CN106222685B - A kind of WO of photoelectrocatalysis water decomposition3The preparation method of-LDH laminated films - Google Patents
A kind of WO of photoelectrocatalysis water decomposition3The preparation method of-LDH laminated films Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 16
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 230000008021 deposition Effects 0.000 claims abstract description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- 206010013786 Dry skin Diseases 0.000 claims description 5
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- 238000004070 electrodeposition Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 230000005611 electricity Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000007539 photo-oxidation reaction Methods 0.000 abstract description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 abstract 1
- 238000004577 artificial photosynthesis Methods 0.000 abstract 1
- 238000004146 energy storage Methods 0.000 abstract 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002915 BiVO4 Inorganic materials 0.000 description 2
- -1 TaON Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910003071 TaON Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of WO of photoelectrocatalysis water decomposition3‑LDH（Layered double hydroxide, layered double-hydroxide）The preparation method of laminated film, comprises the steps of：Ammonium tungstate and concentrated hydrochloric acid is soluble in water, it is transferred to after stirring in autoclave liner, it is inserted into the electro-conductive glass FTO that will have been pre-processed, then solvent thermal reaction is carried out, cooled to room temperature, after electro-conductive glass washing, drying, in air atmosphere, 450 550 DEG C of heat treatment at least 1 h, obtain WO3Film；Again with WO3Film is working electrode, and the aqueous solution of nickel nitrate and ferric nitrate is electrolyte, in WO3Film surface galvanostatic deposition NiFe LDH, finally obtain WO3LDH laminated films；Product produced by the present invention is higher than electricity conversion, and photooxidation water take-off potential is low, has broad application prospects in fields such as photocatalytic degradation, photoelectrocatalysis water decomposition, artificial photosynthesis, light auxiliary energy storage batteries.
Description
Technical field
The present invention relates to field of inorganic nonmetallic material, especially a kind of WO of photoelectrocatalysis water decomposition3-LDH
（Layered double hydroxide）The preparation method of laminated film.
Background technology
Last century 70, increasing environmental pollution and energy shortage problem have allowed it was recognized that the two are latent
Global crisis.For the sustainable development of human society, the pollution-free technology of development environment close friend and alternative cleaning
The energy is extremely urgent.Among numerous environmentally protective and renewable energy source item, the semiconductor of natural daylight energy is utilized
Photocatalysis technology has become one of most promising technology.1972, Japanese scholars Fujishima and Honda were reported for the first time
In TiO2Research [the A. Fujishima and K. Honda. Photolysis- of electrode surface photoelectric decomposition water
decomposition of water at the surface of an irradiated semiconductor. Nature,
1972,238,37-38.], this event for being considered to have milestone significance has greatly been pushed and has been urged based on photocatalysis/photoelectricity
The research of the light energy switch technology of change technology.Unfortunately, the forbidden band of titanium dioxide is wider（3-3.2 eV）, what can be utilized arrives
Up to earth surface solar energy less than 5%（Ultraviolet light, λ<400 nm）, it is made to can't be ideal catalysis material.Currently,
Numerous studies are all concentrated in visible light wave range（400<λ<800 nm）It responds and the narrow band gap with highlight catalytic active is partly led
[A. B. Murphy, P. R. F. Barnes, L. K. Randeniya, I. C. Plumb, I. E. on body material
Grey, M. D. Horne and J. A. Glasscock. Efficiency of solar water splitting
using semiconductor electrodes. Int. J. Hydrogen Energy, 2006, 31, 1999-
2017.], such as WO3、Fe2O3、BiVO4Equal oxides, CdS, Cu2ZnSnS4Sulfides, the nitrogen oxides such as TaON, ZnGaON, with
And nonmetallic compound g-C3N4.
WO3It is a kind of N-shaped semiconductor material with wide forbidden band with good physical and chemical stability, by filling up the low of electronics
It can valence band（Valence band, VB）With empty higher energy conduction band（Conduction band, CB）It constitutes.With other photochemical catalysts
It compares, the energy gap of tungstic acid is relatively narrow, can have preferable absorption in visible-range, can be very good using in sunlight
Visible light resource.But if using only tungstic acid semiconductor, existed easily unstable by photoetch, photo-catalysis capability
The defects of, so this field expands a large amount of research around how improving tungstic acid photo-catalysis capability, it is proposed that many changes
Property means reduce its energy gap with this, enhance the ability of light absorption, while also to promote its light induced electron and hole
Separative efficiency reduces the combined efficiency of electronics and hole, promotes catalytic capability.Common method has WO3With other semiconductors
Material（TiO2、ZnO、BiVO4）Carry out compound, but these methods cannot all reduce WO3Photoelectricity aoxidizes the overpotential of water.
Layered double-hydroxide LDH（Layered double hydroxide）It is a kind of co-catalysis of moisture parsing oxygen
Agent can effectively reduce the overpotential of analysis oxygen, while can constitute hetero-junctions with other semi-conducting materials again to improve electronics
The separating capacity in hole.Currently, utilizing WO3Combine to form WO with layered double-hydroxide LDH3The skill of-LDH laminated films
Art, there is not been reported.
Invention content
In view of the above-mentioned problems, the present invention, which provides one kind, having efficient photoelectricity treater catalytic water capacity of decomposition WO3-LDH（Layered
double hydroxide）The preparation method of laminated film, what this method was realized in：
（1）It is the ammonium tungstate solution of 0.017 g/ml to take mass concentration, adjusts pH=1, is placed in 40 DEG C of environment and stirs to shape
At colourless transparent solution, it is then transferred in the polytetrafluoroethyllining lining of autoclave；
（2）By the FTO electro-conductive glass oblique cuttings pre-processed in inner liner of reaction kettle, solution did not had glass, and conduction is downwards；
（3）Reaction kettle is tamping to be put into baking oven and carries out solvent thermal reaction, is placed in 160 ~ 200 DEG C of environment and reacts at least
1h, cooled to room temperature；Taking-up FTO electro-conductive glass, 40 ~ 100 DEG C of dryings after being washed successively with deionized water, absolute ethyl alcohol,
Obtain nattierblue film；
（4）By electro-conductive glass under air atmosphere protection, it is placed in 450 ~ 550 DEG C of environment and is heat-treated at least 1h, grown
There is WO3FTO electro-conductive glass；
（5）Using three-electrode system, with WO3Film is working electrode, and the aqueous solution of nickel nitrate and ferric nitrate is electrolyte,
In WO3Film surface galvanostatic deposition NiFe-LDH is passed through -0.10 mA/cm of constant current2, 50 ~ 400 s of electro-deposition obtains
WO3- LDH laminated films.
Further, the WO of photoelectrocatalysis water decomposition of the present invention3In the preparation method of-LDH laminated films, pretreatment
Step is：Electro-conductive glass is cut into the small pieces of 3 cm x, 1.5 cm, uses acetone, deionized water, absolute ethyl alcohol ultrasound clear respectively
It washes（The power of ultrasonic cleaning is 100 W）30 min, and cleaned electro-conductive glass is placed in absolute ethyl alcohol and is preserved, before use
It is dried up with hair-dryer.
Further, the WO of photoelectrocatalysis water decomposition of the present invention3In the preparation method of-LDH laminated films, step
（5）The aqueous solution of the nickel nitrate and ferric nitrate obtains by the following method：By 2.181 g Ni (NO3)2·6H2O and
1.784 g Fe(NO3)3·9H2O is added in 100mL water, that is, obtains the solution.
Further, the WO of photoelectrocatalysis water decomposition of the present invention3In the preparation method of-LDH laminated films, step
（1）Adjusting pH=1 refers to adjusting pH=1 with the HCl solution of a concentration of 6 mol/L.
Further, the WO of photoelectrocatalysis water decomposition of the present invention3In the preparation method of-LDH laminated films, step
（5）The three-electrode system refers to, with WO3FTO electro-conductive glass be working electrode, Pt pieces be to electrode, saturation calomel
Electrode is that reference electrode is formed by system.
The present invention is by WO3Combine to form WO with layered double-hydroxide LDH3- LDH laminated films, light induced electron and sky
The separative efficiency in cave is high, and oxygen evolution potential is low, to make its catalytic capability be remarkably enhanced.The WO that the present invention obtains3-
The photooxidation water decomposition current density of LDH laminated films is much larger than pure WO3, and take-off potential is lower show preferable application before
Scape.
Description of the drawings
Fig. 1 is the WO prepared by the embodiment of the present invention 13The electron scanning micrograph of-LDH laminated films.
Fig. 2 is the WO prepared by the embodiment of the present invention 13The transmission electron microscope photo of-LDH laminated films.
Fig. 3 is the WO prepared by the embodiment of the present invention 13The distribution diagram of element of Film laminated film scanning Electronic Speculum.
Fig. 4 is the WO that the embodiment of the present invention 1 obtains3The WO that-LDH laminated films and embodiment 4 obtain3The XPS of film schemes
Spectrum.
Fig. 5 is the photocurrent curve figure of the embodiment of the present invention 1 and 4.
Fig. 6 is the WO that embodiment 4 obtains3Film scanning electromicroscopic photograph.
Specific implementation mode
Embodiment is related to reagent and equipment source：
Ammonium tungstate analyzes pure AR, is purchased from Sinopharm Chemical Reagent Co., Ltd.；
Acetone, absolute ethyl alcohol, hydrochloric acid, six water nickel nitrates, nine water ferric nitrates and anhydrous sodium sulfate are the pure AR of analysis, are purchased from
Nanjing Chemistry Reagent Co., Ltd.；
FTO electro-conductive glass：Pilkington products, thickness 2.2mm, 7 ohm of resistance, light transmittance 80%；
Autoclave：In triumphant Asia KH-50, enclosure material be 304 stainless steels, liner is polytetrafluoroethylene (PTFE)；
Electrochemical workstation：Shanghai Chen Hua Instrument Ltd., CHI660A；
Scanning electron microscope：Japanese Hitachi companies S-4800, accelerating potential 10kV；
Transmission electron microscope：FEI company's Ts ecnai G2, accelerating potential 200kV；
X-ray photoelectron spectroscopy（XPS）：5000 VersaProbe electron spectrometers of PHI.
Pretreated FTO electro-conductive glass described in embodiment is obtained by：FTO electro-conductive glass is cut out to 3 cm x
The small pieces of 1.5 cm use acetone, deionized water and absolute ethyl alcohol to be cleaned by ultrasonic FTO electro-conductive glass 30min respectively（It is cleaned by ultrasonic
Power is 100 W）, the FTO electro-conductive glass after cleaning is placed in absolute ethyl alcohol and is preserved, hair dryer is used before use（About 60 ~ 80
℃）Drying.
Embodiment 1
（1）The ammonium tungstate for weighing 0.5 g is dissolved in 30 ml water, pH value of solution=1 is adjusted with 6 mol/L HCl solutions, 40
Solution is transferred to the polytetrafluoroethyllining lining of 50 ml autoclaves by stirring later until forming colourless transparent solution at DEG C
In；
（2）By pretreated FTO electro-conductive glass piece oblique cutting inside inner liner of reaction kettle, make conductive face-down；
（3）Reaction kettle sealing is tightly put into baking oven and carries out solvent thermal reaction, 180 DEG C of 5 h of thermal response are naturally cooled to
Electro-conductive glass is washed by deionized water, absolute ethyl alcohol and after 40 DEG C dry, obtains nattierblue film by room temperature；
（4）By the electro-conductive glass with film under air atmosphere protection, 500 DEG C of 2 h of isothermal holding obtain yellow
WO3Film.
（5）It is specific as follows using three-electrode system：With WO3FTO electro-conductive glass be working electrode, Pt pieces be to electricity
Pole, saturated calomel electrode are reference electrode, and electrolyte contains 2.181 g Ni (NO3)2·6H2O and 1.784 g Fe (NO3)3·
9H2O and 100 mL water, in WO3Film surface is with -0.10 mA/cm2Current density galvanostatic deposition NiFe-LDH, electricity is heavy
The product time is that 200 s finally obtain WO3- LDH laminated films.
The WO that the present embodiment obtains3- LDH laminated film stereoscan photographs are shown in Fig. 1, it is seen that the WO of preparation3- LDH THIN COMPOSITEs
Film is by rodlike WO3Particle and sheet LDH compositions.
The laminated film transmission electron microscope is shown in Fig. 2, and as shown in Figure 2, the product of synthesis is to crystallize good WO3Be covered in table
The LDH materials in face form.
For the Elemental redistribution of the laminated film constituency scanning electron microscope as shown in figure 3, in Fig. 3, A is the shape for the embodiment 1 chosen
Looks figure, B-E are respectively the distribution map of region W, O, Ni, Fe element, it is seen that element W, O, Fe, Ni are evenly distributed in film
In.
Embodiment 2
（1）The ammonium tungstate for weighing 0.5 g is dissolved in 30 ml water, pH=1 of solution is adjusted with 6 mol/L HCl, at 40 DEG C
Lower stirring is transferred to until forming colourless transparent solution in the polytetrafluoroethyllining lining of 50 ml autoclaves later；
（2）By pretreated FTO electro-conductive glass piece oblique cutting inside inner liner of reaction kettle, make conductive face-down；
（3）Reaction kettle sealing is tightly put into baking oven and carries out solvent thermal reaction, 160 DEG C of 1 h of reaction naturally cool to room
Electro-conductive glass is obtained nattierblue film by temperature after deionized water, absolute ethyl alcohol washing and 60 DEG C of dryings successively；
（4）Under air atmosphere protection, 450 DEG C of heat treatments keep the temperature 1 h, obtain the electro-conductive glass with film of gained
The WO of yellow3Film.
（5）Using three-electrode system, with WO3FTO electro-conductive glass be working electrode, Pt pieces be to electrode, saturation it is sweet
Mercury electrode is reference electrode, and electrolyte contains 2.181 g Ni (NO3)2·6H2O and 1.784 g Fe (NO3)3·9H2O and 100
ML water, in WO3Film surface is with -0.10 mA/cm2Current density galvanostatic deposition NiFe-LDH, electrodeposition time be 50 s,
It is final to obtain WO3- LDH laminated films.
Embodiment 3
（1）The ammonium tungstate for weighing 0.5 g is dissolved in 30 ml water, and the pH to 1 of solution is adjusted with 6 mol/L HCl solutions,
Stirring is transferred to until forming colourless transparent solution in the polytetrafluoroethyllining lining of 50 ml autoclaves later at 40 DEG C；
（2）By pretreated FTO electro-conductive glass piece oblique cutting inside inner liner of reaction kettle, make conductive face-down；
（3）Reaction kettle sealing is tightly put into baking oven and carries out solvent thermal reaction, 200 DEG C of 7 h of reaction naturally cool to room
Temperature obtains nattierblue film by electro-conductive glass after deionized water, absolute ethyl alcohol washing and 100 DEG C of dryings；
（4）Under air atmosphere protection, 550 DEG C of heat treatments keep the temperature 2 h, obtain the electro-conductive glass with film of gained
The WO of yellow3Film.
（5）Using three-electrode system, with WO3FTO electro-conductive glass be working electrode, Pt pieces be to electrode, saturation it is sweet
Mercury electrode is reference electrode, and electrolyte contains 2.181 g Ni (NO3)2·6H2O and 1.784 g Fe (NO3)3·9H2O and 100
ML water, in WO3Film surface is with -0.10 mA/cm2Current density galvanostatic deposition NiFe-LDH, electrodeposition time 400
S finally obtains WO3- LDH laminated films.
Embodiment 4
（1）The ammonium tungstate for weighing 0.5 g is dissolved in 30 ml water, and the pH to 1 of solution is adjusted with 6 mol/L HCl solutions,
40 oCLower stirring is transferred to until forming colourless transparent solution in the polytetrafluoroethyllining lining of 50 ml autoclaves later；
（2）By pretreated electro-conductive glass（FTO）Piece oblique cutting makes conductive face-down inside inner liner of reaction kettle；
（3）Reaction kettle sealing is tightly put into baking oven and carries out solvent thermal reaction, 180 DEG C of 5 h of reaction naturally cool to room
Temperature obtains nattierblue film by electro-conductive glass after deionized water, absolute ethyl alcohol washing and 80 DEG C of dryings；
（4）For the electro-conductive glass with film of gained under air atmosphere protection, 500 DEG C of 2 h of isothermal holding obtain yellow
WO3Film.
The WO that the present embodiment is obtained3Film（The pure WO of LDH is not deposited3Film）As a comparison sample, scanning electron microscope is shone
Piece is as shown in fig. 6, the WO prepared as seen from Figure 63Film is by rodlike WO3Particle forms.
The WO that embodiment 1 obtains3The WO that-LDH laminated films and embodiment 4 obtain3The XPS collection of illustrative plates of film as shown in figure 4,
From fig. 4, it can be seen that 1 product WO of embodiment3Surface is NiFe-LDH, and the valence state composition of 4 product of embodiment is strictly WO3。
The photoelectric current of test product, test specific method are：Test equipment is CHI660A electrochemical workstations, three electrodes
Test system is using Pt pieces as to electrode, saturated calomel electrode（SCE）As reference electrode device, with WO3And WO3- LDH's
FTO glass is working electrode, and light passes through quartz glass electrolytic cell, and from the back sides FTO vertical irradiation, all test areas are fixed on
1cm2, the method for selecting linear scan, 0 ~ 1.5V of sweep interval（vs. SCE）.Electrolyte uses the Na of 0.2 mol/L2SO4It is molten
Liquid, pH value 6.6, logical nitrogen half an hour, dissolved oxygen is removed before testing.Light source uses the 200W xenon lamps of Newport companies,
Additional filter plate（λ>420 nm）.Fig. 5 is the photocurrent curve of embodiment 1 and 4, with pure WO3（Embodiment 4）It compares, WO3-LDH
Laminated film（Embodiment 1）Photooxidation water decomposition current density be much larger than the latter, and take-off potential it is lower show it is preferable
Application prospect.
It is described above to be only used as presently preferred embodiments of the present invention and application, the limitation of the present invention is should not be construed as, it is all
The invention for being modification, replacement and the change in the other forms made of technological thought based on the present invention and realizing belongs to this hair
Bright protection domain.Can several change can be cooked the present invention under the premise of not departing from the present invention for those skilled in the art
Into and modification, these improvement and modification are also considered as protection scope of the present invention.
Claims (4)
1. a kind of WO of photoelectrocatalysis water decomposition3The preparation method of-LDH laminated films, which is characterized in that be as follows：
（1）It is the ammonium tungstate solution of 0.017g/ml to take mass concentration, adjusts pH=1, is placed in stirring in 40 DEG C of temperature and extremely forms nothing
Color clear solution, is transferred in autoclave；
（2）In a kettle by pretreated FTO electro-conductive glass oblique cutting, it is immersed in step（1）In the solution of acquisition, conducting surface
Downwards；
（3）Reaction kettle is placed in 160 ~ 200 DEG C of environment and reacts at least 1h, is cooled to room temperature；FTO electro-conductive glass is taken out, successively
20 ~ 100 DEG C of dryings after being washed with deionized water, absolute ethyl alcohol；
（4）Electro-conductive glass is placed in 450-550 DEG C of temperature and is heat-treated at least 1h, is obtained with WO3The FTO electro-conductive glass of film；
（5）Using three-electrode system, with WO3The FTO electro-conductive glass of film is working electrode, the water of nickel nitrate and ferric nitrate
Solution is electrolyte, in WO3Film surface galvanostatic deposition NiFe-LDH is passed through -0.10 mA/cm of constant current2, electro-deposition 50-
400 s, that is, obtain WO3- LDH laminated films.
2. the WO of photoelectrocatalysis water decomposition according to claim 13The preparation method of-LDH laminated films, which is characterized in that
Step（2）Described in pretreated FTO electro-conductive glass be obtained by：Acetone, deionized water and absolute ethyl alcohol are used respectively
It is cleaned by ultrasonic FTO electro-conductive glass 30min, the FTO electro-conductive glass after cleaning is placed in absolute ethyl alcohol and is preserved, preceding drying is used.
3. the WO of photoelectrocatalysis water decomposition according to claim 23The preparation method of-LDH laminated films, which is characterized in that
Step（5）What the aqueous solution of the nickel nitrate and ferric nitrate was obtained by：By 2.181 g Ni (NO3)2·6H2O and 1.784
g Fe(NO3)3·9H2O is added in 100mL water, that is, obtains the solution.
4. the WO of photoelectrocatalysis water decomposition according to claim 33The preparation method of-LDH laminated films, which is characterized in that
Step（1）PH=1 that adjusts refers to adjusting pH value of solution=1 with the HCl of a concentration of 6 mol/L.
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| CN108355688B (en) * | 2018-01-17 | 2020-11-06 | 南京航空航天大学 | BiVO for photoelectrocatalysis water decomposition4/Ag3PO4Method for producing thin film |
| JP6989421B2 (en) * | 2018-03-13 | 2022-01-05 | 株式会社東芝 | Photocatalyst dispersion, photocatalyst composite material and photocatalyst device |
| CN108714424A (en) * | 2018-05-14 | 2018-10-30 | 中国地质大学（北京） | A kind of preparation method of the three compound crystalline phase WO 3 film of oblique-six sides of Fe2O3 doping |
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| CN112551484A (en) * | 2020-11-17 | 2021-03-26 | 沈阳工业大学 | Artificial photosynthesis processing method using super capacitor as register |
| CN112593248B (en) * | 2020-12-15 | 2021-09-03 | 苏州大学张家港工业技术研究院 | Ruthenium and iron co-doped tungsten oxide and preparation method and application thereof |
| KR102516637B1 (en) * | 2021-05-24 | 2023-04-03 | 울산과학기술원 | Organic photoanode and its manufacturing method |
| CN114236249A (en) * | 2021-12-16 | 2022-03-25 | 安徽大学 | Functional device with electric field induction and light field sensing functions and application |
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