CN106498430A - Low energy consumption electrochemistry hydrogen generating system based on dual-functional nanometer array electrode - Google Patents
Low energy consumption electrochemistry hydrogen generating system based on dual-functional nanometer array electrode Download PDFInfo
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- CN106498430A CN106498430A CN201610952265.0A CN201610952265A CN106498430A CN 106498430 A CN106498430 A CN 106498430A CN 201610952265 A CN201610952265 A CN 201610952265A CN 106498430 A CN106498430 A CN 106498430A
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- transition metal
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 230000005518 electrochemistry Effects 0.000 title claims abstract description 22
- 238000005265 energy consumption Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- 150000003384 small molecules Chemical class 0.000 claims abstract description 11
- -1 phosphide Chemical class 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 150000003624 transition metals Chemical class 0.000 claims description 20
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000011669 selenium Substances 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 4
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001263 FEMA 3042 Substances 0.000 claims description 3
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
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- 150000007523 nucleic acids Chemical class 0.000 claims description 3
- 102000039446 nucleic acids Human genes 0.000 claims description 3
- 108020004707 nucleic acids Proteins 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 3
- 229940033123 tannic acid Drugs 0.000 claims description 3
- 235000015523 tannic acid Nutrition 0.000 claims description 3
- 229920002258 tannic acid Polymers 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001122 Mischmetal Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 2
- 239000000419 plant extract Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 230000001052 transient effect Effects 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims 2
- 239000004917 carbon fiber Substances 0.000 claims 2
- 239000011261 inert gas Substances 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 2
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 claims 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 claims 1
- PMUIBVMKQVKHBE-UHFFFAOYSA-N [S].NC(N)=O Chemical compound [S].NC(N)=O PMUIBVMKQVKHBE-UHFFFAOYSA-N 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 229940024606 amino acid Drugs 0.000 claims 1
- 235000001014 amino acid Nutrition 0.000 claims 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims 1
- 229910010277 boron hydride Inorganic materials 0.000 claims 1
- 238000000224 chemical solution deposition Methods 0.000 claims 1
- 238000004070 electrodeposition Methods 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229940116269 uric acid Drugs 0.000 claims 1
- 229940088594 vitamin Drugs 0.000 claims 1
- 229930003231 vitamin Natural products 0.000 claims 1
- 235000013343 vitamin Nutrition 0.000 claims 1
- 239000011782 vitamin Substances 0.000 claims 1
- 150000003722 vitamin derivatives Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 230000001590 oxidative effect Effects 0.000 abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006056 electrooxidation reaction Methods 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract description 2
- 150000002736 metal compounds Chemical class 0.000 abstract description 2
- 150000004767 nitrides Chemical class 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 150000003346 selenoethers Chemical class 0.000 abstract description 2
- 239000010953 base metal Substances 0.000 abstract 1
- 239000002070 nanowire Substances 0.000 description 24
- 238000003491 array Methods 0.000 description 20
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- 238000001291 vacuum drying Methods 0.000 description 8
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- 238000003756 stirring Methods 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002803 fossil fuel Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002429 hydrazines Chemical class 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910016506 CuCo2O4 Inorganic materials 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 229910003119 ZnCo2O4 Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 239000005357 flat glass Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910003168 MnCo2O4 Inorganic materials 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- KIJJUKCMZVPHFU-UHFFFAOYSA-L [Co](O)O.[Zn] Chemical compound [Co](O)O.[Zn] KIJJUKCMZVPHFU-UHFFFAOYSA-L 0.000 description 1
- CXZVZEVGMGNFPP-UHFFFAOYSA-L [Cu].[Co](O)O Chemical compound [Cu].[Co](O)O CXZVZEVGMGNFPP-UHFFFAOYSA-L 0.000 description 1
- PAMVFMLMCGDWGU-UHFFFAOYSA-N [K].O[PH2]=O Chemical compound [K].O[PH2]=O PAMVFMLMCGDWGU-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 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
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical class O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical class [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical class [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group 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
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Abstract
The invention discloses transistion metal compound (including phosphide, sulfide, selenides, nitride) nano-array is used for low energy consumption electrochemistry hydrogen manufacturing as small molecule electroxidation and water power reduction double-function catalyzing electrode, belong to Hydrogen Energy and fuel cell field.The present invention is simultaneously used for small molecule electroxidation and water power reduction with difunctional base metal array catalysis electrode first, and Electrochemical oxygen evolution reaction is replaced with the low small molecule electro-oxidation reaction of oxidizing potential, construct the two electrolysis systems based on double-function catalyzing electrode, low energy consumption, stable electrochemistry hydrogen manufacturing is achieved, is suitable for large-scale industry hydrogen manufacturing application.
Description
Technical field
The invention belongs to Hydrogen Energy and fuel cell field, more particularly, are related to prepare transistion metal compound (including phosphorus
Compound, sulfide, selenides, nitride) nano-array used as small molecule electroxidation and water power reduction double-function catalyzing electrode
In low energy consumption electrochemistry hydrogen manufacturing.
Background technology
A large amount of consumption of fossil fuel cause serious energy crisis and environmental problem, find the height of alternative fossil fuel
Effect, renewable and clean energy resource become one of most important challenge for currently being faced (Nature 2001,414,353).Hydrogen because
Have can store, efficiently and receive much concern the features such as cleaning (Acc.Chem.Res.2012,45,767).Current more than 95%
Hydrogen comes from fossil fuel, and water electrolysis is used as the important means of industrialization hydrogen manufacturing, relative to fossil fuel, to environment more
Friendly.Water electrolysis hydrogen producing is related to two important fundamental reactions, the i.e. reduction of negative electrode water and anode water oxidation.However, kinetics
Restriction require to provide overvoltage higher than theoretical decomposition voltage accelerating polarization response, cause serious electric energy loss, your gold
Category such as platinum, ruthenium-oxide etc. can be effectively reduced reaction activity base, lift reaction rate, but expensive price limits which in electrolysis water
Large-scale use in industry.Therefore, the electrocatalysis material for developing efficiently, stable, cheap and easy to get is used for water decomposition hydrogen manufacturing and there is weight
Want meaning (Prog.Energy Combust.Sci.2010,36,307；Chem.Soc.Rev.2015,44,181；
Adv.Mater.2016,28,215).And can be entered using the bifunctional electrocatalyst for water being reduced and water oxygenization all has catalysis activity
One step simplify system and reduce processing cost (Science 2014,345,1593).
Water oxygen is the very crucial and extremely complex reaction of a step during electrolysis water, decide electrolysis water energy consumption and
Efficiency, becomes the bottleneck (Science 2006,314,821 of water electrolysis hydrogen production；Science 2008,321,1072；
J.Am.Chem.Soc.2016,138,4006).Replace water oxidation reaction to be easier the electrochemistry small molecule oxidation reaction of oxidation
Lower than traditional electrolyte water hydrogen manufacturing energy consumption, but the electric catalyticing system of report is limited to the use of precious metal catalytic material at present
(Nat.Commun.2014,5,4036) or limited catalytic current density (Angew.Chem.Int.Ed.2016,55,3804),
And the small molecule oxidation based on non-noble metal nano array and water power reduction double-function catalyzing electrode realize the work of low energy consumption hydrogen manufacturing
Have no report.
Content of the invention
In order to solve problems of the prior art, it is contemplated that overcoming the defect of existing catalyst system and catalyzing, there is provided energy
Organic molecule and inorganic molecules electrochemical oxidation and in hgher efficiency, more reliable electrochemistry producing hydrogen, catalyzing electrode are enough applied to
And its application.
The double-function catalyzing electrode reduced for small molecule electroxidation and water power of the present invention include active component and
Conductive carrier, active component are transition metal nano-array.
According to one embodiment of application of the present invention, directly using transition metal nano-array as small molecule electroxidation
Anode and water power reduction negative electrode, realize high-efficiency electrochemical hydrogen manufacturing.
According to one embodiment of application of the present invention, electrolyte is alkalescence or neutral aqueous solution.
The one embodiment of root according to application of the present invention, the transition metal nano-array contain one or more
Transition metal, the transition metal be iron, cobalt, nickel, copper, molybdenum, tungsten, vanadium, titanium, zinc, aluminium, chromium, manganese, gallium, indium, germanium,
Tin.
According to one embodiment of application of the present invention, the transition metal nano-array includes transition metal phosphatization
Thing, transient metal sulfide, transition metal selenides, transition metal nitride.
According to one embodiment of application of the present invention, the transition metal nano-array by nano wire, nanometer rods,
Nanotube, nanometer sheet, nanometer plate or its hierarchy or core shell structure etc. are constituted.
According to one embodiment of application of the present invention, the transition metal nano-array content is 0.1～
50wt%, carrier are one or more mischmetal knot of iron, nickel, vanadium, copper, stainless steel, cobalt, titanium, molybdenum, tungsten, aluminium, zinc, chromium, manganese
Structure (net/paper tinsel/piece), carbon cloth, carbon paper, electro-conductive glass piece and conductive silicon chip.
Compared with prior art, transition metal nano-array is simultaneously used for by the present invention first as double-function catalyzing electrode
Small molecule electroxidation and water power reduction, realize low energy consumption electrochemistry hydrogen manufacturing, show excellent catalysis activity and structural stability,
Have broad application prospects.
Description of the drawings
Fig. 1 is the Ni grown on nickel screen in embodiment 12The scanning electron microscope (SEM) photograph of P nano-chip arrays and its urge as difunctional
Polarizing electrode aoxidizes hydrazine electrochemistry hydrogen manufacturing in the basic conditions.
Fig. 2 is for the scanning electron microscope (SEM) photograph of the FeP nano-chip arrays of growth on carbon cloth in embodiment 2 and as double-function catalyzing electricity
Pole aoxidizes hydrazine electrochemistry hydrogen manufacturing in the basic conditions.
Fig. 3 is the NiS grown in titanium net in embodiment 62Nano-chip arrays are as double-function catalyzing electrode in alkalescence condition
Lower oxidation hydrazine electrochemistry hydrogen manufacturing.
Fig. 4 is to grow Co in embodiment 9 on stainless (steel) wire4N nano-wire arrays are as double-function catalyzing electrode in alkaline bar
Urea electrochemistry hydrogen manufacturing is aoxidized under part.
Specific embodiment
All features disclosed in this specification, or disclosed all methods or during the step of, except mutually exclusive
Feature and/or step beyond, can combine by any way.
Any feature disclosed in this specification, unless specifically stated otherwise, can be equivalent or with similar purpose by other
Alternative features are replaced.I.e., unless specifically stated otherwise, each feature is an example in a series of equivalent or similar characteristics
?.
Embodiment 1：
Step one：The distilled water of 36mL is added in polytetrafluoroethyllining lining, that is, add 1.45g nickel nitrates and 1.40g six
Methine tetramine, and stir until solid be completely dissolved, formed clear solution.
Step 2：Nickel screen is put in the inner liner of reaction kettle of step one, and polytetrafluoroethyllining lining is sealed to stainless steel
In mould, it is placed under sealing condition in thermostatic drying chamber and heating response 10h at 100 DEG C.
Step 3：After the completion of reaction, along with the furnace cooling to room temperature, then nickel screen taking-up, successively with distilled water and absolute ethyl alcohol
Washed, and by washing after carbon cloth be placed in vacuum drying chamber and at 40 DEG C be vacuum dried 24h, obtain Ni
(OH)2Nano-chip arrays.
Step 4：Presoma obtained in step 3 is placed in tube furnace and adds sodium hypophosphite, in argon atmosphere,
2h is reacted under the conditions of 300 DEG C, obtain Ni2P nano-chip arrays, its microstructure are as shown in Figure 1.
Step 5：With two panels Ni2P nano-wire arrays build two electrode systems as hydrazine oxidizing anode and water reduction negative electrode,
With the 1.0M KOH containing 0.5M hydrazines as electrolyte, electrochemistry hydrogen manufacturing under normal temperature condition, concrete catalytic performance result such as Fig. 1 institutes
Show.
Embodiment 2：
Step one：The distilled water of 35mL is added in polytetrafluoroethyllining lining, adds 0.4g Iron trichloride hexahydrates and 0.24g sulphur
Sour sodium is simultaneously stirred until solid is completely dissolved.
Step 2：Carbon cloth is put in the inner liner of reaction kettle of step one, and polytetrafluoroethyllining lining is sealed to stainless steel
In mould, be placed under sealing condition in thermostatic drying chamber and 6h is reacted at 120 DEG C.
Step 3：After the completion of reaction, then carbon cloth is taken out by along with the furnace cooling to room temperature, clean, and by washing after carbon cloth
Be placed in vacuum drying chamber and 24h be vacuum dried at 40 DEG C, obtain Fe2O3Nano-chip arrays.
Step 4：Step 3 is obtained Fe2O3Nano-chip arrays are placed in tube furnace and add potassium hypophosphite, in argon atmospher
In enclosing, 2h is reacted under the conditions of 300 DEG C, obtain FeP nano-chip arrays (Fig. 2).
Step 5：Using two panels FeP nano-chip arrays as hydrazine oxidizing anode and water reduction negative electrode, two electrode systems are built,
With the 1.0M KOH containing 0.5M hydrazines as electrolyte, electrochemistry hydrogen manufacturing under normal temperature condition, concrete catalytic performance result such as Fig. 2 institutes
Show.
Embodiment 3：
Step one：The distilled water of 40mL is added in polytetrafluoroethyllining lining, adds 1mmol zinc nitrates, 2mmol nitric acid
Cobalt, 0.074g ammonium fluorides and 0.3g urea, stirring and dissolving form clear solution.
Step 2：Electro-conductive glass piece is put in the inner liner of reaction kettle of step one, and polytetrafluoroethyllining lining is sealed to
In stainless steel mould, it is placed under sealing condition in thermostatic drying chamber and heating response 6h at 120 DEG C.
Step 3：After the completion of reaction, sheet glass is taken out, clean, and by washing after sheet glass be placed in vacuum drying chamber
In and dry 24h at 40 DEG C, obtain zinc cobalt hydroxide array structure, then in atmosphere 400 DEG C anneal 2 hours, obtain
ZnCo2O4Nano-wire array.
Step 4：Step 3 is obtained ZnCo2O4Nano-wire array is placed in tube furnace and adds potassium hypophosphite, in argon gas
In atmosphere, 3h is reacted under the conditions of 320 DEG C, obtain ZnCoP nano-wire arrays.
Step 5：Using two panels ZnCoP nano-wire array as glucose oxidizing anode and water reduction negative electrode, two electrodes are built
System, with the neutral aqueous solution containing 0.1M glucose as electrolyte, electrochemistry hydrogen manufacturing under normal temperature condition.
Embodiment 4：
Step one：The distilled water of 40mL is added in polytetrafluoroethyllining lining, adds 1mmol copper nitrates, 2mmol nitric acid
Cobalt, 0.074g ammonium fluorides and 0.3g urea, stirring form clear solution.
Step 2：Titanium sheet is put in the inner liner of reaction kettle of step one, and polytetrafluoroethyllining lining is sealed to stainless steel
In mould, it is placed under sealing condition in thermostatic drying chamber and heating response 6h at 120 DEG C.
Step 3：After the completion of reaction, then titanium sheet is taken out, clean, and by washing after titanium sheet be placed in vacuum drying chamber
In and be vacuum dried 24h at 40 DEG C, obtain copper cobalt hydroxide array structure, then 400 DEG C of heat treatments are 2 little in atmosphere
When, obtain CuCo2O4Nano-wire array.
Step 4：Step 3 is obtained CuCo2O4Nano-wire array array is placed in tube furnace and adds potassium hypophosphite,
In argon atmosphere, 2h is reacted under the conditions of 340 DEG C, obtain CuCoP nano-wire arrays.
Step 5：Using two panels CuCoP nano-wire array as amino-acid oxidase anode and water reduction negative electrode, two electrodes are built
System, with the 0.5M KOH containing 0.05M amino acid as electrolyte, electrochemistry hydrogen manufacturing under normal temperature condition.
Embodiment 5：
Step one：2mmol ammonium persulfates and 40mL NaOH are added in 15mL deionized waters, is put into after mixed dissolution and is washed
Net foam copper, reacts 20 minutes under room temperature, obtains Cu (OH) after drying2Nano-wire array presoma.
Step 2：Presoma obtained in step one is placed in ptfe autoclave, 150mL is added dissolved with 0.075M
Cobaltous sulfate and the mixed solution of 1.125M urea, 85 DEG C reaction 4h, then in atmosphere 300 DEG C annealing 2h, obtain CuO/Co3O4
Classifying nano linear array.
Step 3：By CuO/Co obtained in step 23O4Classifying nano linear array is placed in tube furnace and adds hypophosphorous acid
Potassium, in argon atmosphere, under the conditions of 310 DEG C reacts 2.5h, obtains Cu3P/CoP classifying nano linear arrays.
Step 4：With two panels Cu3P/CoP classifying nanos linear array reduces negative electrode as nucleic acid base oxidizing anode and water,
Two electrode systems are built, with the 1.0M KOH containing 0.02M nucleic acid bases as electrolyte, electrochemistry hydrogen manufacturing under normal temperature condition.
Embodiment 6：
Step one：The distilled water of 36mL is added in polytetrafluoroethyllining lining, that is, add 1.46g nickel nitrates and 1.41g six
Methine tetramine, and stir until solid be completely dissolved, formed clear solution.
Step 2：Titanium net is put in the inner liner of reaction kettle of step one, and polytetrafluoroethyllining lining is sealed to stainless steel
In mould, it is placed under sealing condition in thermostatic drying chamber and heating response 10h at 100 DEG C.
Step 3：After the completion of reaction, then titanium net is taken out by along with the furnace cooling to room temperature, successively with distilled water and anhydrous second
Alcohol is washed, and by washing after titanium net be placed in vacuum drying chamber and at 40 DEG C be vacuum dried 24h, obtain Ni (OH)2
Nano-chip arrays.
Step 4：By Ni obtained in step 3 (OH)2Nano-chip arrays are placed in tube furnace, with sulphur powder as sulphur source, in argon
During atmosphere is enclosed, 4h is reacted under the conditions of 400 DEG C, obtain NiS2Nano-chip arrays.
Step 5：With two panels Ni2P nano-wire arrays build two electrode systems as hydrazine oxidizing anode and water reduction negative electrode,
With the 1.0M KOH containing 0.5M hydrazines as electrolyte, electrochemistry hydrogen manufacturing under normal temperature condition, its catalytic performance result such as Fig. 3.
Embodiment 7：
Step one：The distilled water of 40mL is added in polytetrafluoroethyllining lining, adds 1mmol manganese nitrates, 2mmol nitric acid
Cobalt, 0.074g ammonium fluorides and 0.3g urea, stirring and dissolving form clear solution.
Step 2：Carbon paper is put in the inner liner of reaction kettle of step one, and polytetrafluoroethyllining lining is sealed to stainless steel
In mould, it is placed under sealing condition in thermostatic drying chamber and heating response 6h at 120 DEG C.
Step 3：After the completion of reaction, carbon paper is taken out, clean, and by washing after titanium sheet be placed in vacuum drying chamber simultaneously
Dry 24h at 40 DEG C, then in atmosphere 400 DEG C anneal 2 hours, obtain MnCo2O4Nano-wire array.
Step 4：By MnCo obtained in step 32O4Nano-wire array array is placed in tube furnace, with selenium powder as selenium source,
In argon atmosphere, 2h is reacted under the conditions of 450 DEG C, obtain MnCo2Se4Nano-wire array.
Step 5：With two panels MnCo2Se4Nano-wire array builds two electricity as tannic acid oxidizing anode and water reduction negative electrode
Electrode systems, with the 0.5M KOH containing 0.1M tannic acid as electrolyte, electrochemistry hydrogen manufacturing under normal temperature condition.
Embodiment 8：
Step one：The distilled water of 40mL is added in polytetrafluoroethyllining lining, adds 1mmol nickel nitrates, 2mmol nitric acid
Cobalt, 0.074g ammonium fluorides and 0.3g urea, stirring and dissolving form clear solution.
Step 2：Copper sheet is put in the inner liner of reaction kettle of step one, and polytetrafluoroethyllining lining is sealed to stainless steel
In mould, it is placed under sealing condition in thermostatic drying chamber and heating response 8h at 150 DEG C.
Step 3：After the completion of reaction, copper sheet is taken out, clean, and by washing after titanium sheet be placed in vacuum drying chamber simultaneously
Dry 12h at 60 DEG C, then in atmosphere 450 DEG C anneal 1 hour, obtain NiCo2O4Nano-wire array.
Step 4：By NiCo obtained in step 32O4Nano-wire array array is placed in tube furnace, with selenium powder as selenium source,
In argon atmosphere, 3h is reacted under the conditions of 450 DEG C, obtain NiCo2Se4Nano-wire array.
Step 5：With two panels NiCo2Se4Nano-wire array is built as plant extracts oxidizing anode and water reduction negative electrode
Two electrode systems, with the 0.5M KOH containing plant extraction liquid as electrolyte, electrochemistry hydrogen manufacturing under normal temperature condition.
Embodiment 9：
Step one：The distilled water of 35mL is added in polytetrafluoroethyllining lining, controls to add 0.87g nitre in every milliliter of water
Sour cobalt, 0.11g ammonium fluorides and 0.18g urea, stirring and dissolving form clear solution.
Step 2：Stainless (steel) wire is put in the inner liner of reaction kettle of step one, and polytetrafluoroethyllining lining is sealed to not
In rust steel mold, it is placed under sealing condition in thermostatic drying chamber and heating response 12h at 120 DEG C.
Step 3：After the completion of reaction, stainless (steel) wire is taken out, clean, and by washing after silicon chip be placed in vacuum drying chamber
In and at 40 DEG C be vacuum dried 24h, obtain Co (OH) F nanowire array structures.
Step 4：Presoma obtained in step 3 is placed in tube furnace, nitrogen source is enclosed with ammonia, in argon atmosphere,
3h is reacted under the conditions of 400 DEG C, obtain Co4N nano-wire arrays.
Step 5：With two panels Co4N nano-wire arrays build two electrode systems as urea oxidizing anode and water reduction negative electrode
System, with the 1.0M KOH containing 0.55M urea as electrolyte, electrochemistry hydrogen manufacturing under normal temperature condition, concrete catalytic performance result is such as
Shown in Fig. 4.
Claims (9)
1. transition metal nano-array reduces double-function catalyzing electrode in low energy consumption electrochemistry as small molecule electroxidation and water power
Application in hydrogen manufacturing, the catalysis electrode are made up of transition metal nano-array and conductive carrier two parts.
2. application according to claim 1, it is characterised in that transition metal nano-array electrode is placed in electrolyte,
Realize High-efficient Water electrolytic hydrogen production.
3. application according to claim 2, it is characterised in that the electrolyte is alkalescence, the neutral or weakly acidic pH aqueous solution.
4. application according to claim 1, it is characterised in that the transition metal nano-array content be 0.1～
50wt%, carrier are one or more mischmetal knot of iron, nickel, vanadium, copper, stainless steel, cobalt, titanium, molybdenum, tungsten, aluminium, zinc, chromium, manganese
Structure (net/paper tinsel/piece), carbon fiber, carbon cloth, carbon fiber paper, electro-conductive glass piece and conductive silicon chip.
5. application according to claim 1, it is characterised in that the transition metal nano-array contains one or more mistake
Metallic element is crossed, the transition metal is iron, cobalt, nickel, copper, molybdenum, tungsten, vanadium, titanium, zinc, aluminium, chromium, manganese, gallium, indium, germanium, tin.
6. application according to claim 1, it is characterised in that the transition metal nano-array includes transition metal phosphatization
Thing, transient metal sulfide, transition metal selenides, transition metal nitride.
7. application according to claim 1, it is characterised in that the transition metal nano-array is by corresponding transition metal
Simple substance (alloy), oxide or hydroxide nano array presoma pass through under atmosphere of inert gases, in phosphorus source, sulphur source, selenium
Source, nitrogen source are annealed under conditions of existing and are obtained, and presoma can pass through hydro-thermal reaction, electro-deposition, chemical bath deposition in conductive load
On body prepared by growth in situ.
8. application according to claim 7, it is characterised in that the inert gas is that argon gas or nitrogen, annealing temperature are
250～900 DEG C, annealing time is 1～8 hour, and phosphorus source is in sodium hypophosphite, potassium hypophosphite, hypophosphorous acid, red phosphorus or white phosphorus
Plant or multiple；Sulphur source is sulphur powder；Selenium source is selenium powder.
9. application according to claim 1, it is characterised in that the small molecule includes the organic molecule with reproducibility
(sugar, alcohol, aldehyde, amine, amino acid, vitamin, tannic acid, nucleic acid base, plant extracts etc.) and inorganic molecules (urea, sulphur
Urea, uric acid, hydrazine, boron hydride, sulfide, iodide etc.) in one or more.
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