CN105568314A - Preparation method of CuWO4/WO3 heterostructured nanosheet array film - Google Patents

Preparation method of CuWO4/WO3 heterostructured nanosheet array film Download PDF

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Publication number
CN105568314A
CN105568314A CN201510959603.9A CN201510959603A CN105568314A CN 105568314 A CN105568314 A CN 105568314A CN 201510959603 A CN201510959603 A CN 201510959603A CN 105568314 A CN105568314 A CN 105568314A
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chip arrays
water
cuwo4
cuwo
preparation
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徐芳
梅晶晶
陈会敏
白丹丹
蒋凯
武大鹏
高志勇
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Henan Normal University
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Henan Normal University
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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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/60—Constructional parts of cells
    • C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention discloses a preparation method of CuWO4/WO3 heterostructured nanosheet array film, comprising the specific steps: adding concentrated hydrochloric acid and hydrogen peroxide into water and ethanol solution of ammonium paratungstate hydrate, stirring and mixing well to obtain WO3 precursor solution; hydrothermally reacting to prepare WO3 nanosheet array; soaking the WO3 nanosheet array in ethanol solution of a bivalent copper salt, and annealing to obtain the CuWO4/WO3 heterostructured nanosheet array film. In the production obtained by the invention, WO3 nanosheets grow perpendicular to FTO (fluorine-doped tin oxide), CuWO4 nanoparticles are tightly connected to the surface of the WO3 nanosheets, a conductive position of CuWO4 has a more negative conductive position than WO3, light exposure of a film electrode facilitates the separation of photo-induced charge, a photo-anode for photo-electrochemical decomposition of water, and it is possible to improve water decomposition efficiency.

Description

A kind of CuWO 4/ WO 3the preparation method of heterogeneous structural nano chip arrays film
Technical field
The invention belongs to the synthesis technical field of inorganic nano photoelectric material, be specifically related to a kind of CuWO 4/ WO 3the preparation method of heterogeneous structural nano chip arrays film.
Background technology
Along with increasing with the requirement of people to material of world population is more and more higher, the mankind increase sharply to the degree of dependence of the energy and demand, result in the violent decline of fossil oil storage capacity on the earth, and create serious environmental problem.Finding a kind of new clean energy is the target that national governments and scientists are pursued and paid close attention to.In these emerging energies, sun power receives much concern as inexhaustible pollution-free energy source.
Within 1972, Japanese scholars Fujishima and Honda adopts monocrystalline n-TiO 2carry out the success of solar energy photocatalytic hydrogen production by water decomposition, opened the prelude of conductor photocatalysis research, sun power is converted into the application prospect of electric energy and chemical energy also to make people recognize.Photoelectrochemistry hydrogen production by water decomposition technology, based on sun power and water two kinds of renewable materials, does not have by product, does not pollute the environment, and photoelectrochemistry water of decomposition technology takes into account small-scale application and large-scale development simultaneously, is one of approach of solar hydrogen making most magnetism.
WO 3being a kind of semiconductor material of indirect band gap transition, having good chemical stability, is that minority self has one of type n semiconductor material of anti-light corrosive power.WO 3band gap width be ~ 2.65eV, light absorbing wavelength may extend to visible region (~ 470nm), is a kind of light anode material of desirable photoelectrochemistry water of decomposition.WO 3nanometer particle film, owing to there is a large amount of crystal boundary, is unfavorable for the transmission of photogenerated charge; WO 3nano-chip arrays, owing to having the electron propagation ducts of collimation, utilizes the transmission of photogenerated charge.In order to improve WO 3the separation efficiency of light anode photogenerated charge, with other can semi-conductor with mating (as CuWO 4) formed heterojunction be a kind of effective means.
Summary of the invention
The technical problem that the present invention solves there is provided a kind of simple to operate, with low cost and eco-friendly CuWO 4/ WO 3the preparation method of heterogeneous structural nano chip arrays film.
The present invention adopts following technical scheme, a kind of CuWO for solving the problems of the technologies described above 4/ WO 3the preparation method of heterogeneous structural nano chip arrays film, is characterized in that concrete steps are:
(1) 0.2-0.4g ammonium paratungstate hydrate is distributed in the mixed solvent of water and ethanol, then add 1-2mL mass concentration be 37% concentrated hydrochloric acid and 1-2mL mass concentration be the hydrogen peroxide of 35%, be uniformly mixed rear obtained WO 3precursor solution;
(2) by the WO of step (1) gained 3precursor solution is transferred in hydrothermal reaction kettle, and FTO conducting surface is put into hydrothermal reaction kettle down, by FTO conducting surface down in 140-180 DEG C of hydro-thermal reaction 2-6h, room temperature is cooled to the furnace after reaction terminates, take out FTO and rinse rear drying at room temperature, be then placed in retort furnace and obtain WO in 500 DEG C of annealing 2h 3nano-chip arrays;
(3) by the WO of step (2) gained 3nano-chip arrays takes out after being dipped vertically into and reacting 0.5-2h in the ethanolic soln of cupric salt, Cu in the ethanolic soln of wherein cupric salt 2+volumetric molar concentration be 30-70mmol/L, drying at room temperature be placed in retort furnace in 500 DEG C annealing 2h obtain CuWO 4/ WO 3heterogeneous structural nano chip arrays film.
Further preferably, in the water described in step (1) and the mixed solvent of ethanol, the volume ratio of water and ethanol is 1:4 ~ 4:1.
Further preferably, the cupric salt described in step (3) is CuSO 4, Cu (NO 3) 2or Cu (CH 3cOO) 2.
The CuWO that the present invention obtains 4/ WO 3heterogeneous structural nano chip arrays film has higher specific surface area and the electron propagation ducts of collimation, is beneficial to catching and the transmission of optical charge incident light; CuWO 4/ WO 3heterojunction structure is also beneficial to the separation of photogenerated charge, and the light anode therefore as photoelectrochemistry water of decomposition will show excellent character.In addition, the method that hydrothermal method binding soln soaks prepares CuWO 4/ WO 3simple to operate, with low cost and environmental friendliness, is beneficial to promotion and application.
Embodiment
Be described in further details foregoing of the present invention by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
(1) by 0.2g ammonium paratungstate hydrate H 42n 10o 42w 12xH 2o (HMT) is distributed in the mixed solvent of water and ethanol, and wherein the volume ratio of water and ethanol is 4:1, then add 1mL mass concentration be 37% concentrated hydrochloric acid and 1mL mass concentration be the hydrogen peroxide of 35%, be uniformly mixed rear obtained WO 3precursor solution;
(2) by the WO of step (1) gained 3precursor solution liquid is transferred in hydrothermal reaction kettle, and FTO conducting surface is put into this hydrothermal reaction kettle down, by its conducting surface down in 140 DEG C of reactions 2 hours, room temperature is cooled to the furnace after reaction terminates, take out FTO, drying at room temperature after rinsing, and in 500 DEG C of annealing, 2 hours obtained WO in retort furnace 3nano-chip arrays;
(3) by the WO of step (2) gained 3nano-chip arrays is dipped vertically into the CuSO that volumetric molar concentration is 30mmol/L 4ethanolic soln in, react after 0.5 hour take out, drying at room temperature be placed in retort furnace in 500 DEG C annealing 2 hours obtained CuWO 4/ WO 3heterojunction nano-chip arrays film.
Embodiment 2
(1) by 0.3g ammonium paratungstate hydrate H 42n 10o 42w 12xH 2o (HMT) is distributed in the mixed solvent of water and ethanol, and wherein the volume ratio of water and ethanol is 1:1, then add 1mL mass concentration be 37% concentrated hydrochloric acid and 1mL mass concentration be the hydrogen peroxide of 35%, be uniformly mixed rear obtained WO 3precursor solution;
(2) by the WO of step (1) gained 3precursor solution is transferred in hydrothermal reaction kettle, and FTO conducting surface is put into this hydrothermal reaction kettle down, by its conducting surface down in 160 DEG C of reactions 4 hours, room temperature is cooled to the furnace after reaction terminates, take out FTO, drying at room temperature after rinsing, and in 500 DEG C of annealing, 2 hours obtained WO in retort furnace 3nano-chip arrays;
(3) by WO that step (2) obtains 3nano-chip arrays is dipped vertically into the Cu (CH that volumetric molar concentration is 50mmol/L 3cOO) 2ethanolic soln in, react after 1 hour take out, drying at room temperature be placed in retort furnace in 500 DEG C annealing 2 hours obtained CuWO 4/ WO 3heterojunction nano-chip arrays film.
Embodiment 3
(1) by 0.4g ammonium paratungstate hydrate H 42n 10o 42w 12xH 2o (HMT) is distributed in the mixed solvent of water and ethanol, and wherein the volume ratio of water and ethanol is 4:1, then add 2mL mass concentration be 37% concentrated hydrochloric acid and 2mL mass concentration be the hydrogen peroxide of 35%, be uniformly mixed rear obtained WO 3precursor solution;
(2) by the WO of step (1) gained 3precursor solution is transferred in hydrothermal reaction kettle, and FTO conducting surface is put into this hydrothermal reaction kettle down, by its conducting surface down in 180 DEG C of reactions 6 hours, room temperature is cooled to the furnace after reaction terminates, take out FTO, rinse after drying at room temperature, and in retort furnace 500 DEG C annealing 2 hours obtained WO 3nano-chip arrays;
(3) by the WO of step (2) gained 3nano-chip arrays is dipped vertically into the Cu (NO3) that volumetric molar concentration is 70mmol/L 2ethanolic soln in, react after 2 hours take out, drying at room temperature be placed in retort furnace in 500 DEG C annealing 2 hours obtained CuWO 4/ WO 3heterojunction nano-chip arrays film.
Embodiment above describes ultimate principle of the present invention, principal character and advantage; the technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; under the scope not departing from the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of the invention.

Claims (3)

1. a CuWO 4/ WO 3the preparation method of heterogeneous structural nano chip arrays film, is characterized in that concrete steps are:
(1) 0.2-0.4g ammonium paratungstate hydrate is distributed in the mixed solvent of water and ethanol, then add 1-2mL mass concentration be 37% concentrated hydrochloric acid and 1-2mL mass concentration be the hydrogen peroxide of 35%, be uniformly mixed rear obtained WO 3precursor solution;
(2) by the WO of step (1) gained 3precursor solution is transferred in hydrothermal reaction kettle, and FTO conducting surface is put into hydrothermal reaction kettle down, by FTO conducting surface down in 140-180 DEG C of hydro-thermal reaction 2-6h, room temperature is cooled to the furnace after reaction terminates, take out FTO and rinse rear drying at room temperature, be then placed in retort furnace and obtain WO in 500 DEG C of annealing 2h 3nano-chip arrays;
(3) by the WO of step (2) gained 3nano-chip arrays takes out after being dipped vertically into and reacting 0.5-2h in the ethanolic soln of cupric salt, Cu in the ethanolic soln of wherein cupric salt 2+volumetric molar concentration be 30-70mmol/L, drying at room temperature be placed in retort furnace in 500 DEG C annealing 2h obtain CuWO 4/ WO 3heterogeneous structural nano chip arrays film.
2. CuWO according to claim 1 4/ WO 3the preparation method of heterogeneous structural nano chip arrays film, is characterized in that: in the water described in step (1) and the mixed solvent of ethanol, the volume ratio of water and ethanol is 1:4 ~ 4:1.
3. CuWO according to claim 1 4/ WO 3the preparation method of heterogeneous structural nano chip arrays film, is characterized in that: the cupric salt described in step (3) is CuSO 4, Cu (NO 3) 2or Cu (CH 3cOO) 2.
CN201510959603.9A 2015-12-21 2015-12-21 Preparation method of CuWO4/WO3 heterostructured nanosheet array film Pending CN105568314A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106252101A (en) * 2016-09-27 2016-12-21 西北工业大学 The preparation method of ultracapacitor nanometer Cupric wolframate. polyhedron electrode material
CN107442105A (en) * 2017-07-24 2017-12-08 苏州大学 Available for tungsten manganese calcium/mesoporous tungsten trioxide compound for preparing light anode and preparation method thereof
CN108538607A (en) * 2018-04-28 2018-09-14 天津大学 Type II heterojunction WO3-ZnWO4Thin-film photoelectric anode, preparation method and application thereof
CN109295474A (en) * 2018-10-09 2019-02-01 天津城建大学 A kind of CuWO of the nano bar-shape of Co doping4The preparation method of photo-anode film
CN112588303A (en) * 2020-11-23 2021-04-02 安徽大学 Preparation method of selenium-bismuth oxide nanosheet and heterojunction type photoelectrode based on preparation method
CN113293404A (en) * 2020-10-23 2021-08-24 台州学院 Heterojunction photo-anode material and preparation method and application thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
FAQI ZHAN等: "In situ formation of CuWO4/WO3 heterojunction plates array films with enhanced photoelectrochemical properties", 《INTERNATIONAL JOURNAL OF HYDROGEN ENEGY》 *
FENG ZHENG等: "Hydrothermal preparation and optical properties oforientation-controlled WO3 nanorod arrays on ITO substrates", 《CITE THIS: CRYSTENGCOMM》 *
孙宝莲等: "化学法制备高纯三氧化钨", 《中国钼业》 *
杨娇: "WO3纳米片阵列薄膜的制备及其光电化学性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106252101A (en) * 2016-09-27 2016-12-21 西北工业大学 The preparation method of ultracapacitor nanometer Cupric wolframate. polyhedron electrode material
CN106252101B (en) * 2016-09-27 2018-06-08 西北工业大学 The preparation method of ultracapacitor nanometer copper tungstate polyhedron electrode material
CN107442105A (en) * 2017-07-24 2017-12-08 苏州大学 Available for tungsten manganese calcium/mesoporous tungsten trioxide compound for preparing light anode and preparation method thereof
CN108538607A (en) * 2018-04-28 2018-09-14 天津大学 Type II heterojunction WO3-ZnWO4Thin-film photoelectric anode, preparation method and application thereof
CN109295474A (en) * 2018-10-09 2019-02-01 天津城建大学 A kind of CuWO of the nano bar-shape of Co doping4The preparation method of photo-anode film
CN113293404A (en) * 2020-10-23 2021-08-24 台州学院 Heterojunction photo-anode material and preparation method and application thereof
CN112588303A (en) * 2020-11-23 2021-04-02 安徽大学 Preparation method of selenium-bismuth oxide nanosheet and heterojunction type photoelectrode based on preparation method

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