CN106801231B - The WO of molecular level iridium catalyst modification3Complex light anode and its application - Google Patents
The WO of molecular level iridium catalyst modification3Complex light anode and its application Download PDFInfo
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- CN106801231B CN106801231B CN201710067862.XA CN201710067862A CN106801231B CN 106801231 B CN106801231 B CN 106801231B CN 201710067862 A CN201710067862 A CN 201710067862A CN 106801231 B CN106801231 B CN 106801231B
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- iridium catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 50
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910018828 PO3H2 Inorganic materials 0.000 claims abstract description 80
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910001868 water Inorganic materials 0.000 claims abstract description 42
- 238000012986 modification Methods 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000005868 electrolysis reaction Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000000539 dimer Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 238000003828 vacuum filtration Methods 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 abstract description 13
- 239000004065 semiconductor Substances 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 239000003504 photosensitizing agent Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000002356 single layer Substances 0.000 abstract description 4
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 abstract description 3
- 102000057593 human F8 Human genes 0.000 abstract description 3
- 229940047431 recombinate Drugs 0.000 abstract description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 104
- 238000005286 illumination Methods 0.000 description 32
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 30
- 239000000243 solution Substances 0.000 description 25
- 229910021607 Silver chloride Inorganic materials 0.000 description 18
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 18
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 230000005611 electricity Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 238000009790 rate-determining step (RDS) Methods 0.000 description 5
- 238000010345 tape casting Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000008055 phosphate buffer solution Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000001052 transient effect Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 230000029553 photosynthesis Effects 0.000 description 3
- 238000010672 photosynthesis Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000035508 accumulation Effects 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000005445 isotope effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000004237 Crocus Nutrition 0.000 description 1
- 241000596148 Crocus Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- -1 IrOx Compound Chemical class 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000005441 aurora Substances 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002975 chemoattractant Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- FQYYXLUUYXDDKR-UHFFFAOYSA-N hydrogen phosphate;2-pyridin-1-ium-2-ylpyridin-1-ium Chemical group OP(O)(O)=O.N1=CC=CC=C1C1=CC=CC=N1 FQYYXLUUYXDDKR-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
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- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
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- 238000012353 t test Methods 0.000 description 1
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- 230000005945 translocation Effects 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000011345 viscous material Substances 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
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2054—Light-sensitive devices comprising a semiconductor electrode comprising AII-BVI compounds, e.g. CdTe, CdSe, ZnTe, ZnSe, with or without impurities, e.g. doping materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the WO of molecular level iridium catalyst modification3Complex light anode and its application.It uses with visible light-responded inorganic semiconductor material tungstic acid as photosensitizer, with molecular level the iridium catalyst [(H with rock-steady structure4dphbpy)IrIII(Cp*) Cl] Cl be catalyst, single-layer catalyst is loaded in tungstic acid substrate in the way of chemisorption, constitute inorganic semiconductor/molecular catalyst (FTO/WO3/Ir–PO3H2) complex light anode catalyst system, effectively both hole and electron is prevented to recombinate, greatly accelerates the charge transmission between electrode/electrolyte interface, improve separation of charge efficiency and interface reaction kinetics, to realize complex light anode in visible light (λ > 400nm, 100mW/cm2) lower catalytic water oxidation is driven to generate oxygen.
Description
Technical field
The present invention relates to one kind to carry out base group modification by introducing phosphate group in catalyst structure, utilizes chemisorption
Iridium catalyst is loaded on semiconductor tungstic acid electrode as light anode, constructs NEW TYPE OF COMPOSITE light anode and its answer by effect
With.
Background technique
With the rapid development of social economy, demand of the mankind to the energy is growing day by day, the influence and pollution of natural environment
Also gradually increase, energy crisis and environmental pollution have become the huge challenge of human survival and development.For a long time, industry and
The energy of life is mainly derived from fossil fuel, and fossil fuel is basis and the power for supporting development of all countries economy.This energy consumption
Increase satisfaction can be converted to by a kind of solar energy: it is approximately 10 that the sun is irradiated to tellurian energy daily22J。
It therefore deduces that, the energy of consumption in the mankind 1 year is more on the energy ratio earth that the sun provides per hour.Although the mankind early have
About the application of solar energy, but the solar energy utilized is insignificant, and condition is limited.So finding the new utilization sun
Can mode and generate renewable and clean energy resource just and become the hot spot of current scientific circles' research.
There are mainly three types of approach for related solar energy conversion at present: 1. using photovoltaic power generation equipment (Photovoltaic,
PV electric energy) is directly converted light energy into.How to increase its transfer efficiency and solves the problems, such as that fossil fuel environment is effective
Utilize a major challenge of solar energy.2. the plant generated using photosynthesis of plant and crop by-product synthesising biological fuel,
Such as corn transformation is ethyl alcohol, though economic and environment-friendly, the period is long, at high cost.3. manual simulation's photosynthesis.The pass of this approach
Key is, under sunlight irradiation, is acted on by electric charge transfer, charge accumulated and catalyst and realizes electron-hole separation, from
And realize and decompose water, discharge hydrogen and oxygen.
In the photosynthetic early stage research of manual simulation, mainly with Ru, the precious metals complex such as Ir are molecular catalyst,
In the case where being powered on sub- sacrificial body outside, the oxygenolysis of water is realized, or in homogeneous system with TiO2, the metal oxygens such as IrOx
Compound carries out water oxidation reaction as catalyst under chemical reagent or illumination.By the research of last decade, water oxygen is from initial
Chemical catalysis system gradually develop to a variety of reaction systems such as photocatalytic system, electro-catalysis system and photoelectrochemical cell.With
Traditional metal oxide heterogeneous catalyst is compared, and the water oxidation catalysts of many molecular levels can in catalytic activity and structure
It in tonality, has a clear superiority, and inorganic semiconductor material not only has photocatalytic activity, it may have good photostability etc.
Advantage.
Summary of the invention
An object of the present invention is to provide a kind of WO of molecular level iridium catalyst modification3Complex light anode (FTO/WO3/
Ir– PO3H2).By the horizontal iridium catalyst Ir-PO of monomolecular in the way of chemisorption3H2Load to tungstic acid substrate
On, constitute inorganic semiconductor/molecular catalyst (FTO/WO3/Ir–PO3H2) complex light anode catalyst system.In environmental protection, open
There is boundless application prospect in the fields such as hair new energy, solar energy and fuel cell.
The second object of the present invention is to provide a kind of WO of molecular level iridium catalyst modification3It is compound to be catalyzed under visible light
Water oxygenization produces the application in oxygen.
To achieve the above object, the technical solution adopted by the present invention is that: molecular level iridium catalyst modification WO3Complex light
Anode, preparation method include the following steps:
1)FTO/WO3The preparation of electrode: by pretreated WO3WO is prepared with distilled water3Suspension；By WO3Suspension uses
Knife coating or spin-coating method are supported on FTO electro-conductive glass, and naturally dry is dried in vacuum overnight, and is made annealing treatment in Muffle furnace, are obtained
FTO/WO3Electrode；
2) FTO/WO that will be prepared3Electrode is immersed in the methanol solution of molecular level iridium catalyst overnight, after taking-up
It is rinsed with deionized water, is dried in vacuo or is dried with nitrogen, obtain the WO of molecular level iridium catalyst modification3Complex light anode is kept away
Light saves.
The WO of above-mentioned molecular level iridium catalyst modification3Complex light anode, in step 1), the annealing is,
In Muffle furnace, 500 DEG C are warming up to the rate of 5 DEG C/min, 2-3h is calcined, is cooled to room temperature after taking-up.
The WO of above-mentioned molecular level iridium catalyst modification3Complex light anode, the molecular level iridium catalyst, for tool
There is the molecule Ir-PO of four-coordination3H2, chemical molecular formula is [(H4dphbpy)IrIII(Cp*)Cl]Cl；Wherein, H4Dphbpy=
4,4 '-diphosphonic acid -2,2 '-bipyridyls, Cp*=pentamethylcyclopentadiene.
The WO of above-mentioned molecular level iridium catalyst modification3Complex light anode, the molecular level iridium catalyst Ir-
PO3H2Preparation method include the following steps: that with 2,2 '-bipyridyl -4,4 '-bis phosphoric acid diethylesters are raw material, synthesis 4,4 '-two
Phosphoric acid -2,2 '-bipyridyl H4Dphbpy, further with [IrIII(Cp*)(Cl2)]2Dimerization precursor reactant, synthesis have stability
The molecular level iridium catalyst Ir-PO of the four-coordination of structure3H2。
Preferably, the WO of above-mentioned molecular level iridium catalyst modification3Complex light anode, the molecular level iridium catalysis
Agent Ir-PO3H2Preparation method include the following steps:
1) 2,2 '-bipyridyl -4 are prepared, 4 '-bis phosphoric acid diethylesters: under nitrogen protection, takes 4,4 '-two bromo- 2,2 '-connection
Pyridine, Pd (pph3)4, diethyl phosphite and Et3N at 80-90 DEG C, is heated to reflux 3-4h in organic solvent, cooling
To room temperature, ether is added into reaction solution, is filtered by vacuum, filtrate concentrated by rotary evaporation, contact plate, silica gel column chromatography, obtains 2,2 '-connection pyrroles
Pyridine -4,4 '-bis phosphoric acid diethylester；Preferably, the organic solvent is toluene；
2) 4,4 '-diphosphonic acid -2 are prepared, 2 '-bipyridyls: NaOH is dissolved in methanol, is added slowly with stirring 2,2 ' -
4,4 '-bis phosphoric acid diethylester of bipyridyl-, the heating stirring 6-7h at 45-55 DEG C are concentrated by evaporation, and concentrate carries out being acidified to pH
=2, filtering takes precipitating, is dried in vacuo, obtains 4,4 '-diphosphonic acid -2,2 '-bipyridyls；Preferably, it is acidified with hydrochloric acid.
3) molecular level iridium catalyst Ir-PO is prepared3H2: under argon gas protection, by [IrIII(Cp*)(Cl2)]2Dimer exists
It is heated to reflux temperature in methylene chloride, magnetic agitation 20-30 minutes, 4,4 '-diphosphonic acid -2, the dichloro of 2 '-bipyridyls is added
Dichloromethane, magnetic agitation are simultaneously warming up to 40-50 DEG C, back flow reaction 10-11 hours, reaction solution are cooled to room temperature, vacuum mistake
Filter, takes precipitating, obtains target product.
Preferably, in molar ratio, 4,4 '-diphosphonic acid -2,2 '-bipyridyls: [IrIII(Cp*)(Cl2)]2=2:1.
The WO of above-mentioned molecular level iridium catalyst modification3Application of the complex light anode in electrolysis water oxygen.
The beneficial effects of the present invention are:
1. the present invention, design has synthesized molecule iridium catalyst, using phosphoric acid as bridged bond, will divide in such a way that covalent bond adsorbs
Sub- iridium catalyst loads to WO3Electrode surface constructs the tungstic acid semiconductor optical anode of molecular catalyst modification, to building
Novel photoelectric chemical cell has a very important significance.Photoelectrocatalysis the results show that using mode of loading of the present invention, when
When applying bias is 1.23V (vs RHE), under visible light illumination, NEW TYPE OF COMPOSITE light anode FTO/WO3/Ir–PO3H2In pH=
1.0 KNO3Density of photocurrent ratio FTO/WO in solution3Electrode increases 50%, and faradic efficiency 95% effectively improves
Transmission and separative efficiency between semiconductor optical anode charge-hole, catalytic activity are much better than three oxidations of yttrium oxide modification
Tungsten light anode.To realize complex light anode in visible light (λ > 400nm, 100mW/cm2) lower catalytic water oxidation is driven to generate oxygen
Theoretical foundation is provided.
2. the present invention, simulates the photosynthesis of nature, using with visible light-responded three oxygen of inorganic semiconductor material
Change tungsten is photosensitizer, with molecular level the complex of iridium [(H with rock-steady structure4dphbpy)IrIIICp*(Cl)]Cl(Ir-
PO3H2) it is catalyst, single-layer catalyst is loaded in tungstic acid substrate in the way of chemisorption, composition is inorganic partly to be led
Body/molecular catalyst (FTO/WO3/Ir–PO3H2) complex light anode catalyst system, effectively both hole and electron is prevented to recombinate, significantly
The charge transmission between electrode/electrolyte interface is accelerated, separation of charge efficiency and interface reaction kinetics are improved, thus real
Complex light anode is showed in visible light (λ > 400nm, 100mW/cm2) lower catalytic water oxidation is driven to generate oxygen.
3. the present invention, with the WO with photostability3Semiconductor nano material is as photosensitizer, with the molecular water of high activity
Flat complex of iridium [(H4dphbpy)IrIIICp*(Cl)]Cl(Ir-PO3H2), the two is combined, preparation can be in acid, low electricity
Composite anode that is efficient under the conditions of position, stablizing electrolysis aquatic products oxygen；Such light anode has not been reported.Tentatively realize molecular catalyst
Light, electrolysis water device, for water oxygen chemoattractant molecule catalyst application open new approach.
4. the present invention is used with visible light-responded inorganic semiconductor material tungstic acid as photosensitizer, steady to have
Determine molecular level the iridium catalyst [(H of structure4dphbpy)IrIII(Cp*) Cl] Cl be catalyst, in the way of chemisorption
Single-layer catalyst is loaded in tungstic acid substrate, inorganic semiconductor/molecular catalyst (FTO/WO is constituted3/Ir–PO3H2) multiple
The anode-catalyzed system of light combination, effectively prevents both hole and electron to recombinate, and the charge greatly accelerated between electrode/electrolyte interface passes
It is defeated, improve separation of charge efficiency and interface reaction kinetics, thus realize complex light anode visible light (nm of λ > 400,
100mW/cm2) lower catalytic water oxidation is driven to generate oxygen.
Detailed description of the invention
Fig. 1 is WO3The related scans electron microscope picture (SEM figure) of electrode and modified electrode.
Wherein, A:FTO/WO3The SEM photograph of electrode；B:FTO/WO3The SEM photograph of the cross section of electrode；C:Ir-PO3H2
The FTO/WO of modification3SEM photograph before light anode electrolysis；D:Ir-PO3H2The FTO/WO of modification3SEM after light anode electrolysis shines
Piece.
Fig. 2 a is the energy spectrum diagram (EDX figure) of FTO basal electrode.
Fig. 2 b is FTO/WO3The energy spectrum diagram (EDX figure) of basal electrode.
Fig. 2 c is Ir-PO3H2The FTO/WO of modification3/Ir-PO3H2Energy spectrum diagram (EDX figure) before complex light anode electrolysis.
Fig. 2 d is Ir-PO3H2The FTO/WO of modification3/Ir-PO3H2Energy spectrum diagram (EDX figure) after complex light anode electrolysis.
Fig. 3 a is the Raman spectrum of catalyst and different composite electrode.
Wherein, a:Ir-PO3H2Catalyst fines；B:FTO/WO3Substrate；C:FTO/WO3/ IrOx electrode；D:FTO/WO3/
Ir-PO3H2Electrode.
Fig. 3 b is Ir-PO3H2The FTO/WO of modification3/Ir-PO3H2The Raman spectrum enlarged drawing of complex light anode.
Wherein, d:FTO/WO3/Ir-PO3H2Electrode.
Fig. 4 a is Ir-PO3H2The FTO/WO of modification3/Ir-PO3H2The XPS of complex light anode is composed entirely.
Fig. 4 b is Ir-PO3H2The FTO/WO of modification3/Ir-PO3H2The XPS enlarged drawing of complex light anode.
Fig. 5 a is different modifying electrode (pH=1.0,0.1M KNO3Solution) linear scan curve (J-V).
Wherein, the WO under 1:1.4V vs Ag/AgCl bias condition3；WO under 2:1.4V vs Ag/AgCl bias condition3
/IrOx；WO under 3:1.4V vs Ag/AgCl bias condition3/Ir–PO3H2。
Fig. 5 b is the linear scan curve (J-V) of different modifying electrode (pH=7.0,0.1M phosphate buffer solution).
Wherein, the WO under 1:1.2V vs Ag/AgCl bias condition3；Under 2:1.2V vs Ag/AgCl bias condition
WO3/IrOx；WO3/Ir-PO under 3:1.2V vs Ag/AgCl bias condition3H2)。
Fig. 6 a is different modifying electrode (pH=1.0,0.1M KNO3Solution, 1.23V vs RHE bias) i-t curve.
Wherein, 1: illumination (100mW/cm2) under the conditions of WO3；2: illumination (100mW/cm2) under the conditions of WO3/IrOx；
3: illumination (100mW/cm2) under the conditions of WO3/Ir-PO3H2。
Fig. 6 b is the i-t of different modifying electrode (pH=7.0,0.1M phosphate buffer solution, 1.2V vs Ag/AgCl bias)
Curve.
Wherein, 1: illumination (100mW/cm2) under the conditions of WO3；2: illumination (100mW/cm2) under the conditions of WO3/IrOx；3:
Illumination (100mW/cm2) under the conditions of WO3/Ir-PO3H2。
Fig. 7 is pH=1.0 of the different modifying electrode at 20 DEG C, 0.1M KNO3Impedance spectra in solution under illumination condition.
Wherein, experimental condition: frequency range is from 0.1Hz-100KHz, amplitude 5mV, voltage 1.0V vs Ag/AgCl.
Fig. 8 a is FTO/WO3/ IrOx electrode is in H2O and D2The i-t curve of O.
Wherein, experiment condition: the illumination (100mW/cm of AM 1.5G2), pH 1.0,0.1M KNO3Solution, voltage 1.23V
vs.RHE。
Fig. 8 b is FTO/WO3/Ir-PO3H2Electrode is in H2O and D2The i-t curve of O.
Wherein, experiment condition: the illumination (100mW/cm of AM 1.5G2), pH 1.0,0.1M KNO3Solution, voltage 1.23V
vs.RHE。
Fig. 9 a is FTO/WO3The period transient short-circuit current of/IrOx electrode in illumination/not illumination.
Wherein, experiment condition: the illumination (100mW/cm of AM 1.5G2), pH 1.0,0.1M KNO3Solution, voltage 1.23V
vs.RHE。
Fig. 9 b is FTO/WO3/Ir-PO3H2Period transient short-circuit current of the electrode in illumination/not illumination.
Wherein, experiment condition: the illumination (100mW/cm of AM 1.5G2), pH 1.0,0.1M KNO3Solution, voltage 1.23V
vs.RHE。
Figure 10 is FTO/WO3And FTO/WO3/Ir-PO3H2The faradic efficiency of electrode.
Experiment condition: the illumination (100mW/cm of AM 1.5G2), pH 1.0,0.1M KNO3Solution.
Wherein, 1:FTO/WO3Theoretical value；Fang Dian: FTO/WO3Actual value；2:FTO/WO3/Ir-PO3H2Theoretical value；Diamond shape
Point: FTO/WO3/Ir-PO3H2Actual value.
Specific embodiment
Embodiment molecular level iridium catalyst Ir-PO3H2The WO of modification3Complex light anode
(1) molecular level iridium catalyst Ir-PO3H2([(H4dphbpy)IrIII(Cp*) Cl] Cl) preparation
The preparation of 1.2,2 '-bipyridyls -4,4 '-bis phosphoric acid diethylester
Under nitrogen protection, 4,4 '-two bromo- 2 are added in 50.0mL there-necked flask, 2 '-bipyridyl (Br2Bpy) (0.7850g,
0.5 mmol), Pd (pph3)4(0.2500g, 0.5mmol), Et3N (0.7mL), diethyl phosphite (0.7mL), in 15.0mL
In toluene, at 85 DEG C, it is heated to reflux 4h, to fully reacting, is cooled to room temperature, ether is added into reaction solution, is filtered by vacuum,
Precipitating is filtered off, then concentrated by rotary evaporation filtrate carries out contact plate, is finally collected 2,2 '-bipyridyl -4 of product with silica gel column chromatography,
4 '-bis phosphoric acid diethylesters.
1H NMR(CH3OD, 295K, δ/ppm, J/Hz): 8.89 (m, 2H, H3,3′, J=2.0)；8.66 (d, 2H, H6,6′, J
=9.0)；7.95 (ddd, 2H, H5,5′, J=11.0)；4.22 (m, 8H, CH2, J=30.0)；1.37 (s, 12H, CH3, J=
6.0)。
2.4,4 '-diphosphonic acid -2,2 '-bipyridyl (H4Dphbpy preparation)
NaOH (16.0mg, 0.4mmol) is dissolved in the methanol of 10.0mL, 2,2 '-bipyridyls-are added slowly with stirring
4,4 '-bis phosphoric acid diethylesters (0.4280g, 0.1mmol).It after heating stirring 6h, evaporates, concentration adds appropriate dilute hydrochloric acid to carry out acid
Change to pH=2, filtering takes precipitating, is dried in vacuo.
3. molecular level iridium catalyst Ir-PO3H2([(H4dphbpy)IrIII(Cp*) Cl] Cl) preparation
Under argon gas protection, [IrIII(Cp*)(Cl2)]2Dimer (0.1995g, 0.25mmol) is at methylene chloride (10.0mL)
In be heated to reflux temperature, magnetic agitation about 20 minutes.4,4 '-diphosphonic acid -2 of addition, and 2 '-bipyridyls (0.1580g, 0.5
Mmol dichloromethane solution), magnetic agitation are simultaneously warming up to 45 DEG C, reflux 10 hours.After reaction sufficiently, reaction solution is cooled to
Room temperature carries out vacuum filter, obtains crocus precipitating, had both been target product molecular level iridium catalyst Ir-PO3H2, product is true
Sky is dry, and makees desiccant with CaO.
1H NMR(D2O, 295K, δ/ppm, J/Hz): 8.94 (s, 2H, H3,3′ dphbpy, J=9.0)；8.66 (d, 2H, H6 ,6′ dphbpy, J=2.0)；7.95 (dd, 2H, H5,5′ dphbpy, J=18.0)；1.60 (s, 15H, CH3 1-5 Cp*)。
(2) molecular level iridium catalyst Ir-PO3H2The WO of modification3Complex light anode (FTO/WO3/Ir–PO3H2)
1.FTO/WO3The preparation of electrode
WO3Pretreatment: at room temperature, in the agate mortar be added 0.0800g tungsten trioxide powder, while be added 20.0 μ L
Adhesive acetylacetone,2,4-pentanedione and 20.0 μ L emulsifier triton x-100s, then add the distilled water of 300.0 μ L, and grinding about 6~
10min is mixed them thoroughly, and obtains WO3Suspension, for use.
The pretreatment of FTO electro-conductive glass: FTO electro-conductive glass (10 × 10cm) is cut into the fritter of 1.0 × 2.0cm, so
Use acetone, ethyl alcohol, deionized water successively ultrasound 10min, taking-up N respectively afterwards2Drying is stand-by.By WO3Suspension using knife coating or
Spin-coating method is supported on FTO electro-conductive glass (area is 1.0 × 1.0cm), several minutes of naturally dry, is dried in vacuum overnight, takes out
It is put into Muffle furnace and is warming up to 500 DEG C with the rate of 5 DEG C/min, calcine 2h, taken out after cooling, obtain FTO/WO3Electrode.
2.FTO/WO3/Ir–PO3H2Complex light anode
The FTO/WO that will be prepared3Electrode is immersed in the molecular level iridium catalyst Ir-PO of 0.5mM3H2Mistake in methanol solution
Night is rinsed after taking-up with deionized water, is removed the remaining catalyst solution of electrode surface, is dried in vacuo or is dried with nitrogen, obtain
Molecular level iridium catalyst Ir-PO3H2The WO of modification3Complex light anode (FTO/WO3/Ir–PO3H2Complex light anode), it is protected from light guarantor
It deposits.
(3) research of photoelectrochemical behaviour
This tests all linear sweep voltammetry test and potentiostatic deposition test, is all made of Shanghai Chen Hua company
CHI660E electrochemical workstation, using three-electrode system, with light anode (FTO/WO3、FTO/WO3/ IrOx and FTO/WO3/Ir–
PO3H2) it is working electrode, it is done with platinum filament or platinum guaze to electrode, reference electrode is done with Ag/AgCl (3.5M saturated potassium chloride solution),
Electrolyte solution uses aqueous solution, the KNO of respectively pH=1.0,0.1M3The phosphoric acid buffer of solution and pH=7.0,0.1M are molten
Liquid is 100mW/cm using optical power density2Xe lamp carry out illumination experiment.It is washed with deionized water electrode used therein, and is carried out
Optical electro-chemistry test.
1.FTO/WO3/ IrOx modified electrode:
[IrIII(Cp*)(H2O)3]2+Preparation: argon gas protection under, [IrIII(Cp*)(Cl2)]2Dimer (0.1995g,
0.25mmol) it is heated to reflux temperature in deionized water (10.0mL), magnetic agitation about 20 minutes.It is then slowly added into
Ag2SO4(0.0779g) aqueous solution, while having white precipitate generation, it is heated to reflux 12 hours.After completion of the reaction, liquid cooling will be reacted
But to room temperature and vacuum filter is carried out, ethanol in proper amount is added in filtrate and is rotated, is concentrated.Appropriate first is added into concentrate again
Alcohol dissolution, then recrystallized from acetonitrile is added dropwise, then rotated, it is concentrated, vacuum drying obtains clear yellow viscous substance [IrIII(Cp*)
(H2O)3]2+, this matter-pole is soluble easily in water.
FTO/WO3/ IrOx modified electrode: compound concentration is the catalyst [Ir of 0.005MIII(Cp*)(H2O)3]2+Aqueous solution,
With FTO/WO3Electrode is working electrode, and Ag/AgCl electrode is reference electrode, and platinum electrode is made to electrode, with potentiostat into
Row electrochemical deposition.Voltage is 2.5V vs Ag/AgCl, time 10s, then stablizes 5 in the potassium nitrate solution of pH=3.0
S obtains FTO/WO3/ IrOx modified electrode.
2. the physical property characterization of light anode and test
2.1 correlation WO3The electron scanning micrograph (SEM) of nanometer powder
Such as Fig. 1, the present invention is by business WO3Nanometer powder is supported in FTO substrate by knife coating, is prepared for FTO/ WO3
Light anode (Fig. 1 (A)), electrode surface are that unordered porous nano particle is overlapped mutually, and has very big specific surface area, are
Molecular catalyst Ir-PO3H2Adsorbance provide guarantee.From Fig. 1 (B), FTO/WO3The scanning electron microscope of the cross section of electrode
Figure is as can be seen that the thickness of the WO 3 film of blade coating reaches about 5.0 μm.From pattern, answered using what knife coating obtained
Composite electrode specific surface area is bigger, is conducive to the diffusion of electrolyte, is also beneficial to WO3Surface hydroxyl and Ir catalyst phosphorus
Acidic group combines.Fig. 1 (C) is FTO/WO3/Ir–PO3H2Scanning electron microscope (SEM) photograph before complex light anode electrolysis, Fig. 1 (D) is FTO/WO3/
Ir–PO3H2Scanning electron microscope (SEM) photograph after complex light anode electrolysis, passes through comparison, it can be seen that complex light anode electrolysis front and back, surface
Pattern is almost consistent, changes without what, it is possible thereby to illustrate Ir-PO3H2Catalyst is molecular level, and in electrolytic process, is not had
To form bulky grain oxide.
The proof of 2.2 complex light anodes and catalyst molecule level
Such as Fig. 2 a- Fig. 2 d, in order to further prove that iridium catalyst has been adsorbed onto FTO/WO3Electrode surface has carried out a system
The energy dispersion X-ray spectrum (EDX) of column is tested, and demonstrates FTO/WO from the negative3/Ir–PO3H2Complex light anode plays electricity and urges
The active specy for changing water oxidation is Ir-PO3H2Molecule, and Ir-PO in catalytic process3H2Molecule is not converted into have and live
The oxide of property.
If the Raman spectrum of Fig. 3 a and Fig. 3 b are shown, prepared original I r-PO3H2The peak value of catalyst is in 1000-1800
Under nm range and FTO/WO3/Ir–PO3H2Complex light anode is consistent, and FTO/WO3/IrOXElectrode not appearance within this range.
If the x-ray photoelectron spectroscopy (XPS) of Fig. 4 a and Fig. 4 b are shown, WO is shown3Area load molecular level
Ir–PO3H2Catalyst.
3. the photoelectrochemical behaviour of complex light anode is tested
The test of 3.1 photoelectric currents-potentiometric
As shown in figure 5 a and 5b, the present invention uses the mode of loading of knife coating, with photosensitizer WO3For substrate, Ir-
PO3H2Or IrOx be catalyst, under acid pH=1.0 and neutral pH=7.0 environment, investigated system visible light (λ >
Under 400nm) driving, the performance of water oxygen galvanic current potential change.
Such as Fig. 5 a, with pH=1.0,0.1M KNO3Solution is as electrolyte solution, when to FTO/WO3/Ir–PO3H2It is compound
When light anode carries out illumination, which shows good catalytic activity.Such as when to WO3When electrode illumination, adding outside
When voltage 1.5V vs Ag/AgCl, also there is no water oxidation reactions, and work as and be adsorbed with catalyst IrOx or Ir-PO3H2Three
When tungsten oxide light anode, water oxygen occurs in 1.3V vs Ag/AgCl or so, when comparing combination electrode under specific voltage
When density of photocurrent, it is adsorbed with catalyst Ir-PO3H2Tungstic acid light anode show better catalytic performance, such as exist
When 1.23V vs RHE, FTO/WO3The density of photocurrent of electrode is 0.90mA/cm2, FTO/WO3The photoelectric current of/IrOx electrode is close
Degree is 0.88mA/cm2, and FTO/WO3/Ir–PO3H2Density of photocurrent be 1.75mA/cm2, it is approximately FTO/WO3The 2 of electrode
Times.
Such as Fig. 5 b, with pH=7.0,0.1M phosphate buffer solution is as electrolyte solution, complex light anode FTO/WO3/Ir–
PO3H2Excellent performance is also shown in illumination test.Under visible optical drive, WO3Electrode is in 1.3V vs Ag/AgCl
Left and right generation water oxidation reaction, and FTO/WO3/ IrOx modified electrode and FTO/WO3/Ir–PO3H2The water oxygen of complex light anode
Current potential ratio FTO/WO3Light anode difference low 200mV and 350mV or so.The photoelectric current for comparing Different electrodes under specific voltage is close
Degree, in 1.23V vs RHE, FTO/WO3The density of photocurrent of electrode is 0.21mA/cm2, FTO/WO3The photoelectric current of/IrOx
Density is 0.30mA/cm2, and FTO/WO3/Ir–PO3H2Density of photocurrent be 0.41 mA/cm2, it is FTO/WO3The 2 of electrode
Times.
Result above illustrates to be adsorbed with catalyst Ir-PO3H2Tungstic acid light anode with good catalytic water aoxidize
Activity, mainly since it is with lower water oxygen overpotential and lower transition state energy barrier.
3.2 stability test
According to above photoelectric current-potential test as a result, such as Fig. 6 a and Fig. 6 b, and investigate in certain bias (1.23V
Vs RHE and 1.2V vs Ag/AgCl) under tungstic acid/catalyst composite photoelectric aurora electric current stability, i.e., to FTO/
WO3/Ir–PO3H2Complex light anode carry out i-t test, then with the FTO/WO under the same terms3Electrode, FTO/WO3/ IrOx electricity
The photoelectric current of pole compares.
Such as Fig. 6 a, with pH=1.0,0.1M KNO3Solution carries out under 1.23V vs RHE bias as electrolyte solution
Long-time illumination, for FTO/WO3For light anode, density of photocurrent is by 0.65mA/cm2It is reduced rapidly, then with 0.22mA/
cm2The current density of left and right keeps stablizing, and for FTO/WO3/Ir-PO3H2Combination electrode, density of photocurrent can be stable
It is maintained at 0.60mA/cm2The reason of left and right, wherein photoelectric current slightly reduces may be table of the bubble coalescence in electrode of generation
Face blocks the contact of hydrone with electrode activity site.Meanwhile and under the same conditions, to electro deposition oxidation iridium catalyst
Optoelectronic pole (FTO/WO3/ IrOx) carry out density of photocurrent stability test, the density of photocurrent of modified electrode with do not have
The tungstic acid electrode for loading any catalyst, which is compared, not to be improved.Thus explanation is adsorbed with catalyst Ir-PO3H2Three oxidations
Tungsten electrode is with good stability under light illumination.
Such as Fig. 6 b, with pH=7.0, electrolyte solution, 1.2V vs Ag/AgCl are inclined as a comparison for 0.1M phosphate buffer solution
When pressure carries out long-time illumination, combination electrode FTO/WO3And FTO/WO3/ IrOx current density is in 0.10mA/cm2Left and right is protected
It is fixed to keep steady, FTO/WO3/Ir-PO3H2The density of photocurrent of combination electrode is in about 0.24mA/cm2Place keeps stablizing.In general,
Since the interaction force of chemical bond between organometallic complex and tungstic acid is weaker, in a neutral environment when illumination, match
The phenomenon that object is easy to appear De contamination is closed, so the service life of optical drive water oxidation system is generally shorter.
The electrochemical impedance spectroscopy (EIS) of 3.3 complex light anodes characterizes
Test result shows that biggish tungstic acid population can show more boundary defects and bigger resistance and prove electricity
The transmission of lotus.Observation EIS's the result shows that, semicircle is presented in each electrode, so as to the quasi equivalent circuit model of mould, such as schemes
7.In this model, element RΩResistance relevant to charge transmission is indicated, including the resistance of semiconductor catalyst, FTO
The conducting wire of substrate, electrolyte and the entire circuit of connection.Element RctAnd CctIt indicates in the related charge of optoelectronic pole/electrolyte interface
Transfer, the lesser semicircle representative of a radius is better (i.e. higher charge transport ability, faster surface reaction power
It learns).FTO/WO3/Ir-PO3H2Electrode has smaller radius than simple tungstic acid electrode, that is, has better photocatalysis
Activity, but FTO/WO3For/IrOx light anode due to the aggtegation of IrOx, radius is larger, and charge transport ability is weaker.This table
The single layer Ir-PO of bright load3H2Molecular catalyst has high degree of dispersion state, significantly improves the reaction power of its electrode surface
It learns, this is significantly to building photoelectrochemical cell.
4. the kinetic test of complex light anode
The instantaneous density of photocurrent of 4.1 complex light anodes is tested
As Fig. 8 a and Fig. 8 b occurs in FTO/WO under visible light illumination3/Ir-PO3H2Water oxygen in complex light anode
Reaction mechanism (or rate determining step) is to be totally different from FTO/WO3/ IrOx light anode.The kinetic isotope effect of H/D
(KIE) measurement is a strong evidence, by comparing in H2O and D2O current density proves rate determining step.Rate control
Proton translocation and proton couple electronic transfer (PCET) of the step (RDS) processed involved in chemical reaction can be in the power of H/D
It learns and is emerged from isotope effect (KIE) measurement.The oxidation reaction of water is related to the transmitting of four protons and four electronics, thus
Realize that the decomposition of water generates oxygen, which can be used to analyze and be rate limit the step for understanding.
As Fig. 8 a shows FTO/WO3/ IrOx light anode is in D2Current density (the J ≈ 0.11mA cm of O-2) it is H2The one of O
Half, it is consistent with IrOx reported in the literature, show that water oxygen is rate determining step.This means that FTO/WO3/ IrOx light anode
Rate determining step electric charge transfer is from IrOx to water, rather than from WO3To IrOx.
In contrast, such as Fig. 8 b, FTO/WO3/Ir-PO3H2Complex light anode is in D2O and H2Electric current in O is almost the same.It changes
Sentence is talked about, molecular level catalyst Ir-PO3H2The FTO/WO of modification3/Ir-PO3H2The KIE of complex light anode is close to 1.0.Cause
This, the turnover frequency of system is the rate control that catalyst is transferred to by hole.This shows that RDS is from WO3To catalyst electricity
The rate of lotus transfer, rather than the rate of autoxidation occurs for water.It is rate-limiting step that this phenomenon, which shows that hole is transferred to catalyst,
Suddenly, while the speed that also indicates that subsequent hole is transferred to water is very fast.
The test of 4.2 transient short circuit currents
In order to prove this structure with the photoresponse effect of the variation of time, in 1.23V vs RHE, using platinum filament as
To electrode, FTO/WO3/ IrOx and FTO/WO3/Ir-PO3H2Complex light anode generated transient state short circuit in illumination/not illumination
Electric current.
If Fig. 9 a and Fig. 9 b are load IrOx and Ir-PO3H2The WO of catalyst3The i-t curve of electrode.Under illumination condition,
The electronics of combination electrode is excited to electrode surface, generates very big short circuit current, corresponds to a photoresponse peak value, then photoelectricity
Stream is gradually restored to stable state again.Equally, when lamp is turned off, also there is corresponding photoresponse peak value, i.e. generation cathode electricity
Stream.Therefore, the Primary photocurrent in each period is equal to the value of starting point, rather than the terminal in the last one period.This is because
The accumulation of surface voids or in WO3Some charge accumulations that surface is formed, these phenomenons all may cause photoelectric current enhancing.Thus
It obtains, the rate of water decomposition is relatively slow, and a part of electronics cannot participate in water decomposition well, leads to one from IrOx
Light induced electron is divided to be transported to WO rapidly3Surface, another part light induced electron return.
5. the faradic efficiency of complex light anode
To the WO of molecular level iridium catalyst modification3The electro-chemical test of complex light anode in three-electrode cell, with
The KNO of 0.1M3Buffer solution is electrolyte, with Ag/AgCl (3.5M saturated potassium chloride solution) for reference electrode, FTO/WO3/
Ir–PO3H2It is to electrode with platinum guaze for working electrode.When carrying out faradic efficiency test, in a three closed electrolysis
Ag/AgCl (3.5M saturated potassium chloride solution) reference electrode, FTO/WO are installed on pond3/Ir–PO3H2Working electrode, platinum guaze pair
Electrode.After the completion of installing and being closed, deoxygenation is bubbled to test system with argon gas.Using the bias of 1.23V vs RHE, electrolysis is opened
After beginning, with the current density generated in light anode in electrochemical workstation detection electrolytic process, every 1h gas chromatographic detection
The mole of the oxygen released, electrolysis time 4h.The theoretical production quantity of oxygen in electrolytic trial, by being flowed in electrolytic process
The electricity crossed, is calculated according to Faraday's law.Faradic efficiency=O of final light anode2 (actual amounts)/O2 (theoretical amounts)。
Under the illumination condition of AM1.5, when applying bias is 1.23V vs RHE, FTO/WO is tested respectively3With
FTO/WO3/Ir-PO3H2The faradic efficiency of electrode.
As shown in Figure 10, relative to exposed WO3Electrode, FTO/WO3/Ir-PO3H2The faradic efficiency of complex light electrode
It dramatically increases, in 2.5h, η (O2) ≈ 100%, after being electrolysed 4h, η (O2) ≈ 95%.For FTO/WO3Electrode works as electrolysis
After 4h, η (O2) ≈ 56%.FTO/WO3/Ir-PO3H2Combination electrode generates O under illumination condition2Theoretical value and practical O2's
Yield is substantially uniform, further demonstrates molecular catalyst Ir-PO3H2Load, not only increase composite photoelectric current density,
Also FTO/WO greatly improved3Photocatalysis water oxidation efficiency.
Claims (7)
1. the WO of molecular level iridium catalyst modification3Complex light anode, which is characterized in that preparation method includes the following steps:
1) FTO/WO3The preparation of electrode: by pretreated WO3WO is prepared with distilled water3Suspension；By WO3Suspension uses blade coating
Method or spin-coating method are supported on FTO electro-conductive glass, and naturally dry is dried in vacuum overnight, in Muffle furnace, with the speed of 5 °C/min
Rate is warming up to 500 °C, calcines 2-3 h, is cooled to room temperature and is made annealing treatment after taking-up, obtain FTO/WO3Electrode；
2) FTO/WO that will be prepared3Electrode is immersed in the methanol solution of molecular level iridium catalyst overnight, spent after taking-up from
Sub- water rinses, and is dried in vacuo or is dried with nitrogen, and obtains the WO of molecular level iridium catalyst modification3Complex light anode is kept in dark place；
The molecular level iridium catalyst is the molecule Ir-PO with four-coordination3H2, chemical molecular formula is [(H4dphbpy)
IrIII(Cp*)Cl]Cl ；Wherein, Cp*=pentamethylcyclopentadiene.
2. the WO of molecular level iridium catalyst modification according to claim 13Complex light anode, which is characterized in that described
Molecular level iridium catalyst Ir-PO3H2Preparation method include the following steps: with 2,2 '-bipyridyls -4,4 '-bis phosphoric acid diethylester
For raw material, 4,4 '-diphosphonic acid -2,2 '-bipyridyl H are synthesized4Dphbpy, further with [IrIII(Cp*)(Cl2)]2Dimer is anti-
It answers, synthesizes the molecular level iridium catalyst Ir-PO with the four-coordination of stability structure3H2。
3. the WO of molecular level iridium catalyst modification according to claim 23Complex light anode, which is characterized in that described
Molecular level iridium catalyst Ir-PO3H2Preparation method include the following steps:
1) 2,2 '-bipyridyl -4 are prepared, 4 '-bis phosphoric acid diethylesters: under nitrogen protection, takes 4,4 '-two bromo- 2,2 '-bipyridyls,
Pd(pph3)4, diethyl phosphite and Et3N under 80-90 C, is heated to reflux 3-4 h, is cooled to room in organic solvent
Ether is added into reaction solution for temperature, vacuum filtration, filtrate concentrated by rotary evaporation, contact plate, and silica gel column chromatography obtains 2,2 '-bipyridyl -4,
4 '-bis phosphoric acid diethylesters；
2) 4,4 '-diphosphonic acid -2 are prepared, 2 '-bipyridyls: NaOH is dissolved in methanol, is added slowly with stirring 2,2 '-connection pyrroles
4,4 '-bis phosphoric acid diethylester of pyridine-, the heating stirring 6-7 h at 45-55 DEG C are concentrated by evaporation, and concentrate carries out being acidified to pH=2,
Filtering, takes precipitating, is dried in vacuo, obtains 4,4 '-diphosphonic acid -2,2 '-bipyridyls；
3) molecular level iridium catalyst Ir-PO is prepared3H2: under argon gas protection, by [IrIII(Cp*)(Cl2)]2Dimer is in dichloromethane
It is heated to reflux temperature in alkane, magnetic agitation 20-30 minutes, 4,4 '-diphosphonic acid -2 are added, the methylene chloride of 2 '-bipyridyls is molten
Liquid, magnetic agitation are simultaneously warming up to 40-50 °C, back flow reaction 10-11 hours, reaction solution are cooled to room temperature, vacuum filter takes
Precipitating, obtains target product.
4. the WO of molecular level iridium catalyst modification according to claim 33Complex light anode, which is characterized in that described
Organic solvent is toluene.
5. the WO of molecular level iridium catalyst modification according to claim 33Complex light anode, which is characterized in that by mole
Than, 4,4 '-diphosphonic acid -2,2 '-bipyridyls: [IrIII(Cp*)(Cl2)]2 =2:1。
6. the WO of molecular level iridium catalyst modification according to claim 33Complex light anode, which is characterized in that step 2
In, it is acidified with hydrochloric acid.
7. the WO of molecular level iridium catalyst modification described in claim 13Application of the complex light sun in electrolysis water oxygen.
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| CN102491989A (en) * | 2011-11-26 | 2012-06-13 | 南京大学 | Iridium complex, preparation method of iridium complex, method for catalyzing and reducing water by using visible light and dye-sensitized solar cell |
| WO2012124482A1 (en) * | 2011-03-11 | 2012-09-20 | 富士フイルム株式会社 | Metal complex pigment, metal complex pigment composition, photoelectric conversion element, and photoelectrochemical cell |
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| US20140112849A1 (en) * | 2011-06-21 | 2014-04-24 | Umicore Ag & Co., Kg | Method for the depositon of metals on support oxides |
| CN102491989A (en) * | 2011-11-26 | 2012-06-13 | 南京大学 | Iridium complex, preparation method of iridium complex, method for catalyzing and reducing water by using visible light and dye-sensitized solar cell |
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