CN108502859A - 一种复合电极的光化学制备方法 - Google Patents
一种复合电极的光化学制备方法 Download PDFInfo
- Publication number
- CN108502859A CN108502859A CN201810157065.5A CN201810157065A CN108502859A CN 108502859 A CN108502859 A CN 108502859A CN 201810157065 A CN201810157065 A CN 201810157065A CN 108502859 A CN108502859 A CN 108502859A
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- preparation
- electrode
- phosphorous compound
- phosphorus
- reaction
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Links
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 34
- 239000011574 phosphorus Substances 0.000 claims abstract description 33
- 230000003287 optical effect Effects 0.000 claims abstract description 27
- 239000013543 active substance Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 238000005286 illumination Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 17
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 16
- 229910021389 graphene Inorganic materials 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 13
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 12
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- 229910052724 xenon Inorganic materials 0.000 claims description 11
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 9
- 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 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000007717 exclusion Effects 0.000 claims description 5
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- OISMQLUZKQIKII-UHFFFAOYSA-L dichlorocadmium;hydrate Chemical compound O.[Cl-].[Cl-].[Cd+2] OISMQLUZKQIKII-UHFFFAOYSA-L 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 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
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 238000012546 transfer Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- -1 phosphorus compound Chemical class 0.000 abstract description 6
- 230000002829 reductive effect Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 238000013459 approach Methods 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 25
- 239000001257 hydrogen Substances 0.000 description 25
- 229910052739 hydrogen Inorganic materials 0.000 description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- 238000001962 electrophoresis Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 238000007872 degassing Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical class Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002083 X-ray spectrum Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- PMUIBVMKQVKHBE-UHFFFAOYSA-N [S].NC(N)=O Chemical compound [S].NC(N)=O PMUIBVMKQVKHBE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000012407 engineering method Methods 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明公开了一种复合电极的光化学制备方法,属于材料科学和电化学技术领域。本发明通过简便的方法合成了含磷复合物催化剂及其复合电极,在光活性物质光照条件下,金属与磷源生成金属与磷复合物,该含磷复合物在电催化方面表现出优异的性能。本发明的制备方法简便、可控,并且绿色环保,为电极的制备提供一种新思路,制备得到的复合电极具有极低的电荷转移电阻,且为非贵金属催化剂,降低了生产成本,具有一定的工业应用价值。
Description
技术领域
本发明涉及一种复合电极的光化学制备方法,属于材料科学和电化学技术领域。
背景技术
能源是促进人类社会文明的基本物质,随着环境问题日益严重,化石燃料储备日益枯竭,我们的地球已经在努力为不断增长的能源需求买单。因此,发现可持续清洁能源变得尤为迫切。氢气是目前零污染和高能量密度的理想可再生能源。使用太阳能,风能和其他可再生能源发电,利用电能还原水分解制氢是一种简单、有效的方式。为了更好的提高产氢效率和速率,使用电催化剂还原水产氢是非常必要的。铂(Pt)基催化剂是众所周知的有效和稳定的电催化剂,但昂贵的价格和低的丰度限制了其大规模商业应用。因此,开发高活性,丰度高和稳定性好的非贵金属电催化剂是特别必要的。
最近,复合催化剂用于析氢反应并显示出优异的性能。例如,通过热处理合成耦合的二硫化钼/石墨烯纳米片,获得了优异的电催化性能。通过界面工程方法制备偶联的二硫化钼和g-C3N4应用在电催化产氢方面也表现出了优异的性能。利用化学气相沉积技术(CVD)和煅烧方法制备的偶联的磷化镍/石墨烯/镍泡沫(Ni2P-G@NF)也显示出了优异的电催化活性。
在过去的几年中,金属硫化物、硒化物、碳化物、氮化物等等作为产氢电催化剂不断的涌现出来。最近,金属磷化物由于其高活性和对酸稳定性而特别有吸引力。据发明人所知,金属磷化物的制备方法主要有以下几种:
第一种方法是使用三辛基膦(TOP)作为磷源高温条件下(T>300℃)合成金属磷化物,但是三辛基膦高度易燃且具有腐蚀性。
第二种方法,300-400℃高温条件下分解次亚磷酸盐(例如:NaH2PO2)产生剧毒气体PH3,PH3高温条件下还原金属氧化物/金属氢氧化物生成金属磷化物。
第三种方法,利用溶剂热法140-200℃使用红磷、白磷作为磷源合成金属磷化物。
第四种方法,使用氢气高温(T>600℃)还原金属的正磷酸盐制备金属磷化物。
这些方法为金属磷化物的合理设计和可扩展制造提供了多种方向。但它仍然需要创建一些新的合成方法来改善当前方法的不足之处。
发明内容
为了解决上述问题,本发明采用简便、温和、低成本的光化学法制备出含磷复合物电催化剂,该催化剂成本低,性能好,具有较高稳定性和使用价值,且尚无文献报道。本发明开发了清洁高效的可持续能源,使用一种快速、可控的光化学方法制备出复合电极,从而降低了电极的成本以及产氢过电势,提高了电催化水分解的效率和速率,电极的寿命很长,可多次重复利用,这为工业化应用打下良好基础。此外,该复合电极的光化学制备方法不仅快速、可控,而且利用光能制备催化剂更绿色环保。
本发明的第一个目的是提供一种复合电极,含有含磷复合物。
在一种实施方式中,含磷复合物的制备方法,包括在光活性物质光照情况下,金属离子与磷源生成所述含磷复合物;所述含磷复合物中含有磷和金属;所述生成反应中,必要物质为光活性物质、金属源和磷源。
根据上述的制备方法,其特征在于,除了必要物质之外,不加入其它牺牲剂。
在一种实施方式中,所述含磷复合物的制备方法是:将光活性物质加入到反应容器中,然后添加分散在溶剂中的金属源和磷源,混合均匀后除去反应体系中的氧气,然后后置于光照下搅拌反应,生成含磷复合物。
在一种实施方式中,所述含磷复合物为磷化镍/类石墨烯碳氮化合物复合催化剂;其制备方法包括:(1)取一定量的类石墨烯碳氮化合物(g-C3N4)加入25mL单口圆底烧瓶,加入一定量次磷酸钠(分子式NaH2PO2)和硫酸镍的混合水溶液,加入适量水,混合均匀后通入氮气30-40min以除去反应体系中氧气,然后置于氙灯下光照,光照时保持均匀搅拌;(2)反应结束后,使用离心分离将固体分离,去离子水离心洗涤5-8次,乙醇洗涤1-3次,将所得固体物质氮气吹燥,所得黑色固体物质即为产品磷化镍/类石墨烯碳氮化合物复合催化剂。
在一种实施方式中,所述类石墨烯碳氮化合物的制备具体是:取适量硫脲置于坩埚中,将坩埚置于马弗炉中550℃煅烧2h,待马弗炉降至室温取出坩埚,将黄色固体研磨后、置于坩埚中,将坩埚置于马弗炉中500℃煅烧2h,待马弗炉降至室温取出黄白色粉末即为类石墨烯碳氮化合物(C3N4)。
在一种实施方式中,所述含磷复合物为磷化钴/硫化镉纳米棒复合催化剂;所述方法,具体是:
(1)取一定量的硫化镉纳米棒加入25mL单口圆底烧瓶,加入一定量次磷酸钠(分子式NaH2PO2)和氯化钴的混合水溶液,混合均匀后通入氮气30-40min以除去反应体系中氧气,然后置于氙灯下光照,光照时保持均匀搅拌,通过不同的光照时间调节CoxP含量;
(2)反应结束后,使用离心分离将固体分离,去离子水离心洗涤5-8次,乙醇洗涤1-3次,将所得固体物质干燥,所得固体物质即为产品CoxP/硫化镉纳米棒复合催化剂。
在一种实施方式中,所述硫化镉纳米棒的制备具体是:取适量2.5水合氯化镉、硫脲与一定体积乙二胺置于100mL高压反应釜中,将反应釜置于160℃烘箱中水热处理48h,反应结束后将反应釜置于自然条件下降至室温,过滤得到黄色固体并用去离子水洗涤10次左右,乙醇洗涤1-2次,将得到固体置于60℃烘箱干燥一整晚,得到的黄色固体即为硫化镉纳米棒。
本发明的第二个目的是提供所述复合电极的制备方法,包括在光活性物质光照情况下,金属离子与磷源生成含磷复合物;所述生成反应中,必要物质为光活性物质、金属源和磷源;所述光活性物质,或者获得的含磷复合物,固定或者连接在导电基底上。
在一种实施方式中,所述光活性物质,或者获得的含磷复合物,固定或者连接在导电基底上,可以通过电泳法、旋涂法、滴涂法、水热法、电沉积法、煅烧法等方法实现。
在一种实施方式中,所述光活性物质是通过电泳的方法附着在导电基底上。
在一种实施方式中,所述光活性物质附着在导电基底上的方法,具体是:取10mg的g-C3N4黄白色粉末放入250mL烧杯中,加入10mg六水合硝酸镁和100mL异丙醇溶液,超声处理3h。然后用铂电极作为阳极在电泳仪中电泳10min,取出制备好的电极并用去离子水冲洗,烘干。
在一种实施方式中,所述复合电极,还包括先将光活性物质固定或者连接到相应的导电基底上。
在一种实施方式中,所述导电基底可以是泡沫镍、ITO、FTO、镍片、镍网、钛片、钛网、铜片、铜网、不锈钢片、不锈钢网、碳纤维布、透明导电布中的一种或几种。
光活性物质是指在能够在光子的激发下吸收光子能量的物质。
在一种实施方式中,所述磷源中,磷的价态可以是-3到+5价的。所述磷源,可以是各种形态的磷源,比如单质,无机磷,有机磷等。在一些实施方式中,所述磷源可以是无机磷,比如以下任意一种或者多种组合:次磷酸根、亚磷酸根、或正磷酸根(H2PO2 -,H2PO3 -,H2PO4 -)。可以是以下任意一种或者多种组合:NaH2PO2、NaH2PO3、NaH2PO4。在另一些实施方式中,所述磷源可以为有机物,比如三辛基膦等有机磷。在一些实施方式中,所述磷源为单质磷,比如红磷和白磷等。
在一种实施方式中,所述金属离子中的金属,可以是过渡金属,还可以是In、Pt、Pd、Rh、Re、Ir。可选地,所述过渡金属可以是铁、钴、镍、铜、锰、锌、铝等,还可以是铬、钼、钨等。
在一种实施方式中,所述金属离子,可选地,是由金属盐提供的。可选地,所述金属盐,可以是氯盐、溴盐、硝酸盐、亚硝酸盐、硫酸盐、亚硫酸盐、乙酸盐等。
在一种实施方式中,所述金属离子的供体可分散在反应体系中。
在一种实施方式中,所述光,是指能够能够激发光活性物质、与光活性物质能级匹配的光。
在一种实施方式中,所述光的波长,以光活性物质的需要为准。通常波长范围在200-1300nm的光效果较好,能提供相应波长光的均可以作为光源,可以是太阳光,也可以是人造光源,比如氙灯、紫外灯、LED灯、激光等。对光的强度没有特殊要求,光强度大的,沉积速度快些。
在一种实施方式中,所述光活性物质,可以是任意具有光响应、光活性的物质。
在一种实施方式中,所述光活性物质,可以是以下任意一种或者多种:金属氧化物、硫化物、卤氧化物、钨酸盐、硅、碳氮化合物等。
在一种实施方式中,所述光活性物质,可以是以下任意一种或者多种:TiO2,BiOX(X=Cl,Br,I),CdX(X=S,Se,Te),BiWO6,BiVO4,Cu2O,Si,C3N4,ZnO,ZnS,ZnSe,氧化锌-氧化钌(ZnO-RuO2)、硫镓铜矿(CuGaS2)、磷化镓(GaP)、砷化镓(GaAs)或其组合。
在一种实施方式中,所述光活性物质,可以是粉体形态;比如纳米线、纳米线阵列、纳米管、纳米管阵列、纳米颗粒、含有多孔的纳米结构或其组合。
在一种实施方式中,所述反应的体系中,磷和金属离子的浓度在10-3mol L-1到饱和范围内时,容易在较短时间内完成沉积过程。
在一种实施方式中,所述反应的体系中,磷和金属离子的摩尔比没有特别的限制。其摩尔比在10-3-1000时容易实现沉积。
在一种实施方式中,所述方法是在低浓度氧气或者无氧气的体系中进行。在光化学反应中,采取措施降低体系中氧气浓度,有助于较快实现沉积过程。比如通入一定的惰性气体脱气,或者加入还原剂,或者抽走氧气等,均可以。
在一种实施方式中,所述无氧气的体系,是指在惰性气体的保护下进行。可选地,所述惰性气体可以是氮气、氩气等。
在一种实施方式中,所述方法,是在溶剂体系中进行;所述磷源和金属离子供体部分溶于或者完全溶于该溶剂体系中。
在一种实施方式中,所述溶剂为水,醇类,酸类,有机溶剂,或者上述的混合溶剂等,都可以。
在一种实施方式中,所述方法,包括间隔搅拌或者持续搅拌。
在一种实施方式中,所述复合电极为磷化镍@g-C3N4复合电极。
在一种实施方式中,所述复合电极的制备是先将光活性物质g-C3N4固定或者连接到导电基底上得到基础电极,然后将基础电极放置在含有次磷酸钠和镍离子的溶液中,排除体系中的氧气,将体系光照,反应结束后即得到磷化镍/g-C3N4/NF复合电极。
在一种实施方式中,采用电泳和光化学两步法法制备出了磷化镍@g-C3N4/NF复合电极,具体包括:
(1)烧制g-C3N4
首先称取一定量的硫脲置于坩埚中,然后将坩埚放在马弗炉中升温到550℃(升温速率2℃/min)并保持2h,自然降至室温后,取出坩埚,将得到的黄色固体在瓷研钵中研磨一定时间,再倒回坩埚中,置于马弗炉中升温到500℃(升温速率2℃/min)并保持2h,降至室温后取出坩埚,研磨黄白色粉末一定的时间,此即是g-C3N4。
(2)泡沫镍的预处理
将1×2cm的泡沫镍分别在3mol/L的盐酸溶液、丙酮、去离子水以及乙醇溶液中进行超声预处理15min,每种溶液中分别清洗三次,然后放在80℃烘箱中干燥待用。
(3)电泳g-C3N4
取10mg的g-C3N4黄白色粉末放入250mL烧杯中,加入10mg六水合硝酸镁和100mL异丙醇溶液,超声处理3h。然后用铂电极作为阳极在电泳仪中电泳10min,取出制备好的电极并用去离子水冲洗,烘干。
(4)光化学法制备磷化镍/g-C3N4/NF电极
将14mL的次磷酸钠溶液(0.2mol/L)和4mL氯化镍(0.1mol/L)加入25mL圆底烧瓶中,再加入2mL的去离子水,摇匀,将制备好的电极放入烧瓶中,然后向密封好的烧瓶中通入氮气40min以排除氧气等杂气。再将烧瓶放在300W氙灯下光照,光照时候均匀搅拌。反应结束后,用去离子水冲洗,烘干。
本发明通过两步简便的方法实现了含磷复合物和光活性物质电极的复合,利用光敏剂g-C3N4在光照条件下激发出的电子使磷化镍还原在g-C3N4上,该材料在电催化方面表现出优异的电催化性能。本发明具有以下显著特点:
(1)本发明独创性的光化学法成功复合磷化镍/g-C3N4电极,该制备方法简便、可控,并且绿色环保,为电极的制备提供一种新思路。
(2)本发明通过磷化镍和g-C3N4的复合,充分发挥了两者的协同效应,克服了单种物质性能上的缺陷。实验证明,该复合电极具有极低的电荷转移电阻,减小了电荷转移阻力,使电子更容易还原水分解产生氢气。
(3)本发明所采用的的电极为非贵金属催化剂,降低了生产成本,并且具有较低的过电势和较高的稳定性,具有一定的工业应用价值。
附图说明
图1是实施例1所得NixP@g-C3N4/NF电极的照片以及透射电镜图;
图2是实施例1所得NixP@g-C3N4/NF电极的扫描电镜图;
图3是实施例1所得NixP@g-C3N4/NF电极的扫描电镜能量色散X射线光谱;
图4是实施例1所得NixP@g-C3N4催化剂的傅立叶变换红外光谱图;
图5是实施例1所得NixP@g-C3N4/NF电极的线性扫描伏安图;
图6是实施例3所得NixP@g-C3N4催化剂负载在不同基底上的线性扫描伏安图;
图7是实施例1所得NixP@g-C3N4/NF电极的电化学阻抗谱图(图中插图为NiXP@g-C3N4/NF电极阻抗谱图的放大图);
具体实施方案
下面是对本发明进行具体描述。
为了更具体的说明本发明的方法,下面给出本发明的实施例,但本发明的应用不仅限于此。
实施例1:NixP@g-C3N4催化剂及NixP@g-C3N4/NF电极的制备与表征
新型NixP@g-C3N4/NF电极的制备步骤如下:
(1)烧制g-C3N4
首先称取一定量的硫脲置于坩埚中,然后将坩埚放在马弗炉中升温到550℃(升温速率2℃/min)并保持2h,自然降至室温后,取出坩埚,将得到的黄色固体在瓷研钵中研磨一定时间,再倒回坩埚中,置于马弗炉中升温到500℃(升温速率2℃/min)并保持2h,降至室温后取出坩埚,研磨黄白色粉末一定的时间,此即是g-C3N4。
(2)泡沫镍的预处理
将1×2cm的泡沫镍分别在3mol/L的盐酸溶液、丙酮、去离子水以及乙醇溶液中进行超声预处理15min,每种溶液中分别清洗三次,然后放在80℃烘箱中干燥待用。
(3)电泳g-C3N4
取10mg的g-C3N4黄白色粉末放入250mL烧杯中,加入10mg六水合硝酸镁和100mL异丙醇溶液,超声处理3h。然后用铂电极作为阳极在电泳仪中电泳10min,取出制备好的电极并用去离子水冲洗,烘干。
(4)光化学法制备NixP/g-C3N4/NF电极
将14mL的次磷酸钠溶液(0.2mol/L)和4mL氯化镍(0.1mol/L)加入25mL圆底烧瓶中,再加入2mL的去离子水,摇匀,将制备好的电极放入烧瓶中,然后向密封好的烧瓶中通入氮气40min以排除氧气等杂气。再将烧瓶放在300W氙灯下光照,光照时候均匀搅拌。反应结束后,用去离子水冲洗,烘干。
图1分别是制得电极的照片以及透射电镜图,从照片中可以看出催化剂紧密的负载在泡沫镍基底上,从透射电镜图中可以看出NixP呈球状并均匀分布在g-C3N4上,其中在图中NixP是黑色的,g-C3N4以片状形态出现。
图2是制得NixP@g-C3N4/NF电极的扫描电镜图,从图中可以看出NixP纳米颗粒紧紧的负载在g-C3N4纳米片上。
图3为所得NixP@g-C3N4/NF电极的扫描电镜能量色散X射线光谱;从图中可以直观地看出电极上Ni,P,C和N元素的存在,证明NixP@g-C3N4复合物催化剂成功制备出来。其中,电极上面Na,Cl和O元素的出现分别是由于样品表面杂质和样品暴露在空气中被氧化所导致的。
图4是所得NixP@g-C3N4催化剂的傅立叶变换红外光谱图;从图中可以直观地看出对于g-C3N4的谱图来看,共有三个特征吸收峰在波长为3294cm-1,1200-1700cm-1以及810cm-1处。在3294cm-1处出现的较宽的峰是由于NH2或者N-H键的伸缩振动引起的。在1654cm-1、1575cm-1和1411cm-1处的吸收峰是因为经典的CN杂环伸缩振动所引起的。在波长为810cm-1处出现的峰来源于三嗪环结构的面外弯曲。以上结果证明g-C3N4样品被成功制备。从NixP@g-C3N4的傅里叶变换红外光谱图来看,在波长为3450cm-1和1635cm-1处出现的吸收峰是由于O-H伸缩振动引起的,对应于吸附在样品表面的水分子。在波长为579cm-1位置出现的吸收峰证明了Ni-P键的存在,说明了NixP物质的合成。
实施例2:NixP@g-C3N4/NF电极与其他电极的电化学性能测试对比
(1)其他电极的制备:
取实施例1中的g-C3N410mg放入250mL烧杯中,加入10mg六水合硝酸镁和100mL异丙醇溶液,超声处理3h。上述溶液作为电泳液,泡沫镍作为阴极,铂电极作为阳极在电泳仪中电泳10min,取出制备好的电极并用去离子水冲洗,烘干,即是g-C3N4/NF电极。
为了进一步对比催化剂性能,20wt%的商业Pt/C催化剂分散在乙醇和水的溶液中,体积比是4:1,然后再加入40微升的Nafion溶液,超生20min,然后将上述混合好的均相催化剂负载到泡沫镍上,最后,样品放在60℃烘箱中干燥3h,即得负载了Pt/C催化剂的电极。
(2)电化学性能测试:
以0.5mol/L硫酸(PH=0)作为电解质溶液,g-C3N4/NF电极作为工作电极,Ag/AgCl电极作为参比电极,铂网作为对电极,0.5mol/L硫酸溶液中进行循环伏安循环26次,然后在CHI660E电化学工作站上进行线性扫描电化学性能测试,测试结果如图5中的g-C3N4/NF曲线。为了进一步对比,以0.5mol/L硫酸作为电解质溶液,负载了Pt/C催化剂电极作为工作电极,Ag/AgCl电极作为参比电极,铂网作为对电极,0.5mol/L硫酸溶液中进行循环伏安循环26次,然后在CHI660E电化学工作站上进行线性扫描电化学性能测试,测试结果如图5中的Pt/C曲线。以0.5mol/L硫酸作为电解质溶液,预处理过的NF电极作为工作电极,Ag/AgCl电极作为参比电极,铂网作为对电极0.5mol/L,硫酸溶液中进行循环伏安循环26次,然后在CHI660E电化学工作站上进行线性扫描电化学性能测试,测试结果如图5中NF曲线。
其中,图5中的NixP@g-C3N4/NF电极的线性扫描伏安图,其测试条件如下:以0.5mol/L硫酸(PH=0)作为电解质溶液,NixP@g-C3N4/NF电极作为工作电极,Ag/AgCl电极作为参比电极,铂网作为对电极0.5mol/L硫酸溶液中进行循环伏安循环26次,然后在CHI660E电化学工作站上进行线性扫描电化学性能测试。
从图5的NiXP@g-C3N4/NF曲线、g-C3N4/NF曲线、Pt/C曲线、NF曲线,可以直观地看出:在同样的电流密度下,和g-C3N4/NF的线性扫描伏安图相比,NixP@g-C3N4/NF具有相当低的过电位,也就是说当NixP沉积到g-C3N4/NF电极表面的时候,会极大的提高电极析氢反应的活性。NixP@g-C3N4/NF电极仅仅需要126mV和149mV的过电位去分别驱动10mAcm-2和20mAcm-2的电流密度,其过电位比g-C3N4/NF以及NF的过电位降低了很多。除此之外,NixP@g-C3N4/NF电极在较负的电位下其阴极电流密度增加的非常迅速,也就是具有一个高效的电流响应速度,并且其在电流密度为100mAcm-2时的过电势只有217mV。
实施例3:基于NiXP@g-C3N4的不同基底的电极
(1)取实施例1中的g-C3N410mg放入250mL烧杯中,加入10mg六水合硝酸镁和100mL异丙醇溶液,超声处理3h。分别用处理好的FTO和铜片作为阴极,铂电极作为阳极在电泳仪中电泳10min,取出制备好的电极并用去离子水冲洗,烘干。将14mL的次磷酸钠溶液(0.2mol/L)和4mL氯化镍(0.1mol/L)加入25mL圆底烧瓶中,再加入2mL的去离子水,摇匀,将制备好的电极放入烧瓶中,然后向密封好的烧瓶中通入氮气40min以排除氧气等杂气。再将烧瓶放在300W氙灯下光照,光照时候均匀搅拌。反应结束后,用去离子水冲洗,烘干。即分别得到NixP@g-C3N4/FTO和NixP@g-C3N4/Cu片电极。
(2)以0.5mol/L硫酸(PH=0)作为电解质溶液,NixP@g-C3N4/FTO和NixP@g-C3N4/Cu片电极分别作为工作电极,Ag/AgCl电极作为参比电极,铂网作为对电极,0.5mol/L硫酸溶液中进行循环伏安循环26次,然后在CHI660E电化学工作站上进行线性扫描电化学性能测试,测试结果如图6中的NixP@g-C3N4/FTO和NixP@g-C3N4/Cu片电极曲线。在同样电位下,当泡沫镍被用来作为基底的时候电极的电流密度达到最大。
由实施例1-3可看出,本发明所制备的NiXP@g-C3N4/NF电极电催化析氢性能最好且价格低廉,是一种高效、环保的电催化产氢催化剂。
实施例4:NixP@g-C3N4/NF电极的电化学阻抗测试
电化学阻抗谱图中的电荷转移阻力(Rct)表示NiXP@g-C3N4催化剂与质子间的转移阻力大小,其数值可以从电化学阻抗谱图中曲线半圆直径可以得出,进而可以考察所制NiXP@g-C3N4/NF电极的产氢机理。
以0.5mol/L硫酸(PH=0)作为电解质溶液,NixP@g-C3N4/NF作为工作电极,Ag/AgCl电极作为参比电极,铂网作为对电极0.5mol/L硫酸溶液中进行循环伏安循环26次,然后在CHI660E电化学工作站上进行电化学阻抗谱性能测试,测试结果如图7,从图中可以看出NixP@g-C3N4/NF电极的电荷转移电阻仅仅只有3.27欧姆,而只有g-C3N4催化剂(大概是150欧姆)或泡沫镍(大概是65欧姆)时的电荷转移电阻非常大,这表明NiXP@g-C3N4催化剂与质子间的转移阻力非常小,这也正是NiXP和g-C3N4协同作用后的结果。
实施例5:含磷复合物的制备
按照如下方法制备含磷复合物
(1)取20.25mmol二点五水合氯化镉,40.75mmol硫脲和60mL乙二胺置于100mL高压反应釜中,将反应釜置于160℃烘箱中水热处理48h,反应结束后将反应釜置于自然条件下降至室温,过滤得到黄色固体并用去离子水洗涤10次,乙醇洗涤2次,将得到固体置于60℃烘箱干燥一整晚,得到的黄色固体即为硫化镉纳米棒;
(2)取50mg硫化镉纳米棒置于25mL单口烧瓶中,随后加入2mL氯化钴水溶液(0.1M),7mL次磷酸钠(分子式NaH2PO2)水溶液(0.1mol/L),1mL去离子水,超声分散处理1min,然后使用氮气脱气40min除去反应体系中氧气;
(3)待脱气完成后,将圆底烧瓶置于300W氙光灯下照射不同时间得到不同含量磷钴后,将所得固体离心分离,去离子水洗涤5次,乙醇洗涤2次,将所得固体使用氮气吹干,得到的固体即为CoxP/硫化镉纳米棒复合催化剂。并将催化剂命名为CoxP-T/CdS NRs(其中T代表光照时间,单位:min)。
取步骤(1)得到的硫化镉3mg置于100mL光催化反应器中,随后加入5mL三乙醇胺,45mL水。超声处理30s,使用氮气脱气1h排除体系中氧气,将圆底烧瓶置于300W氙光(配有420nm截止滤光片)下照射,反应结束后,用热导-气相色谱检测反应中生成的氢气,反应8h后其产氢速率为7.4mmol·g-1h-1。
将CoxP-50/CdS NRs复合催化剂取3mg置于100mL光催化反应器中,100mL光催化反应器中,随后加入5mL三乙醇胺,45mL去离子水。超声处理30s,使用氮气脱气1h排除体系中氧气,将圆底烧瓶置于300W氙光(配有420nm截止滤光片)下照射,反应结束后,用热导-气相色谱检测反应中生成的氢气,反应8h后其产氢速率为165.8mmol·g-1h-1,比单纯的硫化镉纳米棒产氢速率提高22倍。
将CoxP-50/CdS NRs复合催化剂取1mg置于100mL光催化反应器中,随后加入,15g九水合硫化钠,11g无水亚硫酸钠,50mL去离子水。超声处理30s,使用氮气脱气1h排除体系中氧气,将圆底烧瓶置于300W氙光(配有420nm截止滤光片)下照射,反应结束后,用热导-气相色谱检测反应中生成的氢气,每隔5h使用热导-气相色谱检测反应中生成的氢气并进行一次脱气排除反应体系中氢气,然后继续光照处理,反应25h后催化活性仍无明显降低。
实施例6:含磷复合物的制备
按照如下方法制备含磷复合物:
(1)取20g硫脲置于4个坩埚中,将坩埚置于马弗炉中以2度每分的升温速率升至550℃,煅烧两小时,待降至室温取出坩埚,将固体研磨成粉末,将盛有固体粉末的坩埚置于马弗炉,以2度每分升温速率升至500℃,煅烧两小时,待降至室温取出黄白色固体粉末获得类石墨烯碳氮化合物;
(2)取30mg石墨烯碳氮化合物置于25mL单口烧瓶中,随后加入4mL硫化镍水溶液(0.1mol/L),4mL次磷酸钠(分子式NaH2PO2)水溶液(0.7mol/L),2mL水,超声分散处理30s,然后使用氮气脱气40min除去反应体系中氧气;
(3)待脱气完成后,将圆底烧瓶置于300W氙光灯下照射20min后,将所得固体离心分离,去离子水洗涤5次,乙醇洗涤2次,将所得固体使用氮气吹干,所得黑色物质即为NixP/类石墨烯碳氮化合物复合催化剂。所制备NixP/类石墨烯碳氮化合物复合催化剂命名为NixP-20/g-C3N4。
取类石墨烯碳氮化合物取5mg置于25mL圆底烧瓶中,随后加入2mL三乙醇胺和8mL水,超声分散处理30s,然后使用氮气脱气40min除去反应体系中氧气;将圆底烧瓶置于300W氙光(配有AM 1.5G滤光片)下照射,反应结束后,用热导-气相色谱检测反应中生成的氢气,反应2h后其产氢速率为27μmol·g-1h-1。
NixP/类石墨烯碳氮化合物复合催化剂取5mg置于25mL圆底烧瓶中,随后加入2mL三乙醇胺,8mL水。超声处理30s,使用氮气脱气40min排除体系中氧气,将圆底烧瓶置于太阳光模拟器下光照,反应结束后,用热导-气相色谱检测反应中生成的氢气,反应2h后其产氢速率为8585μmol·g-1h-1,比单纯的类石墨烯碳氮化合物产氢速率提高317倍。
NixP/类石墨烯碳氮化合物复合催化剂取5mg置于25mL圆底烧瓶中,随后加入1mL乳酸、9mL水,该混合溶液pH=2。超声处理30s,使用氮气脱气40min排除体系中氧气,将圆底烧瓶置于太阳光模拟器下光照。待反应75h后催化剂活性仍无明显降低。
虽然本发明已以较佳实施例公开如上,但其并非用以限定本发明,任何熟悉此技术的人,在不脱离本发明的精神和范围内,都可做各种的改动与修饰,因此本发明的保护范围应该以权利要求书所界定的为准。
Claims (10)
1.一种含磷复合物或其制备方法,其特征在于,所述含磷复合物的制备方法包括光活性物质在光照情况下,金属离子与磷源生成所述含磷复合物;所述含磷复合物中含有磷和金属;所述生成反应中,必要物质为光活性物质、金属源和磷源。
2.根据权利要求1所述的含磷复合物或其制备方法,其特征在于,除了必要物质之外,不加入其它牺牲剂。
3.根据权利要求1所述的含磷复合物或其制备方法,其特征在于,所述含磷复合物为CoxP/硫化镉纳米棒复合催化剂;所述方法,具体是:
(1)取一定量的硫化镉纳米棒加入25mL单口圆底烧瓶,加入一定量次磷酸钠(分子式NaH2PO2)和氯化钴的混合水溶液,混合均匀后通入氮气30-40min以除去反应体系中氧气,然后置于氙灯下光照,光照时保持均匀搅拌,通过不同的光照时间调节CoxP含量;
(2)反应结束后,使用离心分离将固体分离,去离子水离心洗涤5-8次,乙醇洗涤1-3次,将所得固体物质干燥,所得固体物质即为产品CoxP/硫化镉纳米棒复合催化剂。
4.根据权利要求3所述的含磷复合物或其制备方法,其特征在于,所述硫化镉纳米棒的制备具体是:取适量2.5水合氯化镉、硫脲与一定体积乙二胺置于100mL高压反应釜中,将反应釜置于160℃烘箱中水热处理48h,反应结束后将反应釜置于自然条件下降至室温,过滤得到黄色固体并用去离子水洗涤10次左右,乙醇洗涤1-2次,将得到固体置于60℃烘箱干燥一整晚,得到的黄色固体即为硫化镉纳米棒。
5.一种复合电极,其特征在于,含有权利要求1~4任一所述方法制备得到的含磷复合物,比如CoxP/硫化镉纳米棒复合催化剂或者磷化镍/类石墨烯碳氮化合物复合催化剂。
6.一种复合电极的制备方法,其特征在于,包括在光活性物质光照情况下,金属离子与磷源生成含磷复合物;所述生成反应中,必要物质为光活性物质、金属源和磷源;所述光活性物质,或者获得的含磷复合物,固定或者连接在导电基底上。
7.根据权利要求6所述的制备方法,其特征在于,所述磷源中,磷的价态可以是-3到+5价的。可选地,所述磷源,可以是各种形态的磷源,比如单质(红磷和白磷等)、无机磷(次磷酸根、亚磷酸根、或正磷酸根等)、有机磷(三辛基膦等)等。可选地,所述金属离子中的金属,可以是过渡金属,还可以是In、Pt、Pd、Rh、Re、Ir。可选地,所述过渡金属可以是铁、钴、镍、铜、锰、锌、铝等,还可以是铬、钼、钨等。
8.根据权利要求6~7任一所述的制备方法,其特征在于,所述导电基底可以是泡沫镍、ITO、FTO、镍片、镍网、钛片、钛网、铜片、铜网、不锈钢片、不锈钢网、碳纤维布、透明导电布中的一种或几种。
9.根据权利要求6~8任一所述的制备方法,其特征在于,所述复合电极为磷化镍@g-C3N4复合电极。
10.根据权利要求6~9任一所述的制备方法,其特征在于,所述复合电极的制备是先将光活性物质g-C3N4固定或者连接到导电基底上得到基础电极,然后将基础电极放置在含有次磷酸钠和镍离子的溶液中,排除体系中的氧气,将体系光照,反应结束后即得到磷化镍/g-C3N4/NF复合电极。
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