CN107400899B - Tungstic acid complex light electrode and preparation method thereof and the application in photoelectrocatalysis decomposes water - Google Patents

Tungstic acid complex light electrode and preparation method thereof and the application in photoelectrocatalysis decomposes water Download PDF

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CN107400899B
CN107400899B CN201710681059.5A CN201710681059A CN107400899B CN 107400899 B CN107400899 B CN 107400899B CN 201710681059 A CN201710681059 A CN 201710681059A CN 107400899 B CN107400899 B CN 107400899B
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electrode
complex light
tungstic acid
tungstic
acid complex
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CN107400899A (en
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张晓凡
张炳雁
孔维倩
张守仁
杨保成
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Huanghe Science and Technology College
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    • 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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • 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
    • 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
    • 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
    • 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 invention discloses a kind of preparation method of tungstic acid complex light electrode, comprise the following steps：WO 3 film is first generated on electro-conductive glass, obtains substrate, then tungstic trioxide nano-slice optoelectronic pole is made through hydro-thermal, annealing in substrate；Then it is annealed to obtain reduced graphene modification tungsten trioxide photoelectrode using spin-coating method coating graphene oxide on tungstic trioxide nano-slice optoelectronic pole；Again in three-electrode system, tungsten trioxide photoelectrode is modified as working electrode using reduced graphene, using the aqueous solution containing ferric trichloride, nickel chloride, sodium fluoride, potassium chloride and hydrogen peroxide as electrolyte, circle is swept using cyclic voltammetry circulation, then take out working electrode, it is washed, dry, to obtain the final product.The present invention is added the electric conductivity of optoelectronic pole and the transfer efficiency of photo-generated carrier, promotes electrode interface oxygen evolution reaction, improved the efficiency that optoelectronic pole photoelectrocatalysis decomposes water using reduced graphene and the nickel doping co-modified tungsten trioxide photoelectrode of FeOOH.

Description

Tungstic acid complex light electrode and preparation method thereof and photoelectrocatalysis decompose water in Application
Technical field
The invention belongs to optoelectronic materials technology, and in particular to a kind of tungstic acid complex light electrode and its preparation side Method and the application in photoelectrocatalysis decomposes water.
Background technology
Solar energy is converted into Hydrogen Energy by water decomposition using semiconductor photoelectrocatalysielectrode technology, and with this chemical energy of hydrogen Form storage then utilize, be to solve one of current most promising mode of energy crisis.1972, Fujishima was first Report TiO2Optoelectronic pole can utilize decomposing water with solar energy [A.Fujishima, K.Honda, Nature, 1972,238 (5358): 37-38, the prelude of optical electro-chemistry decomposition water has been pulled open from this.1976, Honda was first by WO3It is used for photoelectricity as light anode Water [G.Hodes, D.Cahen, J.Manassen, Nature, 1976,260 is catalytically decomposed:312-313], so as to cause research The extensive concern of person.
Tungstic acid (WO3) it is a kind of N-shaped indirect band-gap semiconductor, energy gap is 2.5~2.8eV, theoretical absorption side Band is 430~500nm, has unique PhotoelectrochemicalProperties Properties.Because its energy gap is narrow, the valence band current potential ratio where hole Higher (+3.10~3.20V vs.NHE), is a kind of oxide semiconductor catalyst very with application prospect.In addition, it Also there is nontoxic, stability is strong in an acidic solution, nature rich in mineral resources, cost are low etc..Therefore, WO3Too The fields such as sun can be changed, photocatalytic degradation, electrochromism have obtained extensive research.But WO3It is easy there is also photo-generate electron-hole Compound, Electrochemical oxygen evolution reacts the deficiencies of slow, limits its application.The side of its photoelectric catalytically active of the raising of document report at present Method mainly includes constructing nanostructured, carbon material modification (carbon dots, graphene etc.), semiconductor coupling, doping and modification co-catalysis Agent etc., wherein co-catalyst main function are the overpotential for reducing reaction, promote the transfer of electronics, prevent electron-hole It is compound, so as to improve the photoelectrocatalysis efficiency of material.But for modifying WO3Co-catalyst species it is limited, mainly including Co- Pi, FeOOH and NiFe LDH etc..Research shows that in alkaline environment Ni adulterates FeOOH (Ni:FeOOH) separated out in electrocatalytic oxidation Present in terms of reaction than NiOOH and FeOOH highers catalytic activity [Y.Liang, Y.Yu, Y.Huang, et al., J.Mater.Chem.A,2017,5,13336-13340].Recently, Zheng Xiao beautiful jades seminar utilizes Hydrothermal Synthesiss Ni:FeOOH [L.Cai, J.Zhao, H.Li, et al., ACS Energy Lett., 2016,1,624-632], and it is applied to modification WO3/BiVO4Optoelectronic pole, effectively increases its photoelectric catalytically active, demonstrates Ni:FeOOH promotes photoelectrocatalysis to decompose water reaction Feasibility.Therefore, Ni is constructed:FeOOH modifies WO3Complex light electrode is expected to the separation and transfer of increase photogenerated charge, and then Promote interface oxygen evolution reaction, finally improve photoelectric catalytically active.
Graphene has the big (2630m of specific surface area2g-1), charge carrier mobility height (200000cm2V-1s-1) and electricity Resistance rate low (10-6Ω cm) and the advantages such as chemical stability is good, it is used widely in the field such as electro-catalysis and photoelectrocatalysis.Research Show that, in electro-catalysis field, graphene can improve the electric conductivity and specific surface area of elctro-catalyst (co-catalyst), so as to improve Electro-catalysis OER and the HER activity of catalyst.In photoelectrocatalysis field, graphene modified semiconductor photoelectrode, not only facilitates and carries The electric conductivity of high material, and the absorption to light also contributes, and also has in terms of the photoelectric catalytically active of optoelectronic pole is improved extensively Research.But graphene is combined into co-modified semiconductor with co-catalyst at present with improve the research of its photoelectric catalytically active compared with Few, Jae Sung Lee seminars are reported after RGO is mixed with NiFe LDH modifies Fe again2O3Optoelectronic pole can effectively improve light After electro catalytic activity [D.Youn, Y.Park, J.Kim, et al., J.Power Sources, 2015,294,437-443].Most Closely, Wei Min seminars, which combine RGO/NiFe LDH, is used for TiO2Good effect has been arrived in the modification and acquirement of optoelectronic pole [F.Ning,M.Shao,S.Xu,et al.,Energy Environ.Sci.,2016,9,2633-2643].But by RGO with Ni:The co-modified WO of FeOOH3For photoelectrocatalysis decompose water research there is presently no report.
The content of the invention
Based on the deficiencies of the prior art, object of the present invention is to provide tungstic acid complex light electrode, reduction is passed through Graphene and the co-modified tungsten trioxide photoelectrode of ferronickel oxyhydroxide, to improve charge transfer effciency.
Present invention also offers the preparation method of tungstic acid complex light electrode, and tungstic acid complex light electrode is in light Application in electrocatalytic decomposition water.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of preparation method of tungstic acid complex light electrode, comprises the following steps：
(1) wolframic acid and polyvinyl alcohol are added in hydrogenperoxide steam generator, it is molten to obtain Seed Layer to homogeneous solution is formed for stirring Liquid；By Seed Layer solution using spin-coating method coated on electro-conductive glass, then 450 will be warming up to by the electro-conductive glass of coating~ 550 DEG C, insulation 1.5~3 it is small when after, be cooled to room temperature, obtain substrate；Wherein, the addition of wolframic acid is in hydrogenperoxide steam generator 70~80g/L, the addition of polyvinyl alcohol are 20~40g/L；
(2) hydrogenperoxide steam generator of wolframic acid, oxalic acid, urea, hydrochloric acid are added in acetonitrile, stirring to formation homogeneous solution, Obtain hydro-thermal reaction liquid；Substrate obtained by step (1) is placed in hydro-thermal reaction liquid, it is small in 160~200 DEG C of hydro-thermal reactions 1~6 When, taken out after being cooled to room temperature, it is washed, dry, then at 450~550 DEG C of insulations 1.5~3 it is small when after, be cooled to room temperature, obtain To tungstic trioxide nano-slice optoelectronic pole；Wherein, the molar ratio of wolframic acid, oxalic acid, urea, hydrochloric acid and acetonitrile is (6~9): (10~ 20): (15~25): (100~200): (1 × 104~1.5 × 104)；
(3) aqueous solution of graphene oxide is coated on tungstic trioxide nano-slice photoelectricity obtained by step (2) using spin-coating method On extremely, graphene oxide modification tungsten trioxide photoelectrode is obtained；Under argon gas or nitrogen atmosphere, graphene oxide is modified into three oxygen Change tungsten optoelectronic pole and be warming up to 450~550 DEG C, keep 1.5~3 it is small when after, be cooled to room temperature, obtain reduced graphene and modify three oxygen Change tungsten optoelectronic pole；
(4) tungsten trioxide photoelectrode is modified as working electrode using reduced graphene obtained by step (3), platinized platinum for electrode, Saturated calomel electrode forms three-electrode system for reference electrode, to be fluorinated containing ferric trichloride, nickel chloride, 4.5~5.5mmol/L The aqueous solution of sodium, 0.08~0.12mol/L potassium chloride and 0.98~1.02mol/L hydrogen peroxide is electrolyte, is lied prostrate using circulation The potential region of An Facong -0.5 ± 0.05V to 0.5 ± 0.05V vs.SCE carries out circulation and sweeps circle, then takes out working electrode, It is washed, dry, to obtain the final product；Wherein, the molar concentration of ferric trichloride is 1.0~7.0mmol/L in electrolyte, mole of nickel chloride Concentration is the 20%~80% of ferric trichloride molar concentration.
Preferably, spin-coating method described in step (1) is specially on electro-conductive glass by Seed Layer solution drop coating, and rotating speed is 2500~3500 revs/min, maintain 20~40 seconds, as a spin coating cycle, spin coating periodicity totally 5~20 times, each spin coating The drop coating amount of seed liquor is 80~120 μ L/cm in cycle2。
Preferably, the concentration of hydrogenperoxide steam generator described in step (1) is 25~30wt%.
Preferably, described in step (2) in the hydrogenperoxide steam generator of wolframic acid wolframic acid concentration for 0.04~0.06mol/L, The concentration of hydrogen peroxide is 1.4~2mol/L.
Preferably, spin-coating method described in step (3) is specially and receives the water-soluble drop-coated of graphene oxide in tungstic acid On rice piece optoelectronic pole, rotating speed is 2500~4000 revs/min, is maintained 20~40 seconds, as a spin coating cycle, spin coating periodicity Totally 5~20 times, the coated weight of each spin coating cycle internal oxidition graphene is 0.02~0.05mg/cm2。
Preferably, the concentration of graphene oxide is 0.2~0.5g/ in the aqueous solution of graphene oxide described in step (3) L。
Preferably, it is to sweep 1~30 circle with the speed circulation of sweeping of 180~220mV/s that circle is swept in circulation described in step (4).
Preferably, electro-conductive glass described in step (1) is fluorine-doped tin oxide electro-conductive glass.
The tungstic acid complex light electrode being prepared using the above method.
Application of the above-mentioned tungstic acid complex light electrode in photoelectrocatalysis decomposes water.
The electro-conductive glass and graphene oxide are ordinary commercial products.
The present invention is by tungstic acid hydrothermal growth to conductive glass surface, then by reduced graphene and the oxidation of ferronickel hydroxyl Thing is attached to semiconductor material surface, forms uniform co-catalysis layer；Repaiied altogether using reduced graphene and ferronickel oxyhydroxide Tungsten trioxide photoelectrode is adornd, under the synergistic effect of reduced graphene and nickel doping FeOOH, improves leading for optoelectronic pole Electrical and photo-generated carrier transfer efficiency, promotes electrode interface oxygen evolution reaction, final to improve optoelectronic pole photoelectrocatalysis point The efficiency of Xie Shui, this method, which is also applied for modifying other semiconductors, is applied to photoelectrocatalysis, optical electro-chemistry sensor and electro-catalysis Deng field.
Brief description of the drawings
Fig. 1 is the WO of the gained of embodiment 13Optoelectronic pole, WO3/ RGO optoelectronic poles, WO3/RGO/Ni:FeOOH optoelectronic poles and right 1 gained WO of ratio3/Ni:The SEM figures of FeOOH；
Fig. 2 is 1 gained WO of embodiment3And WO3/RGO/Ni:The 1 gained WO of the full spectrograms (a) of XPS and embodiment of FeOOH3/ RGO/Ni:The C1s high-resolution XPS figures (b) of FeOOH；
Fig. 3 is the WO of the gained of embodiment 13Optoelectronic pole, WO3/ RGO optoelectronic poles, WO3/RGO/Ni:FeOOH optoelectronic poles and contrast 1 gained WO of example3/Ni:The linear sweep voltammetry curve of FeOOH optoelectronic poles；
Fig. 4 is the WO of the gained of embodiment 13Optoelectronic pole, WO3/ RGO optoelectronic poles, WO3/RGO/Ni:FeOOH optoelectronic poles and contrast 1 gained WO of example3/Ni:The electrochemical impedance spectroscopy of FeOOH optoelectronic poles；
Fig. 5 is the WO of the gained of embodiment 13Optoelectronic pole, WO3/ RGO optoelectronic poles, WO3/RGO/Ni:FeOOH optoelectronic poles and contrast 1 gained WO of example3/Ni:The fluorescence spectrum of FeOOH optoelectronic poles.
Embodiment
In order to make the technical purpose of the present invention, technical solution and beneficial effect clearer, with reference to specific embodiment Technical scheme is further illustrated, but the embodiment is intended to explain the present invention, and it is not intended that right The limitation of the present invention, in the examples where no specific technique or condition is specified, according to the described technology of document in the art or Condition is carried out according to product description.
There is fluorine-doped tin oxide electro-conductive glass (FTO electro-conductive glass) purchased from Wuhan lattice solar energy science and technology in following embodiments Limit company, thickness 2.2mm, resistance are 14 Ω, light transmittance 90%.The graphene oxide (GO) is purchased from Suzhou perseverance ball The single-layer graphene oxide of science and technology.The temperature control heating platform is using German import PZ28-3TD titanium-bases thermal station and PR 5-3T journeys Sequence controller.
Embodiment 1
A kind of preparation method of tungstic acid complex light electrode, comprises the following steps：
(1) 0.625g wolframic acids and 0.25g polyvinyl alcohol are added in 8.5mL hydrogenperoxide steam generators, is stirred overnight, makes its shape Into homogeneous solution, Seed Layer solution is obtained；FTO electro-conductive glass is passed through into acetone, absolute ethyl alcohol and each ultrasound of deionized water successively After 15 minutes, dried up with nitrogen；Then FTO electro-conductive glass is placed in the rotating disk of spin coating instrument, 150 is pipetted with liquid-transfering gun For μ L Seed Layer solution drop coatings on electro-conductive glass, coated area is fixed as 1.5cm2, rotating speed is 3000 revs/min, is maintained 30 seconds, with This is a spin coating cycle, spin coating periodicity totally 5 times, and colorless film is coated with FTO electro-conductive glass；Again by by coating FTO electro-conductive glass is placed on temperature control titanium-base warm table, and 500 DEG C, when holding 2 is small are warming up to 5 DEG C/min of heating rate Afterwards, it is cooled to room temperature, obtains substrate；Wherein, the concentration of hydrogenperoxide steam generator is 30wt%；
(2) it is 6mol/L salt by the hydrogenperoxide steam generator of 1.5mL wolframic acids, 0.01g oxalic acid, 0.01g urea, 0.25mL concentration Acid is added in 6.25mL acetonitriles, is stirred 20 minutes, is completely dissolved solid and forms homogeneous solution, obtain hydro-thermal reaction liquid；Will Hydro-thermal reaction liquid is transferred in reaction kettle liner, and substrate obtained by step (1) is inserted into hydro-thermal reaction liquid, in 180 DEG C of hydro-thermals React 2 it is small when, taken out after being cooled to room temperature, dry up, then be placed on temperature control titanium-base warm table through milli-Q water, nitrogen, Be warming up to 500 DEG C with 5 DEG C/min of heating rate, keep 2 it is small when after, be cooled to room temperature, obtain tungstic trioxide nano-slice photoelectricity Pole (WO3Optoelectronic pole)；Wherein, in the hydrogenperoxide steam generator of wolframic acid the concentration of wolframic acid be 0.05mol/L, the concentration of hydrogen peroxide be 1.7mol/L；
(3) by above-mentioned gained WO3Nanometer sheet film is placed in the rotating disk of spin coating instrument, and 100 μ L oxygen are pipetted with liquid-transfering gun The aqueous solution (0.2mg/mL) of graphite alkene is added dropwise in WO3Optoelectronic pole, coated area are fixed as 1cm2, rotating 3000 Rev/min, maintain 30 seconds, as a spin coating cycle, repetition spin coating cycle 10 times, obtains three oxidation of graphene oxide modification Tungsten optoelectronic pole (WO3/ GO optoelectronic poles)；By WO3/ GO optoelectronic poles are placed in tube furnace, under an argon atmosphere, are warming up to 500 DEG C, are protected Hold 2 it is small when after, be cooled to room temperature, obtain reduced graphene modification tungsten trioxide photoelectrode (WO3/ RGO optoelectronic poles)；
(4) with WO obtained by step (3)3/ RGO photoelectricity extremely working electrode, platinized platinum are to electrode, saturated calomel electrode (SCE, sat.KCl) for reference electrode form three-electrode system, with containing 5mmol/L ferric trichlorides, 3mmol/L nickel chlorides, The aqueous solution of 5mmol/L sodium fluorides, 0.1mol/L potassium chloride and 1mol/L hydrogen peroxide is electrolyte, using cyclic voltammetry The potential region of (vs.SCE) from -0.5V to 0.45V, sweeps 10 circles with the speed circulation of sweeping of 200mV/s, then takes out working electrode, Clean through ultra-pure water, and dried up with nitrogen, up to tungstic acid complex light electrode (WO3/RGO/Ni:FeOOH optoelectronic poles).
Embodiment 2
A kind of preparation method of tungstic acid complex light electrode, comprises the following steps：
(1) 0.595g wolframic acids and 0.17g polyvinyl alcohol are added in 8.5mL hydrogenperoxide steam generators, is stirred overnight, makes its shape Into homogeneous solution, Seed Layer solution is obtained；FTO electro-conductive glass is passed through into acetone, absolute ethyl alcohol and each ultrasound of deionized water successively After 15 minutes, dried up with nitrogen；Then FTO electro-conductive glass is placed in the rotating disk of spin coating instrument, 120 is pipetted with liquid-transfering gun For μ L Seed Layer solution drop coatings on electro-conductive glass, coated area is fixed as 1.5cm2, rotating speed is 3500 revs/min, is maintained 20 seconds, with This is a spin coating cycle, spin coating periodicity totally 20 times, and colorless film is coated with FTO electro-conductive glass；Coating will be passed through again FTO electro-conductive glass be placed on temperature control titanium-base warm table, be warming up to 450 DEG C with 5 DEG C/min of heating rate, keep 3 small Shi Hou, is cooled to room temperature, and obtains substrate；Wherein, the concentration of hydrogenperoxide steam generator is 25wt%；
(2) it is 6mol/L by the hydrogenperoxide steam generator of 1.5mL wolframic acids, 0.009g oxalic acid, 0.009g urea, 0.2mL concentration Hydrochloric acid is added in 6.25mL acetonitriles, is stirred 20 minutes, is completely dissolved solid and forms homogeneous solution, obtain hydro-thermal reaction liquid； Hydro-thermal reaction liquid is transferred in reaction kettle liner, and substrate obtained by step (1) is inserted into hydro-thermal reaction liquid, in 160 DEG C of water When thermal response 6 is small, taken out after being cooled to room temperature, dry up through milli-Q water, nitrogen, then be placed on temperature control titanium-base warm table On, be warming up to 450 DEG C with 5 DEG C/min of heating rate, keep 3 it is small when after, be cooled to room temperature, obtain tungstic trioxide nano-slice Optoelectronic pole (WO3Optoelectronic pole)；Wherein, in the hydrogenperoxide steam generator of wolframic acid wolframic acid concentration for 0.04mol/L, hydrogen peroxide it is dense Spend for 1.4mol/L；
(3) by above-mentioned gained WO3Nanometer sheet film is placed in the rotating disk of spin coating instrument, and 100 μ L oxygen are pipetted with liquid-transfering gun The aqueous solution (0.3mg/mL) of graphite alkene is added dropwise in WO3Optoelectronic pole, coated area are fixed as 1cm2, rotating 4000 Rev/min, maintain 20 seconds, as a spin coating cycle, repetition spin coating cycle 20 times, obtains three oxidation of graphene oxide modification Tungsten optoelectronic pole (WO3/ GO optoelectronic poles)；By WO3/ GO optoelectronic poles are placed in tube furnace, under an argon atmosphere, are warming up to 450 DEG C, are protected Hold 1.5 it is small when after, be cooled to room temperature, obtain reduced graphene modification tungsten trioxide photoelectrode (WO3/ RGO optoelectronic poles)；
(4) with WO obtained by step (3)3/ RGO photoelectricity extremely working electrode, platinized platinum are to electrode, saturated calomel electrode (SCE, sat.KCl) for reference electrode form three-electrode system, with containing 1mmol/L ferric trichlorides, 0.8mmol/L nickel chlorides, The aqueous solution of 5mmol/L sodium fluorides, 0.1mol/L potassium chloride and 1mol/L hydrogen peroxide is electrolyte, using cyclic voltammetry The potential region of (vs.SCE) from -0.5V to 0.5V, sweeps 30 circles with the speed circulation of sweeping of 180mV/s, then takes out working electrode, pass through Ultra-pure water cleans, and is dried up with nitrogen, up to tungstic acid complex light electrode (WO3/RGO/Ni:FeOOH optoelectronic poles).
Embodiment 3
A kind of preparation method of tungstic acid complex light electrode, comprises the following steps：
(1) 0.68g wolframic acids and 0.34g polyvinyl alcohol are added in 8.5mL hydrogenperoxide steam generators, is stirred overnight, makes its shape Into homogeneous solution, Seed Layer solution is obtained；FTO electro-conductive glass is passed through into acetone, absolute ethyl alcohol and each ultrasound of deionized water successively After 15 minutes, dried up with nitrogen；Then FTO electro-conductive glass is placed in the rotating disk of spin coating instrument, 180 is pipetted with liquid-transfering gun For μ L Seed Layer solution drop coatings on electro-conductive glass, coated area is fixed as 1.5cm2, rotating speed is 2500 revs/min, is maintained 40 seconds, with This is a spin coating cycle, spin coating periodicity totally 10 times, and colorless film is coated with FTO electro-conductive glass；Coating will be passed through again FTO electro-conductive glass be placed on temperature control titanium-base warm table, be warming up to 550 DEG C with 5 DEG C/min of heating rate, keep 1.5 After hour, it is cooled to room temperature, obtains substrate；Wherein, the concentration of hydrogenperoxide steam generator is 28wt%；
(2) it is 6mol/L by the hydrogenperoxide steam generator of 1.5mL wolframic acids, 0.018g oxalic acid, 0.015g urea, 0.3mL concentration Hydrochloric acid is added in 6.25mL acetonitriles, is stirred 20 minutes, is completely dissolved solid and forms homogeneous solution, obtain hydro-thermal reaction liquid； Hydro-thermal reaction liquid is transferred in reaction kettle liner, and substrate obtained by step (1) is inserted into hydro-thermal reaction liquid, in 200 DEG C of water When thermal response 1 is small, taken out after being cooled to room temperature, dry up through milli-Q water, nitrogen, then be placed on temperature control titanium-base warm table On, be warming up to 550 DEG C with 5 DEG C/min of heating rate, keep 1.5 it is small when after, be cooled to room temperature, obtain tungsten trioxide nano Piece optoelectronic pole (WO3Optoelectronic pole)；Wherein, in the hydrogenperoxide steam generator of wolframic acid the concentration of wolframic acid be 0.06mol/L, hydrogen peroxide Concentration is 2mol/L；
(3) by above-mentioned gained WO3Nanometer sheet film is placed in the rotating disk of spin coating instrument, and 100 μ L oxygen are pipetted with liquid-transfering gun The aqueous solution (0.5mg/mL) of graphite alkene is added dropwise in WO3Optoelectronic pole, coated area are fixed as 1cm2, rotating 2500 Rev/min, maintain 40 seconds, as a spin coating cycle, repetition spin coating cycle 10 times, obtains three oxidation of graphene oxide modification Tungsten optoelectronic pole (WO3/ GO optoelectronic poles)；By WO3/ GO optoelectronic poles are placed in tube furnace, in a nitrogen atmosphere, are warming up to 550 DEG C, are protected Hold 3 it is small when after, be cooled to room temperature, obtain reduced graphene modification tungsten trioxide photoelectrode (WO3/ RGO optoelectronic poles)；
(4) with WO obtained by step (3)3/ RGO photoelectricity extremely working electrode, platinized platinum are to electrode, saturated calomel electrode (SCE, sat.KCl) for reference electrode form three-electrode system, with containing 7mmol/L ferric trichlorides, 1.4mmol/L nickel chlorides, The aqueous solution of 5mmol/L sodium fluorides, 0.1mol/L potassium chloride and 1mol/L hydrogen peroxide is electrolyte, using cyclic voltammetry The potential region of (vs.SCE) from -0.45V to 0.45V, sweeps 3 circles with the speed circulation of sweeping of 220mV/s, then takes out working electrode, Clean through ultra-pure water, and dried up with nitrogen, up to tungstic acid complex light electrode (WO3/RGO/Ni:FeOOH optoelectronic poles).Contrast Example 1
A kind of preparation method of tungstic acid complex light electrode, comprises the following steps：
(1) 0.625g wolframic acids and 0.25g polyvinyl alcohol are added in 8.5mL hydrogenperoxide steam generators, is stirred overnight, makes its shape Into homogeneous solution, Seed Layer solution is obtained；FTO electro-conductive glass is passed through into acetone, absolute ethyl alcohol and each ultrasound of deionized water successively After 15 minutes, dried up with nitrogen；Then FTO electro-conductive glass is placed in the rotating disk of spin coating instrument, 150 is pipetted with liquid-transfering gun For μ L Seed Layer solution drop coatings on electro-conductive glass, coated area is fixed as 1.5cm2, rotating speed is 3000 revs/min, is maintained 30 seconds, with This is a spin coating cycle, spin coating periodicity totally 5 times, and colorless film is coated with FTO electro-conductive glass；Again by by coating FTO electro-conductive glass is placed on temperature control titanium-base warm table, and 500 DEG C, when holding 2 is small are warming up to 5 DEG C/min of heating rate Afterwards, it is cooled to room temperature, obtains substrate；
(2) it is 6mol/L salt by the hydrogenperoxide steam generator of 1.5mL wolframic acids, 0.01g oxalic acid, 0.01g urea, 0.25mL concentration Acid is added in 6.25mL acetonitriles, is stirred 20 minutes, is completely dissolved solid and forms homogeneous solution, obtain hydro-thermal reaction liquid；Will Hydro-thermal reaction liquid is transferred in reaction kettle liner, and substrate obtained by step (1) is inserted into hydro-thermal reaction liquid, in 180 DEG C of hydro-thermals React 2 it is small when, taken out after being cooled to room temperature, dry up, then be placed on temperature control titanium-base warm table through milli-Q water, nitrogen, Be warming up to 500 DEG C with 5 DEG C/min of heating rate, keep 2 it is small when after, be cooled to room temperature, obtain tungstic trioxide nano-slice photoelectricity Pole (WO3Optoelectronic pole)；
(3) with WO obtained by step (2)3Photoelectricity extremely working electrode, platinized platinum be to electrode, saturated calomel electrode (SCE, Sat.KCl three-electrode system) is formed for reference electrode, to contain 5mmol/L ferric trichlorides, 3mmol/L nickel chlorides, 5mmol/L The aqueous solution of sodium fluoride, 0.1mol/L potassium chloride and 1mol/L hydrogen peroxide is electrolyte, using cyclic voltammetry from -0.5V to The potential region of 0.45V (vs.SCE), sweeps 10 circles with the speed circulation of sweeping of 200mV/s, then takes out working electrode, clear through ultra-pure water Wash, and dried up with nitrogen, up to tungstic acid complex light electrode (WO3/Ni:FeOOH optoelectronic poles).
Characterization and detection
To WO made from embodiment 13Optoelectronic pole, WO3/ RGO optoelectronic poles and WO3/RGO/Ni:FeOOH optoelectronic poles carry out SEM Characterization, as a result respectively as shown in Fig. 1 (a), (b), (c).From Fig. 1 (a), obtained after hydro-thermal reaction and annealing WO3For nanometer chip architecture, lamellar spacing about 18~35nm；From Fig. 1 (b), after overwinding Tu, annealing, RGO is covered in WO3The surface of nanometer sheet, is clear that RGO shows the irregular fold surface with layer structure in Fig. 1 (b)； By Fig. 1 (c) as it can be seen that and WO3Unlike/RGO electrodes, nano-particle, that is, Ni of many very littles after electrodeposition process:FeOOH It is covered in RGO and WO3In nanometer sheet.To WO made from comparative example 13/Ni:FeOOH optoelectronic poles carry out SEM characterizations, as a result such as Fig. 1 (d) shown in.From Fig. 1 (d), Ni after electro-deposition:FeOOH is not placed only in WO3Nanometer sheet top, in WO3The side of nanometer sheet It is also distributed, so as to be conducive to transfer and separation of the photohole at interface, is conducive to improve the photoelectric catalytically active of optoelectronic pole.
To 1 gained WO of embodiment3Optoelectronic pole and WO3/RGO/Ni:FeOOH optoelectronic poles carry out XPS characterizations, as a result such as Fig. 2 institutes Show.From Fig. 2 (a), with WO3Optoelectronic pole is compared, and is annealed by spin coating and is modified RGO and electrochemical deposition Ni:Occur after FeOOH Two new XPS peaks, and these peaks are respectively belonging to the XPS characteristic peaks of Ni (850-880eV) and Fe (710-730eV).The knot Fruit has obtained Ni after illustrating electrochemical deposition:FeOOH.Fig. 2 (b) is WO3/RGO/Ni:Carbon (C 1s) in FeOOH optoelectronic poles High-resolution XPS as a result, from Fig. 2 (b), three peaks in carbon XPS figures are respectively belonging to C-C, C-O and C (O)-O of RGO Peak, it is meant that RGO and Ni after modification:FeOOH is closely linked, and the result is consistent with the test result of SEM.
Optical electro-chemistry decomposes water Performance Test System and uses three-electrode system, respectively with photoelectricity to be measured extremely working electrode, Platinized platinum is that saturated calomel electrode is reference electrode, and electrolyte is 0.5mol/L aqueous sodium persulfate solutions to electrode.Electrochemical test Device is CHI 760E electrochemical workstations (Shanghai Chen Hua Instrument Ltd.), the use of light source is 500W xenon sources (CEL- S500, middle religion Jin Yuan), the spectrum of light source is passed through close to simulated solar irradiation spectrum, luminous power by applying AM 1.5G optical filters Power meter calibration is 100mW cm-2；Test method is linear scan cyclic voltammetry, and it is 10mV s to sweep speed-1.Photoelectrocatalysis The potential test scope that linear scanning curve (LSV) can be tested is 0.6V~1.6V vs.RHE, and it is 10mV s to sweep speed-1, electrolyte For 0.5mol/L aqueous sodium persulfate solutions, high-purity N must be passed through before test into electrolyte2Remove dissolved oxygen therein, duration of ventilation For 40min.EIS spectrums are used to study electric charge transfer of the optoelectronic pole material in photoelectrocatalysis reaction process, recombination process.
Fig. 3 is the WO of the gained of embodiment 13Optoelectronic pole, WO3/ RGO optoelectronic poles and WO3/RGO/Ni:FeOOH optoelectronic poles and right 1 gained WO of ratio3/Ni:The linear volt-ampere curve of FeOOH optoelectronic poles.With WO3Compare, under 1.23V vs.RHE and illumination condition (100mW cm-2, AM 1.5G), WO3/ RGO, WO3/Ni:FeOOH and WO3/RGO/Ni:The photoelectric current of FeOOH optoelectronic poles increases respectively 1.47,1.45 and 1.88 times are added.And the WO in 1.29V vs.RHE3/ RGO and WO3/Ni:The photoelectric current numerical value of FeOOH is identical, Unlike, with the increase of voltage, WO3/Ni:The photoelectric current of FeOOH basically reaches saturation (1.15mA cm-2), and WO3/ The photoelectric current of RGO optoelectronic poles is still being continuously increased, and is finally reached saturation, and numerical value is up to 1.41mA cm-2.With reference to WO3/RGO/ Ni:The photoelectric current of FeOOH optoelectronic poles is above WO3/ RGO and WO3/Ni:FeOOH, test result indicates that RGO and Ni:FeOOH exists It is synergistic effect in terms of improving photoelectric catalytically active.From the figure 3, it may be seen that the density of photocurrent in optoelectronic pole reaches 0.03mA cm-2 When, WO3The current potential of/RGO is substantially and WO3Unanimously, WO3/Ni:FeOOH and WO3/RGO/Ni:The current potential difference of FeOOH optoelectronic poles It is negative to have moved 30mV and 83mV.It is described on end, Ni:The main contributions of FeOOH are to reduce activation energy needed for its reaction, reduction photoelectricity The pacesetter potential of pole, and the main contributions of RGO are to improve saturation current, this may modify the light that can improve material with RGO Absorbent properties are related.
In order to deeper into the transfer process for understanding electric charge on semiconductor/electrolyte interface, test the gained of embodiment 1 WO3Optoelectronic pole, WO3/ RGO optoelectronic poles and WO3/RGO/Ni:1 gained WO of FeOOH optoelectronic poles and comparative example3/Ni:FeOOH optoelectronic poles Electrochemical impedance spectroscopy under illumination conditions, the results are shown in Figure 4.As shown in Figure 4, in 1.23V vs.RHE and illumination condition Under, WO3/RGO/Ni:The semicircle of FeOOH optoelectronic poles is minimum, illustrates its interfacial charge transfer resistance (R havingct) minimum, this meaning Taste separation and faster interfacial charge transfer process of the optoelectronic pole with more preferable photo-generated carrier.
In order to further illustrate RGO and Ni:The co-modified WO of FeOOH3Separation, transfer of photo-generated carrier etc. can be improved afterwards Process, further tests the WO of the gained of embodiment 13Optoelectronic pole, WO3/ RGO optoelectronic poles and WO3/RGO/Ni:FeOOH optoelectronic poles And 1 gained WO of comparative example3/Ni:The fluorescence spectrum of FeOOH optoelectronic poles, the results are shown in Figure 5.With WO3Compare, WO3/ RGO, WO3/ Ni:FeOOH and WO3/RGO/Ni:The fluorescence intensity of FeOOH has different degrees of decay, and WO3/RGO/Ni:FeOOH's is glimmering Light intensity decays are maximum, reflect RGO and Ni indirectly:The FeOOH co-modified service lifes that can extend photo-generated carrier.
After testing, the WO obtained by embodiment 23/RGO/Ni:The photoelectric current of FeOOH optoelectronic poles is higher than obtained by embodiment 2 WO3WO obtained by/RGO optoelectronic poles and comparative example 13/Ni:FeOOH, the WO obtained by embodiment 33/RGO/Ni:FeOOH light The photoelectric current of electrode is higher than the WO obtained by embodiment 33WO obtained by/RGO optoelectronic poles and comparative example 13/Ni:FeOOH。
It is described on end, RGO and Ni:FeOOH is co-modified can to effectively improve WO3The photoelectrocatalysis of optoelectronic pole decomposes water and lives Property.Wherein Ni:The main contributions of FeOOH be to reduce its reaction needed for activation energy, reduce the pacesetter potential of optoelectronic pole, and RGO Main contributions be improve saturation current, this may with RGO modify can improve material absorbing properties it is related.Simulating Sunlight irradiates (AM 1.5G, 100mW cm2) and 1.23V vs.RHE voltages under, with WO3Compare, WO3/RGO/Ni:FeOOH electricity The density of photocurrent of pole adds 1.88 times, and density of photocurrent reaches 0.03mA cm-2When, current potential, which is born, has moved 83mV.
Finally illustrate, in the present invention, preparing the parameter of electrode can adjust in respective range, it will be apparent that afflux Body, semi-conducting material, graphene and cocatalyst materials can make corresponding replacement or modified.Above example only to Illustrate technical scheme and unrestricted, although having been carried out by referring to the preferred embodiment of the present invention to the present invention Description, it should be appreciated by those of ordinary skill in the art that various change can be made to it in the form and details Become, the spirit and scope of the present invention limited without departing from the appended claims.

Claims (10)

1. a kind of preparation method of tungstic acid complex light electrode, it is characterised in that comprise the following steps：
(1) wolframic acid and polyvinyl alcohol are added in hydrogenperoxide steam generator, stirring obtains Seed Layer solution to homogeneous solution is formed； Seed Layer solution is coated on electro-conductive glass using spin-coating method, then 450~550 will be warming up to by the electro-conductive glass of coating DEG C, insulation 1.5~3 it is small when after, be cooled to room temperature, obtain substrate；Wherein, in hydrogenperoxide steam generator the addition of wolframic acid for 70~ 80g/L, the addition of polyvinyl alcohol are 20~40g/L；
(2) hydrogenperoxide steam generator of wolframic acid, oxalic acid, urea, hydrochloric acid are added in acetonitrile, stirring is obtained to homogeneous solution is formed Hydro-thermal reaction liquid；Substrate obtained by step (1) is placed in hydro-thermal reaction liquid, it is cold when 160~200 DEG C of hydro-thermal reactions 1~6 are small But it is washed, dry to taking out after room temperature, then at 450~550 DEG C of insulations 1.5~3 it is small when after, be cooled to room temperature, obtain three oxygen Change tungsten nanometer sheet optoelectronic pole；Wherein, the molar ratio of wolframic acid, oxalic acid, urea, hydrochloric acid and acetonitrile is (6~9):(10~20):(15 ~25):(100~200):(1×104~1.5 × 104)；
(3) aqueous solution of graphene oxide is coated on obtained by step (2) on tungstic trioxide nano-slice optoelectronic pole using spin-coating method, Obtain graphene oxide modification tungsten trioxide photoelectrode；Under argon gas or nitrogen atmosphere, graphene oxide is modified into tungstic acid Optoelectronic pole is warming up to 450~550 DEG C, keep 1.5~3 it is small when after, be cooled to room temperature, obtain reduced graphene modification tungstic acid Optoelectronic pole；
(4) tungsten trioxide photoelectrode is modified as working electrode using reduced graphene obtained by step (3), platinized platinum is to electrode, saturation Calomel electrode for reference electrode form three-electrode system, with containing ferric trichloride, nickel chloride, 4.5~5.5mmol/L sodium fluorides, The aqueous solution of 0.08~0.12mol/L potassium chloride and 0.98~1.02mol/L hydrogen peroxide is electrolyte, using cyclic voltammetry From -0.5 ± 0.05V to 0.5 ± 0.05V, the potential region of vs.SCE carries out circulation and sweeps circle, working electrode is then taken out, through washing Wash, is dry, to obtain the final product；Wherein, the molar concentration of ferric trichloride is 1.0~7.0mmol/L in electrolyte, the molar concentration of nickel chloride For the 20%~80% of ferric trichloride molar concentration.
2. the preparation method of tungstic acid complex light electrode according to claim 1, it is characterised in that：Described in step (1) Spin-coating method is specially that rotating speed is 2500~3500 revs/min, is maintained 20~40 seconds on electro-conductive glass by Seed Layer solution drop coating, As a spin coating cycle, spin coating periodicity totally 5~20 times, the drop coating amount of seed liquor is 80~120 μ in each spin coating cycle L/cm2。
3. the preparation method of tungstic acid complex light electrode according to claim 1, it is characterised in that：Described in step (1) The concentration of hydrogenperoxide steam generator is 25~30wt%.
4. the preparation method of tungstic acid complex light electrode according to claim 1, it is characterised in that：Described in step (2) In the hydrogenperoxide steam generator of wolframic acid the concentration of wolframic acid be 0.04~0.06mol/L, the concentration of hydrogen peroxide be 1.4~2mol/L.
5. the preparation method of tungstic acid complex light electrode according to claim 1, it is characterised in that：Described in step (3) Spin-coating method is specially that rotating speed is 2000~4000 on tungstic trioxide nano-slice optoelectronic pole by the water-soluble drop-coated of graphene oxide Rev/min, maintain 20~40 seconds, as a spin coating cycle, spin coating periodicity totally 5~20 times, each spin coating cycle internal oxidition The coated weight of graphene is 0.02~0.05mg/cm2。
6. the preparation method of tungstic acid complex light electrode according to claim 1, it is characterised in that：Described in step (3) The concentration of graphene oxide is 0.2~0.5g/L in the aqueous solution of graphene oxide.
7. the preparation method of tungstic acid complex light electrode according to claim 1, it is characterised in that：Described in step (4) It is to sweep 1~30 circle with the speed circulation of sweeping of 180~220mV/s that circle is swept in circulation.
8. the preparation method of tungstic acid complex light electrode according to claim 1, it is characterised in that：Described in step (1) Electro-conductive glass is fluorine-doped tin oxide electro-conductive glass.
9. the tungstic acid complex light electrode being prepared using any the method for claim 1~8.
10. application of the tungstic acid complex light electrode described in claim 9 in photoelectrocatalysis decomposes water.
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