CN106801231A - 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 PDF

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CN106801231A
CN106801231A CN201710067862.XA CN201710067862A CN106801231A CN 106801231 A CN106801231 A CN 106801231A CN 201710067862 A CN201710067862 A CN 201710067862A CN 106801231 A CN106801231 A CN 106801231A
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molecular level
fto
iridium catalyst
light anode
complex light
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CN106801231B (en
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夏立新
童海丽
姜毅
张谦
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Liaoning University
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    • 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
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    • 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 OR LIGHT-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

Abstract

The present invention relates to the WO of molecular level iridium catalyst modification3Complex light anode and its application.It is sensitising agent to use with visible light-responded inorganic semiconductor material tungstic acid, 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 using the mode of chemisorbed, constitute inorganic semiconductor/molecular catalyst (FTO/WO3/Ir–PO3H2) complex light anode catalyst system and catalyzing, effectively prevent both hole and electron to recombinate, the electric charge transmission between electrode/electrolyte interface is greatly accelerated, separation of charge efficiency and interface reaction kinetics are improve, it is achieved thereby that complex light anode is in visible ray (λ>400nm,100mW/cm2) drive lower catalytic water oxidation to produce oxygen.

Description

The WO of molecular level iridium catalyst modification3Complex light anode and its application
Technical field
Base group modification is carried out by introducing phosphate group in catalyst structure the present invention relates to one kind, using chemisorbed Effect, iridium catalyst is loaded to as light anode on semiconductor tungstic acid electrode, is built NEW TYPE OF COMPOSITE light anode and its is answered With.
Background technology
With the fast development of social economy, the mankind are growing day by day to the demand of the energy, 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。 Therefore deduce that, on the energy ratio earth that the sun is provided per hour more than 1 year energy of consumption of the mankind.Although the mankind early have Application on solar energy, but the solar energy for being utilized is insignificant, and condition is limited.So, find the new utilization sun The mode of energy simultaneously produces renewable and clean energy resource just as the focus of current scientific circles research.
Relevant solar energy conversion mainly has three kinds of approach at present：1. using photovoltaic power generation equipment (Photovoltaic, PV electric energy) is directly converted light energy into.How to increase its conversion efficiency and solve the problems, such as that fossil fuel environment is effective Using a major challenge of solar energy.2. the plant for being produced using photosynthesis of plant and crop by-product synthesising biological fuel, Such as corn transformation is ethanol, though economic and environment-friendly, the cycle is long, high cost.3. manual simulation's photosynthesis.The pass of this approach Key is, under sunlight, is acted on by electric charge transfer, charge accumulated and catalyst and realizes that electron-hole is separated, from And decomposition water is realized, discharge hydrogen and oxygen.
In the photosynthetic early stage research of manual simulation, mainly with Ru, the precious metals complex such as Ir is molecular catalyst, In the case of powering up sub- sacrificial body outside, the oxidation Decomposition of water is realized in homogeneous system, or with TiO2, the metal oxygen 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 into various reaction systems such as photocatalytic system, electro-catalysis system and photoelectrochemical cell.With Traditional metal oxide heterogeneous catalyst is compared, and the water oxidation catalyst of many molecular levels can in catalysis activity and structure In tonality, have a clear superiority, and inorganic semiconductor material not only has photocatalytic activity, it may have good photostability etc. Advantage.
The content 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).Using the mode of chemisorbed by the horizontal iridium catalyst Ir-PO of monomolecular3H2Load to tungstic acid substrate On, constitute inorganic semiconductor/molecular catalyst (FTO/WO3/Ir–PO3H2) complex light anode catalyst system and catalyzing.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：The WO of molecular level iridium catalyst modification3Complex light Anode, preparation method comprises the following steps：
1)FTO/WO3The preparation of electrode：The WO that will be pre-processed3WO is prepared with distilled water3Suspension；By WO3Suspension is used Knife coating or spin-coating method are supported on FTO electro-conductive glass, are dried naturally, dried in vacuum overnight, are 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 With deionized water rinsing, vacuum drying or nitrogen are dried up, and obtain the WO of molecular level iridium catalyst modification3Complex light anode, keeps away Light is preserved.
The WO of above-mentioned molecular level iridium catalyst modification3Complex light anode, step 1) in, described annealing is, In Muffle furnace, 500 DEG C are warming up to the speed of 5 DEG C/min, calcine 2-3h, room temperature is cooled to after taking-up.
The WO of above-mentioned molecular level iridium catalyst modification3Complex light anode, described molecular level iridium catalyst is tool There is the molecule Ir-PO of four-coordination3H2, its chemical molecular formula is [(H4dphbpy)IrIII(Cp*)Cl]Cl；Wherein, H4Dphbpy= 4,4 '-diphosphonic acid -2,2 '-bipyridyl, Cp*=pentamethylcyclopentadienes.
The WO of above-mentioned molecular level iridium catalyst modification3Complex light anode, described molecular level iridium catalyst Ir- PO3H2Preparation method comprise the following steps：With 2,2 '-bipyridyl -4,4 '-bis phosphoric acid diethylester is raw material, synthesis 4,4 '-two Phosphoric acid -2,2 '-bipyridyl H4Dphbpy, further with [IrIII(Cp*)(Cl2)]2Dimerization precursor reactant, synthesis has 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, described molecular level iridium catalysis Agent Ir-PO3H2Preparation method comprise the following steps：
1) 2,2 '-bipyridyl -4,4 is prepared '-bis phosphoric acid diethylester：Under nitrogen protection, 4,4 '-two bromo- 2,2 '-connection is taken Pyridine, Pd (pph3)4, diethyl phosphite and Et3N, in organic solvent, at 80-90 DEG C, is heated to reflux 3-4h, is cooled to Room temperature, to adding ether in reaction solution, vacuum filtration, filtrate concentrated by rotary evaporation puts plate, silica gel column chromatography, obtain 2,2 '-bipyridyl- 4,4 '-bis phosphoric acid diethylester；Preferably, described organic solvent is toluene；
2) 4,4 '-diphosphonic acid -2,2 is prepared '-bipyridyl：NaOH is dissolved in methyl alcohol, it is added slowly with stirring 2,2 '- Bipyridyl -4,4 '-bis phosphoric acid diethylester, in heating stirring 6-7h at 45-55 DEG C, is concentrated by evaporation, and concentrate carries out being acidified to pH =2, filtering takes precipitation, is vacuum dried, and obtains 4,4 '-diphosphonic acid -2,2 '-bipyridyl；Preferably, it is acidified with hydrochloric acid.
3) molecular level iridium catalyst Ir-PO are prepared3H2：Under argon gas protection, by [IrIII(Cp*)(Cl2)]2Dimer exists Reflux temperature is heated in dichloromethane, magnetic agitation 20-30 minutes, 4,4 '-diphosphonic acid -2, the dichloro of 2 '-bipyridyl is added Dichloromethane, magnetic agitation is simultaneously warming up to 40-50 DEG C, back flow reaction 10-11 hours, reaction solution is cooled into room temperature, vacuum mistake Filter, takes precipitation, obtains target product.
Preferably, in molar ratio, 4,4 '-diphosphonic acid -2,2 '-bipyridyl:[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 invention are as follows：
1. the present invention, designs and has synthesized molecule iridium catalyst, with phosphoric acid as bridged bond, will divide by way of covalent bond is adsorbed Sub- iridium catalyst loads to WO3Electrode surface, constructs the tungstic acid semiconductor optical anode of molecular catalyst modification, to building Novel photoelectric chemical cell tool is of great significance.Photoelectrocatalysis result shows, using mode of loading of the present invention, when When applying bias are 1.23V (vs RHE), under visible light illumination, NEW TYPE OF COMPOSITE light anode FTO/WO3/Ir–PO3H2In pH= 1.0 KNO3Density of photocurrent in solution compares FTO/WO3Electrode increased 50%, and faradic efficiency is 95%, is effectively increased Transmission and separative efficiency between semiconductor optical anode electric charge-hole, catalysis activity are much better than the tungstic acid of yttrium oxide modification Light anode.To realize complex light anode in visible ray (λ>400nm,100mW/cm2) drive lower catalytic water oxidation to produce oxygen to carry For theoretical foundation.
2. the present invention, simulates the photosynthesis of nature, using with the visible light-responded oxygen of inorganic semiconductor material three Change tungsten is sensitising agent, 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 using the mode of chemisorbed, composition is inorganic partly to be led Body/molecular catalyst (FTO/WO3/Ir–PO3H2) complex light anode catalyst system and catalyzing, effectively prevent both hole and electron to recombinate, significantly The electric charge transmission between electrode/electrolyte interface is accelerated, separation of charge efficiency and interface reaction kinetics are improve, so that real Complex light anode is showed in visible ray (λ>400nm,100mW/cm2) drive lower catalytic water oxidation to produce oxygen.
3. of the invention, with the WO with photostability3Semiconductor nano material as sensitising agent, with the molecular water of high activity Flat complex of iridium [(H4dphbpy)IrIIICp*(Cl)]Cl(Ir-PO3H2), both are combined, preparation can be in acid, low electricity Efficient under the conditions of position, stabilization electrolysis aquatic products oxygen composite anode；This kind of light anode has no report.Tentatively realize molecular catalyst Light, the device of electric decomposition water, be that the application of water oxygen chemoattractant molecule catalyst opens new approach.
4. of the invention, it is sensitising agent to use with visible light-responded inorganic semiconductor material tungstic acid, with steady Molecular level the iridium catalyst [(H of fixed structure4dphbpy)IrIII(Cp*) Cl] Cl be catalyst, using the mode of chemisorbed 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 closing light, effectively prevents both hole and electron to recombinate, and the electric charge greatly accelerated between electrode/electrolyte interface is passed It is defeated, separation of charge efficiency and interface reaction kinetics are improve, it is achieved thereby that complex light anode is in visible ray (λ>400 nm, 100mW/cm2) drive lower catalytic water oxidation to produce oxygen.
Brief description of the drawings
Fig. 1 is WO3The related scans electron microscope picture (SEM figures) 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 are the energy spectrum diagrams (EDX figures) of FTO basal electrodes.
Fig. 2 b are FTO/WO3The energy spectrum diagram (EDX figures) of basal electrode.
Fig. 2 c are Ir-PO3H2The FTO/WO of modification3/Ir-PO3H2Energy spectrum diagram (EDX figures) before complex light anode electrolysis.
Fig. 2 d are Ir-PO3H2The FTO/WO of modification3/Ir-PO3H2Energy spectrum diagram (EDX figures) after complex light anode electrolysis.
Fig. 3 a are the Raman spectrums of catalyst and different composite electrode.
Wherein, a：Ir–PO3H2Catalyst fines；b：FTO/WO3Substrate；c：FTO/WO3/ IrOx electrodes；d：FTO/WO3/ Ir-PO3H2Electrode.
Fig. 3 b are 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 are Ir-PO3H2The FTO/WO of modification3/Ir-PO3H2The XPS of complex light anode is composed entirely.
Fig. 4 b are Ir-PO3H2The FTO/WO of modification3/Ir-PO3H2The XPS enlarged drawings of complex light anode.
Fig. 5 a are different modifying electrode (pH=1.0,0.1M KNO3Solution) linear scan curve (J-V).
Wherein, 1：WO under 1.4V vs Ag/AgCl bias conditions3；2：Under 1.4V vs Ag/AgCl bias conditions WO3/IrOx；3：WO under 1.4V vs Ag/AgCl bias conditions3/Ir–PO3H2。
Fig. 5 b are the linear scan curves (J-V) of different modifying electrode (pH=7.0,0.1M phosphate buffer solution).
Wherein, 1：WO under 1.2V vs Ag/AgCl bias conditions3；2：Under 1.2V vs Ag/AgCl bias conditions WO3/IrOx；3：WO3/Ir-PO under 1.2V vs Ag/AgCl bias conditions3H2)。
Fig. 6 a are different modifying electrode (pH=1.0,0.1M KNO3Solution, 1.23V vs RHE bias) i-t curves.
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 are the i-t of different modifying electrode (pH=7.0,0.1M phosphate buffer solution, 1.2V vs Ag/AgCl biass) 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 are FTO/WO3/ IrOx electrodes are in H2O and D2The i-t curves of O.
Wherein, experiment condition：Illumination (the 100mW/cm of AM 1.5G2), pH 1.0,0.1M KNO3Solution, voltage 1.23V vs.RHE。
Fig. 8 b are FTO/WO3/Ir-PO3H2Electrode is in H2O and D2The i-t curves of O.
Wherein, experiment condition：Illumination (the 100mW/cm of AM 1.5G2), pH 1.0,0.1M KNO3Solution, voltage 1.23V vs.RHE。
Fig. 9 a are FTO/WO3The cycle transient short-circuit current of/IrOx electrodes in illumination/not illumination.
Wherein, experiment condition：Illumination (the 100mW/cm of AM 1.5G2), pH 1.0,0.1M KNO3Solution, voltage 1.23V vs.RHE。
Fig. 9 b are FTO/WO3/Ir-PO3H2Cycle transient short-circuit current of the electrode in illumination/not illumination.
Wherein, experiment condition：Illumination (the 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：Illumination (the 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；Rhombus 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
1.2,2 '-bipyridyl -4,4 '-bis phosphoric acid diethylester preparation
Under nitrogen protection, 4,4 '-two bromo- 2,2 '-bipyridyl (Br are added in 50.0mL there-necked flasks2Bpy) (0.7850g, 0.5mmol), Pd (pph3)4(0.2500g, 0.5mmol), Et3N (0.7mL), diethyl phosphite (0.7mL), in 15.0mL first In benzene, in 4h at 85 DEG C, is heated to reflux, question response completely, is cooled to room temperature, is filtered to ether, vacuum filtration is added in reaction solution Precipitation is gone, then concentrated by rotary evaporation filtrate carry out a plate, be finally collected product 2 with silica gel column chromatography, 2 '-bipyridyl -4, 4 '-bis phosphoric acid diethylester.
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 methyl alcohol of 10.0mL, 2 are added slowly with stirring, 2 '-bipyridyl- 4,4 '-bis phosphoric acid diethylester (0.4280g, 0.1mmol).After heating stirring 6h, evaporation, concentration, plus appropriate watery hydrochloric acid carries out acid Change to pH=2, filtering takes precipitation, is vacuum dried.
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 dichloromethane (10.0mL) In be heated to reflux temperature, magnetic agitation about 20 minutes.Addition 4,4 '-diphosphonic acid -2,2 '-bipyridyl (0.1580g, Dichloromethane solution 0.5mmol), magnetic agitation is simultaneously warming up to 45 DEG C, backflow 10 hours.It is after reaction fully, reaction solution is cold But to room temperature, vacuum filter is carried out, obtains crocus precipitation, be both target product molecular level iridium catalyst Ir-PO3H2, will produce Thing is vacuum dried, and makees drier 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, 0.0800g tungsten trioxide powders are added in agate mortar, while adding 20.0 μ L Adhesive acetylacetone,2,4-pentanedione and 20.0 μ L emulsifying agent triton x-100s, then add the distilled water of 300.0 μ L, and grinding about 6~ 10min, is sufficiently mixed it, obtains WO3Suspension, it is stand-by.
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, ethanol, deionized water ultrasound 10min successively, 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), and several minutes are dried naturally, and dried in vacuum overnight takes out It is put into Muffle furnace and is warming up to 500 DEG C with the speed of 5 DEG C/min, calcine 2h, taken out after cooling, obtains 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 At night, deionized water rinsing is used after taking-up, remove the catalyst solution of electrode surface residual, vacuum drying or nitrogen drying, obtained Molecular level iridium catalyst Ir-PO3H2The WO of modification3Complex light anode (FTO/WO3/Ir–PO3H2Complex light anode), lucifuge is protected Deposit.
(3) research of photoelectrochemical behaviour
The all of linear sweep voltammetry test of this experiment and potentiostatic deposition test, using Shanghai Chen Hua company CHI660E electrochemical workstations, using three-electrode system, with light anode (FTO/WO3、FTO/WO3/ IrOx and FTO/WO3/Ir– PO3H2) it is working electrode, done to electrode with platinum filament or platinum guaze, reference electrode is done with Ag/AgCl (3.5M saturated potassium chloride solutions), Electrolyte solution uses the aqueous solution, respectively pH=1.0, the KNO of 0.1M3The phosphoric acid buffer of solution and pH=7.0,0.1M is molten Liquid, is 100mW/cm using optical power density2Xe lamps carry out illumination experiment.Net electrode used therein is washed with deionized water, and carries out Optical Electro-Chemistry is tested.
1.FTO/WO3/ IrOx modified electrodes：
[IrIII(Cp*)(H2O)3]2+Preparation：Under argon gas protection, [IrIII(Cp*)(Cl2)]2Dimer (0.1995g, Reflux temperature, magnetic agitation about 20 minutes 0.25mmol) are heated in deionized water (10.0mL).It is then slowly added into Ag2SO4(0.0779g) aqueous solution, while there is white precipitate to produce, is heated to reflux 12 hours.After completion of the reaction, it is reaction solution is cold But to room temperature and vacuum filter is carried out, adds ethanol in proper amount to be rotated in filtrate, concentrated.Again to adding appropriate first in concentrate Alcohol dissolves, then recrystallized from acetonitrile is added dropwise, then is rotated, and concentrates, and vacuumizes drying, obtains clear yellow viscous material [IrIII(Cp*) (H2O)3]2+, this matter-pole is soluble in water.
FTO/WO3/ IrOx modified electrodes：Compound concentration is the catalyst [Ir of 0.005MIII(Cp*)(H2O)3]2+The aqueous solution, With FTO/WO3Electrode is working electrode, and Ag/AgCl electrodes are reference electrode, and platinum electrode is made to electrode, carried out with potentiostat Electrochemical deposition.Voltage is 2.5V vs Ag/AgCl, and the time is 10s, then the stabilization 5s in the potassium nitrate solution of pH=3.0, is obtained FTO/WO3/ IrOx modified electrodes.
2. the physical property of light anode is characterized and test
2.1 correlation WO3The electron scanning micrograph (SEM) of nanometer powder
Such as Fig. 1, it is of the invention by business WO3Nanometer powder is supported in FTO substrates by knife coating, is prepared for FTO/WO3Light Anode (Fig. 1 (A)), electrode surface is that unordered porous nano particle is overlapped mutually, and with very big specific surface area, to divide Muonic catalysis agent Ir-PO3H2Adsorbance provide ensure.From Fig. 1 (B), FTO/WO3The scanning electron microscope (SEM) photograph of the cross section of electrode As can be seen that the thickness of the WO 3 film of blade coating reaches about 5.0 μm.From pattern, being combined that knife coating is obtained is used Electrode specific surface area is conducive to the diffusion of electrolyte than larger, is also beneficial to WO3Surface hydroxyl and Ir catalyst phosphate With reference to.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, by contrast, it can be seen that before and after complex light anode electrolysis, surface topography It is almost consistent, there is no anything to change, it is possible thereby to illustrate Ir-PO3H2During catalyst is molecular level, and electrolytic process, there is no shape Into 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, having carried out one is Energy dispersion X-ray spectrum (EDX) test of row, demonstrates FTO/WO from the negative3/Ir–PO3H2Complex light anode plays electricity and urges The active specy for changing water oxidation is Ir-PO3H2Ir-PO in molecule, and catalytic process3H2Molecule is not converted into having and lives The oxide of property.
As the Raman spectrum of Fig. 3 a and Fig. 3 b shows, prepared original I r-PO3H2The peak value of catalyst is in 1000- Under 1800nm scopes and FTO/WO3/Ir–PO3H2Complex light anode is consistent, and FTO/WO3/IrOXElectrode does not go out within this range Peak.
Such as x-ray photoelectron power spectrum (XPS) display of Fig. 4 a and Fig. 4 b, WO is indicated3Area load molecular level Ir–PO3H2Catalyst.
3. the photoelectrochemical behaviour test of complex light anode
3.1 photoelectric currents-potentiometric test
As shown in figure 5 a and 5b, the present invention uses the mode of loading of knife coating, with sensitising agent WO3It is substrate, Ir-PO3H2 Or IrOx is catalyst, under acid pH=1.0 and neutral pH=7.0 environment, has investigated system in visible ray (λ>400nm) drive Under dynamic, the performance of water oxygen galvanic current potential change.
Such as Fig. 5 a, with pH=1.0,0.1M KNO3Solution as electrolyte solution, when to FTO/WO3/Ir–PO3H2It is compound When light anode carries out illumination, the combination electrode shows good catalysis activity.Such as when to WO3During electrode illumination, additional During voltage 1.5V vs Ag/AgCl, there is no water oxidation reaction yet, and work as and be adsorbed with catalyst IrOx or Ir-PO3H2Three During tungsten oxide light anode, there is water oxygen, the combination electrode under specific voltage is compared in 1.3V vs Ag/AgCl or so During density of photocurrent, catalyst Ir-PO are adsorbed with3H2Tungstic acid light anode show more preferable catalytic performance, such as exist During 1.23V vs RHE, FTO/WO3The density of photocurrent of electrode is 0.90mA/cm2, FTO/WO3The photoelectric current of/IrOx electrodes is close It is 0.88mA/cm to spend2, and FTO/WO3/Ir–PO3H2Density of photocurrent be 1.75mA/cm2, it is approximately FTO/WO32 times of electrode.
Such as Fig. 5 b, with pH=7.0,0.1M phosphate buffer solutions are used as electrolyte solution, complex light anode FTO/WO3/Ir– PO3H2Excellent performance is also show 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 electrodes and FTO/WO3/Ir–PO3H2The water oxygen of complex light anode Current potential compares FTO/WO3Light anode low respectively 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 is close It is 0.30mA/cm to spend2, and FTO/WO3/Ir–PO3H2Density of photocurrent be 0.41mA/cm2, it is FTO/WO32 times of electrode.
Result above illustrates to be adsorbed with catalyst Ir-PO3H2Tungstic acid light anode there is good catalytic water to aoxidize Activity, has relatively low water oxygen overpotential and relatively low transition state energy barrier mainly due to it.
3.2 stability tests
Photoelectric current-potential test result according to more than, such as Fig. 6 a and Fig. 6 b have been investigated in certain bias (1.23V again 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 carries out i-t tests, then with the same terms under FTO/WO3Electrode, FTO/WO3/ IrOx electricity The photoelectric current of pole is contrasted.
Such as Fig. 6 a, with pH=1.0,0.1M KNO3Solution is carried out as electrolyte solution under 1.23V vs RHE biass Long-time illumination, for FTO/WO3For light anode, density of photocurrent is by 0.65mA/cm2It is rapid to reduce, then with 0.22mA/ cm2The current density of left and right keeps stabilization, and for FTO/WO3/Ir-PO3H2Combination electrode, what density of photocurrent can be stablized It is maintained at 0.60mA/cm2Left and right, is probably the table of the bubble coalescence in electrode of generation the reason for wherein photoelectric current is slightly reduced Face, blocks the contact of hydrone and electrode activity site.Meanwhile, and under the same conditions, to electro deposition oxidation iridium catalyst Optoelectronic pole (FTO/WO3/ IrOx) carry out the stability test of density of photocurrent, the density of photocurrent of its modified electrode with do not have The tungstic acid electrode of any catalyst is loaded compared to without raising.Thus explanation is adsorbed with catalyst Ir-PO3H2Three oxidations Tungsten electrode has good stability under light illumination.
Such as Fig. 6 b, with pH=7.0,0.1M phosphate buffer solutions electrolyte solution as a comparison, 1.2V vs Ag/AgCl are inclined When pressure carries out long-time illumination, combination electrode FTO/WO3And FTO/WO3/ IrOx current densities are 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 stabilization.In general, Because the interaction force of chemical bond between organometallic complex and tungstic acid is weaker, under neutral environment during illumination, match somebody with somebody Easily there is the phenomenon of De contamination in compound, so the life-span of optical drive water oxidation system is typically shorter.
The electrochemical impedance spectroscopy (EIS) of 3.3 complex light anodes is characterized
Test result shows that larger tungstic acid population can represent more boundary defects and bigger resistance proves electricity The transmission of lotus.The result for observing EIS shows that each electrode is presented semicircle, such that it is able to the quasi equivalent circuit model of mould, such as schemes 7.In this model, element RΩThe resistance related to electric charge transmission is represented, including the resistance of semiconductor catalyst, FTO The wire of substrate, electrolyte and the whole circuit of connection.Element RctAnd CctRepresent in the relevant electric charge of optoelectronic pole/electrolyte interface Transfer, it is more preferable (charge transport ability, faster surface reaction power i.e. higher that a less semicircle of radius is represented Learn).FTO/WO3/Ir-PO3H2Electrode has smaller radius than simple tungstic acid electrode, i.e., with more preferable photocatalysis Activity, but FTO/WO3/ IrOx light anodes are larger due to the aggtegation of IrOx, radius, and charge transport ability is weaker.This table The individual layer Ir-PO of bright load3H2Molecular catalyst has high degree of dispersion state, significantly improves the reaction power of its electrode surface Learn, this is significantly to building photoelectrochemical cell.
4. the kinetic test of complex light anode
The instantaneous density of photocurrent test of 4.1 complex light anodes
Such as Fig. 8 a and Fig. 8 b, under visible light illumination, occur in FTO/WO3/Ir-PO3H2Water oxygen in complex light anode Reaction mechanism (or rate determining step) is to be totally different from FTO/WO3/ IrOx light anodes.The kinetic isotope effect of H/D (KIE) measurement is a strong evidence, by comparing in H2O and D2O current densities prove rate determining step.Speed control The proton translocation and proton couple electronic transfer (PCET) that step (RDS) processed is related in chemical reaction can be in the power of H/D Learn during isotope effect (KIE) is measured and emerge from.The oxidation reaction of water is related to the transmission of four protons and four electronics, so that Realize that the decomposition of water produces oxygen, the technology can be used to analyze and be rate limit the step for understanding.
As Fig. 8 a show, FTO/WO3/ IrOx light anodes are in D2Current density (the J ≈ 0.11mA cm of O-2) it is H2The one of O Half, the IrOx with document report is consistent, shows that water oxygen is rate determining step.This means FTO/WO3/ IrOx light anodes 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 identical.Change 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.Therefore, The turnover frequency of system is the speed control that catalyst is transferred to by hole.This shows that RDS is from WO3To catalyst charge , there is the speed of autoxidation rather than water in the speed of transfer.This phenomenon shows that it is rate-limiting step that hole is transferred to catalyst Suddenly, while also indicating that the speed that subsequent hole is transferred to water is very fast.
4.2 transient short circuit currents are tested
In order to prove the photoresponse effect of this structure change over time, in 1.23V vs RHE, using platinum filament as To electrode, FTO/WO3/ IrOx and FTO/WO3/Ir-PO3H2The complex light anode transient state short circuit produced 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 curves of electrode.Under illumination condition, The electronics of combination electrode is excited to electrode surface, produces 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, that is, produce negative electrode electricity Stream.Therefore, the Primary photocurrent in each cycle is equal to the value of starting point, rather than the terminal in last cycle.This be due to The accumulation of surface voids or in WO3Some charge accumulations that surface is formed, these phenomenons may all cause the photoelectric current to strengthen.Thus Draw, the speed of water decomposition is relatively slow, a part of electronics can not well participate in water decomposition, cause the part from IrOx Light induced electron is transported to rapidly WO3Surface, another part light induced electron is returned.
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 0.1M3Cushioning liquid is electrolyte, with Ag/AgCl (3.5M saturated potassium chloride solutions) as reference electrode, FTO/WO3/Ir– PO3H2It is working electrode, is to electrode with platinum guaze.When carrying out faradic efficiency test, on a closed three-electrode cell Install Ag/AgCl (3.5M saturated potassium chloride solutions) reference electrode, FTO/WO3/Ir–PO3H2Working electrode, platinum guaze is to electrode. After the completion of installing and being closed, with argon gas to test system bubbling deoxygenation.Using the bias of 1.23V vs RHE, after electrolysis starts, With the current density produced in light anode in electrochemical workstation detection electrolytic process, discharged with gas chromatographic detection every 1h The mole of the oxygen for coming, electrolysis time is 4h.The theoretical growing amount of oxygen in electrolytic trial, by the electricity flowed through in electrolytic process Amount, is calculated according to Faraday's law.Faradic efficiency=the O of final light anode2 (actual amounts)/O2 (theoretical amounts)。
Under the illumination condition of AM1.5, when applying bias are 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 Dramatically increase, in 2.5h, η (O2) ≈ 100%, after 4h is electrolysed, η (O2) ≈ 95%.For FTO/WO3Electrode, works as electrolysis After 4h, η (O2) ≈ 56%.FTO/WO3/Ir-PO3H2Combination electrode produces O under illumination condition2Theoretical value and actual 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 (9)

1. the WO that molecular level iridium catalyst is modified3Complex light anode, it is characterised in that preparation method comprises the following steps：
1)FTO/WO3The preparation of electrode：The WO that will be pre-processed3WO is prepared with distilled water3Suspension；By WO3Suspension uses blade coating Method or spin-coating method are supported on FTO electro-conductive glass, are dried naturally, dried in vacuum overnight, are made annealing treatment in Muffle furnace, obtain FTO/ WO3Electrode；
2) FTO/WO that will be prepared3Electrode be immersed in the methanol solution of molecular level iridium catalyst overnight, after taking-up spend from Sub- water is rinsed, and vacuum drying or nitrogen are dried up, and obtain the WO of molecular level iridium catalyst modification3Complex light anode, keeps in dark place.
2. the WO that molecular level iridium catalyst according to claim 1 is modified3Complex light anode, it is characterised in that step 1) In, described annealing is, in Muffle furnace, 500 DEG C is warming up to the speed of 5 DEG C/min, calcines 2-3h, is cooled down after taking-up To room temperature.
3. the WO that molecular level iridium catalyst according to claim 1 is modified3Complex light anode, it is characterised in that described Molecular level iridium catalyst is the molecule Ir-PO with four-coordination3H2, its chemical molecular formula is [(H4dphbpy)IrIII(Cp*) Cl]Cl；Wherein, Cp*=pentamethylcyclopentadienes.
4. the WO that molecular level iridium catalyst according to claim 3 is modified3Complex light anode, it is characterised in that described Molecular level iridium catalyst Ir-PO3H2Preparation method comprise the following steps：With 2,2 '-bipyridyl -4,4 '-bis phosphoric acid diethylester It is raw material, synthesis 4,4 '-diphosphonic acid -2,2 '-bipyridyl H4Dphbpy, further with [IrIII(Cp*)(Cl2)]2Dimer is anti- Should, the molecular level iridium catalyst Ir-PO of four-coordination of the synthesis with stability structure3H2。
5. the WO that molecular level iridium catalyst according to claim 4 is modified3Complex light anode, it is characterised in that described Molecular level iridium catalyst Ir-PO3H2Preparation method comprise the following steps：
1) 2,2 '-bipyridyl -4,4 is prepared '-bis phosphoric acid diethylester：Under nitrogen protection, 4,4 '-two bromo- 2 are taken, 2 '-bipyridyl, Pd(pph3)4, diethyl phosphite and Et3N, in organic solvent, at 80-90 DEG C, is heated to reflux 3-4h, is cooled to room temperature, To adding ether in reaction solution, vacuum filtration, filtrate concentrated by rotary evaporation puts plate, silica gel column chromatography, obtains 2,2 '-bipyridyl -4,4 ' - Bis phosphoric acid diethylester；
2) 4,4 '-diphosphonic acid -2,2 is prepared '-bipyridyl：NaOH is dissolved in methyl alcohol, 2,2 '-connection pyrrole is added slowly with stirring Pyridine -4,4 '-bis phosphoric acid diethylester, in heating stirring 6-7h at 45-55 DEG C, is concentrated by evaporation, and concentrate carries out being acidified to pH=2, Filtering, takes precipitation, is vacuum dried, and obtains 4,4 '-diphosphonic acid -2,2 '-bipyridyl；
3) molecular level iridium catalyst Ir-PO are prepared3H2：Under argon gas protection, by [IrIII(Cp*)(Cl2)]2Dimer is in dichloromethane Reflux temperature is heated in alkane, magnetic agitation 20-30 minutes, 4 is added, 4 '-diphosphonic acid -2, the dichloromethane of 2 '-bipyridyl is molten Liquid, magnetic agitation is simultaneously warming up to 40-50 DEG C, back flow reaction 10-11 hours, and reaction solution is cooled into room temperature, vacuum filter, and it is heavy to take Form sediment, obtain target product.
6. the WO that molecular level iridium catalyst according to claim 5 is modified3Complex light anode, it is characterised in that described Organic solvent is toluene.
7. the WO that molecular level iridium catalyst according to claim 5 is modified3Complex light anode, it is characterised in that by mole Than 4,4 '-diphosphonic acid -2,2 '-bipyridyl:[IrIII(Cp*)(Cl2)]2=2:1.
8. the WO that molecular level iridium catalyst according to claim 5 is modified3Complex light anode, it is characterised in that step 2) In, it is acidified with hydrochloric acid.
9. the WO that the molecular level iridium catalyst described in claim 1 is modified3Application of the complex light sun in electrolysis water oxygen.
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