaluate the electrochemical hydrogen evolution activity under neutral conditions.
1. Analyzing by adopting a standard three-electrode electrochemical linear voltammetry, wherein a reference electrode is a mercury-mercury oxide electrode, a counter electrode is a carbon sheet, an electrolyte is 1M sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution, a working electrode is a prepared integral catalytic electrode, and the effective exposure area is 1 x 1 cm;
2. and (3) testing temperature: 25 ℃;
3. the hydrogen evolution activity sequence is as follows (table 1):
nickel-based amorphous cobalt molybdenum phosphorus alloy monolithic electrode (example 1) > nickel-based amorphous cobalt molybdenum phosphorus alloy monolithic electrode (example 2) ═ copper-based amorphous cobalt molybdenum phosphorus alloy monolithic electrode (example 3) > titanium-based amorphous cobalt molybdenum phosphorus alloy monolithic electrode (example 5) > copper-zinc-based amorphous cobalt molybdenum phosphorus alloy monolithic electrode (example 6) > nickel-iron-based amorphous cobalt molybdenum iron alloy monolithic electrode (example 4) > nickel-based amorphous cobalt molybdenum phosphorus alloy monolithic electrode (comparative example 1);
the invention can regulate and control the catalytic activity by adjusting the components of the plating solution precursor and the plating process, and the catalytic activity of the ternary amorphous alloy monolithic electrode is generally superior to that of a binary component catalytic electrode.
TABLE 1 evaluation results of catalyst Activity under alkalinity
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The water electrolysis material is characterized in that foam metal is used as a conductive substrate, and an alloy catalytic material is deposited on the surface of the conductive substrate; the alloy catalytic material is an amorphous alloy.
2. The water electrolysis material according to claim 1, wherein the foam metal is at least one of foam copper, foam nickel, foam titanium or foam alloy, the pore size of the foam metal is 50-700 PPI, and the thickness of the foam metal is 1-20 mm; the amorphous alloy is cobalt-based, nickel-based, molybdenum-based or iron-based.
3. The electrolytic water material of claim 2, wherein the amorphous alloy is one or more of amorphous nickel-cobalt alloy, amorphous nickel-iron alloy, amorphous nickel-molybdenum alloy, amorphous cobalt-iron alloy, amorphous cobalt-molybdenum alloy, amorphous ferromolybdenum alloy, amorphous nickel-iron-phosphorus alloy, amorphous nickel-iron-sulfur alloy, amorphous nickel-iron-nitrogen alloy, amorphous nickel-cobalt-sulfur alloy, amorphous nickel-cobalt-phosphorus alloy, amorphous nickel-cobalt-nitrogen alloy, amorphous nickel-molybdenum-phosphorus alloy, amorphous nickel-molybdenum-sulfur alloy, amorphous nickel-molybdenum-nitrogen alloy, amorphous cobalt-iron-phosphorus alloy, amorphous cobalt-iron-sulfur alloy, amorphous cobalt-iron-nitrogen alloy, amorphous cobalt-molybdenum-phosphorus alloy, amorphous cobalt-molybdenum-sulfur alloy, amorphous cobalt-molybdenum-iron-nitrogen alloy, amorphous molybdenum-iron-phosphorus alloy, amorphous molybdenum-iron-sulfur alloy, and amorphous molybdenum-iron-nitrogen alloy.
4. A method of producing an electrolytic water material according to claims 1-3, comprising the steps of:
(1) sequentially placing the foam metal substrate in ultrapure water, acetone, ultrapure water, dilute hydrochloric acid, ultrapure water, absolute ethyl alcohol and ultrapure water, respectively performing ultrasonic treatment for 10-30 min, and then performing vacuum drying at 50-70 ℃ for 1-12 h to obtain a substrate material with a clean surface;
(2) dissolving the plating solution precursor in a solvent, and performing ultrasonic dispersion for 30-90 min to obtain a plating solution; the solvent is one or more of ethanol, water, dimethyl sulfoxide or tartaric acid;
(3) placing the substrate material with a clean surface in electroplating solution, and electroplating in an electroplating system;
(4) and (3) placing the electroplated material in ultrapure water for ultrasonic washing for 10-30 min, then carrying out vacuum drying for 1-12 h at 50-70 ℃, and sealing for storage.
5. The method according to claim 4, wherein in the step (1), the concentration of the dilute hydrochloric acid is 1-5 mol-L-1(ii) a The ultrapure water resistance was 18.2 M.OMEGA.cm.
6. The method according to claim 4, wherein in the step (2), the plating solution precursor is at least one of cobalt sulfate, cobalt chloride, cobalt acetate, nickel sulfate, copper sulfate, nickel chloride, iron sulfate, sodium molybdate, ammonium molybdate, sodium citrate, sodium sulfate, potassium sulfate, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen hypophosphite, ammonia water, sodium hydroxide, or dilute sulfuric acid; the total molar concentration of the precursor of the electroplating solution is 0.01 to up20mol·L-1。
7. The manufacturing method according to claim 4, wherein in the step (3), the electroplating system is a two-electrode system or a three-electrode system; in the two-electrode system, the working cathode is a foam metal substrate, and the counter electrode comprises one of a carbon plate, metal nickel, metal copper or metal titanium; in the three-electrode system, a working cathode is a foam metal substrate, a counter electrode comprises one of a carbon plate, metal nickel, metal copper or metal titanium, and a reference electrode comprises one of saturated calomel, mercury-chromium oxide or silver-silver chloride electrodes;
the electroplating is one of constant current electroplating, constant current pulse electroplating, constant potential electroplating or constant potential pulse electroplating; the current density applied in electroplating is 0.001-5A cm-2(ii) a The applied voltage for electroplating is 0.001-10V; the electroplating temperature is 25-100 ℃; the electroplating time is 0-720 min;
when constant current pulse plating or constant potential pulse plating is adopted, the time duty ratio is 1: 1-1: 500 (seconds), and the cycle period is 500-;
and magnetically stirring the electroplating solution in the electroplating process, wherein the stirring speed is 100-1200 rpm.
8. Use of the water electrolysis material of claims 1-3 as an integral active catalytic electrode in the cathodic hydrogen evolution reaction of alkaline, neutral electrolyzed water.
9. The use of claim 8, wherein the alkaline hydrogen evolution electrolyte is one or more of a sodium hydroxide solution, a potassium hydroxide solution or a sodium carbonate solution; the neutral hydrogen-separating electrolyte is one or more of pure water solution, sodium sulfate solution, potassium sulfate solution, disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution or dipotassium hydrogen sulfate-potassium dihydrogen phosphate buffer solution.
10. The use according to claim 8, wherein the current density in the cathodic hydrogen evolution reaction of electrolyzed water is 0.001-10A-cm-2Preferably electric currentThe density is 0.001 to 5A/cm-2。
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