CN101734866A - Method for preparing nano tungsten trioxide thin film - Google Patents

Method for preparing nano tungsten trioxide thin film Download PDF

Info

Publication number
CN101734866A
CN101734866A CN200910311691A CN200910311691A CN101734866A CN 101734866 A CN101734866 A CN 101734866A CN 200910311691 A CN200910311691 A CN 200910311691A CN 200910311691 A CN200910311691 A CN 200910311691A CN 101734866 A CN101734866 A CN 101734866A
Authority
CN
China
Prior art keywords
thin film
tungsten trioxide
nano tungsten
trioxide thin
film preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN200910311691A
Other languages
Chinese (zh)
Inventor
陈启元
李洁
李文章
刘立阳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN200910311691A priority Critical patent/CN101734866A/en
Publication of CN101734866A publication Critical patent/CN101734866A/en
Pending legal-status Critical Current

Links

Images

Abstract

The invention relates to a method for preparing a nano tungsten trioxide thin film, in particular to a method for preparing a nano tungsten trioxide thin film used for a semiconductor photoelectrode of a photocatalytic or photoelectrochemical cell. The method for synthesizing the nano tungsten trioxide thin film comprises the following steps: dissolving water-soluble poly-tungstate in water, adding dispersant and modifier to the solution to obtain precursor solution which can be saved for more than 3 months, coating the surface of a substrate with the dipping and drawing method or the spin-coating method, and calcinating the substrate at high temperature in the air to decompose organic components to obtain the nano tungsten trioxide thin film. The method for preparing the nano tungsten trioxide thin film has the characteristics of simple steps and convenient operation. The nano tungsten trioxide thin film prepared with the method has high purity and excellent photoelectric performance, can be firmly combined with the substrate and is free from the size limitation.

Description

A kind of preparation method of nano tungsten trioxide thin film
Technical field
The present invention relates to a kind of nano tungsten trioxide thin film preparation method, particularly relate to a kind of preparation of nano tungsten trioxide thin film of the semi-conducting electrode that is used for photochemical catalysis or photoelectrochemistrpool pool.
Background technology
Solar energy electrochemical cell hydrogen manufacturing (PEC) technology is based on sun power and water, and these two kinds of materials all are reproducible, and the PEC technology does not have byproduct, can not bring pollution to environment, but and both small-scale application of PEC technology, but large-scale development again.Therefore, this technology is directly to utilize the most attractive hydrogen manufacturing approach of solar hydrogen making.
The performance of forming the semiconductor material of optoelectronic pole has determined the efficient of PEC.Because semiconductor material has certain selectivity to sunlight, simultaneously be easy to corrode on the interface of it and liquid, thereby reduced semi-conductive performance, so the semiconductor material of low energy gap of research and development and high corrosion resistance is the emphasis of present PEC research.
Compare with traditional titanium dioxide, zinc oxide semiconductor material, tungstic oxide has narrower energy gap (2.5eV), can absorb the advantage of solar spectrum medium wavelength greater than the 500nm visible light, and it is cheap, good chemical stability, nontoxicity being arranged, characteristics such as photoetch do not take place, is a kind of good Application of Solar Energy semiconductor material.WO 3 film material preparation method commonly used at present has: atomic layer deposition method (J.Amer.Chem.Soc., 2006,128,9638), chemical Vapor deposition process (J.Amer.Chem.Soc., 2006,128,1587; Chem.Mater., 2003,15,2786), Sol-Gel method (J.Amer.Chem.Soc., 2001,123,10639) and electrodip process (Adv.Mater., 2003,15,1269).Based on the WO 3 film method equipment requirements height that atomic layer deposition method, chemical Vapor deposition process and electrodip process grow up, complicated process of preparation, the cost height, and can't prepare large-area film.It is simple that sol-gel method has technology, and cost is lower, can be in the advantages such as base coated film of big area, arbitrary shape.But representative technology with present sol-gel method: the alcoholization method of tungstate acidization, tungstate ion exchange process, tungsten chloride, the precursor sol that obtains can't be placed for a long time, changes gel easily into; These method precursor liquids have all been introduced foreign ion in addition.As being the WO 3 film that raw material synthetic precursor makes with the sodium wolframate, the existence of alkalimetal ion easily makes WO 3Change M into xWO 3, reduce photocatalytic activity and photoelectricity conversion performance.All be applied to fields such as photochromic, gas sensitive with the WO 3 film major part of present existing prepared.Therefore, it is simple to develop a kind of production technique, and cost is low, high purity, and the tungstic oxide PEC semi-conducting electrode material of high electricity conversion is imperative.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of nano tungsten trioxide thin film, its precursor liquid is stable, and is reusable, also has the simplification production technique, reduce cost, the product purity height of gained, combine firmly, be not subjected to advantages such as limitation of size and excellent photoelectric performance with substrate.
The present invention realized by the following technical programs,
A kind of nano tungsten trioxide thin film preparation method comprises precursor liquid preparation, base coated film, high-temperature calcination, it is characterized in that, and be that the water-soluble poly tungstate of the 2wt-50wt% aqueous solution adds the 10-50wt% dispersion agent with concentration, make the tungstic oxide precursor liquid.
Described poly tungstate is [NH 4] 6W 7O 246H 2O, [NH 4] 6[W 12O 39], [NH 4] 10H 2[W 2O 7] 6[NH 4] 6H 2W 12OnH 2O's is wherein at least a.
Described dispersion agent is polyoxyethylene glycol, polyvinyl alcohol, Terpineol 350 or polyoxyethylene-poly-oxypropylene polyoxyethylene.
The molecular weight of described polyoxyethylene glycol comprises 200-20000.
In order to improve the stability of precursor liquid, can place for a long time and use repeatedly, in the described water-soluble poly tungstate aqueous solution, can add the properties-correcting agent that is no more than 20wt%.
Described properties-correcting agent is citric acid, Triton X-100, oleic acid or methyl ethyl diketone.
Preparation is during precursor liquid, add various raw materials after, magnetic force continues to stir 3-5h, at 70-90 ℃ of water-bath 1.5-3h, obtains transparent precursor liquid again.
Described plated film substrate is aluminium, stainless steel, glass, graphite or silicon chip.
A kind of nano tungsten trioxide thin film of the present invention and preparation method thereof specifically comprises following process:
1, precursor liquid preparation: an amount of water-soluble poly tungstate is dissolved in the secondary deionized water, adds certain amount of dispersant and properties-correcting agent again, magnetic stirring apparatus continues to stir, and constant temperature leaves standstill again, obtains precursor liquid.The effect of dispersion agent is to constitute a large amount of netted pilotaxitic texture, becomes to be difficult for producing the crack in the brilliant process at dry, high temperature; And the effect of properties-correcting agent improves the stability of precursor liquid, in the process of hot conditions film growth, can prevent the nano tungsten trioxide particle agglomeration in addition, causes film to come off.
2, film coating method: adopt dip-coating method or spin-coating method plated film in substrate to be applied, and mummification under the certain temperature condition.Substrate to be coated such as should clean earlier at pre-treatment.The substrate material is the wherein a kind of of aluminium, stainless steel, glass, graphite, silicon chip.
3, roasting method: after the base coated film drying, but be positioned over the retort furnace high-temperature roasting of temperature programmed control.Temperature rise rate 1-10 ℃/min, maturing temperature 350-600 ℃, thermal treatment 2-5h, thus obtain nano tungsten trioxide thin film.
The beneficial effect that the present invention obtains is: 1) adopting water-soluble poly tungstate is presoma, and by adding dispersion agent and properties-correcting agent, final WO 3 film and substrate stability are fine, obscission can not occur.In addition, precursor liquid was preserved more than 3 months, can not produce the coagulative precipitation phenomenon, still kept steady state, can reuse, and is not only easy and simple to handle, also greatly reduces preparation cost; 2) precursor liquid does not have to introduce the metallic element, particularly alkali metal (Na except that W +, K +).Because the existence of alkali metal causes generating tungsten bronze(s) M easily xWO 3(M is a basic metal) influences WO 3Photocatalytic activity and photoelectricity conversion performance.And dispersion agent and properties-correcting agent that the present invention adopts are organism fully, the easy oxidation removal of high temperature; 3) adopt the WO 3 film of this prepared to have excellent photoelectric performance: at 60mW/cm 2Under the mercury lamp condition of light intensity, the bias voltage of 1.5V is issued to 3.9mA/cm 2Current density, photoelectric properties are to prepare WO than being dissolved in hydrogen peroxide process with tungsten powder 3High 2-3 doubly.
Description of drawings
The FESEM figure of the nano tungsten trioxide thin film that Fig. 1 makes for embodiment 1;
The FESEM figure of the nano tungsten trioxide thin film that Fig. 2 makes for embodiment 2;
The FESEM figure of the nano tungsten trioxide thin film that Fig. 3 makes for embodiment 3;
The FESEM figure of the nano tungsten trioxide thin film that Fig. 4 makes for embodiment 4;
The FESEM figure of the nano tungsten trioxide thin film that Fig. 5 makes for embodiment 5;
The FESEM figure of the nano tungsten trioxide thin film that Fig. 6 makes for embodiment 6;
The X diffracting spectrum of the nano tungsten trioxide thin film that Fig. 7 makes for embodiment 1;
The X diffracting spectrum of the nano tungsten trioxide thin film that Fig. 8 makes for embodiment 6;
Fig. 9 is the photoelectric current-voltage response curves of embodiment 1 nano tungsten trioxide thin film.
Embodiment
Embodiment 1
The conductive glass substrate is cleaned: the Virahol saturated solution of the FTO conductive glass being put into KOH soaked 24 hours; Clean with distilled water flushing; Distilled water ultrasonic cleaning 30 minutes; Acetone ultrasonic cleaning 30 minutes; Dehydrated alcohol ultrasonic cleaning 30 minutes; N is washed in secondary deionized water ultrasonic cleaning 30 minutes again 3 times 2Dry up standby.
Take by weighing 9.8g (NH 4) 6W 7O 246H 2O is dissolved in the 20ml secondary deionized water, adds the cetomacrogol 1000 of 5g, and magnetic force continues to stir 4h, at 80 ℃ of water-bath 2h, obtains transparent precursor liquid again.
Adopt the dip-coating method plated film, with the speed of 2cm/min the FTO conductive glass is lifted out from the precursor liquid for preparing, leave standstill 5min, put into 70 ℃ oven drying 1h, the temperature rise rate with 5 ℃/min rises to 500 ℃ then, insulation 3h.Open fire door and naturally cool to room temperature, can obtain nano tungsten trioxide thin film.Fig. 1, Fig. 7 are respectively the FESEM figure and the X diffracting spectrum of the nano tungsten trioxide thin film that makes; Fig. 9 is WO 3The photoelectric current voltage response curves of film.
Embodiment 2
Present embodiment is similar to embodiment 1, and difference is: step 2) except adding the cetomacrogol 1000 of 5g, other adds the 2.5g citric acid, and stirring, water-bath are left standstill and are obtained precursor liquid, and plated film, calcining promptly obtain nano tungsten trioxide thin film.Fig. 2 is the FESEM figure of the nano tungsten trioxide thin film that makes.
Embodiment 3
Present embodiment is similar to embodiment 1, and difference is: step 2) take by weighing 9.8g (NH 4) 6H 2W 12OnH 2O is dissolved in the 20ml secondary deionized water, adds poly(oxyethylene glycol) 400 and the 2.5g oleic acid of 10g, and stirring, water-bath are left standstill and obtained precursor liquid, and plated film, calcining promptly obtain nano tungsten trioxide thin film.Fig. 3 is the FESEM figure of the nano tungsten trioxide thin film that makes.
Embodiment 4
Present embodiment is similar to embodiment 1, and difference is: step 2) take by weighing 4.9g[NH 4] 6[W 12O 39] be dissolved in the 20ml secondary deionized water, adding the 5g polyethylene glycol 6000, stirring, water-bath are left standstill and are obtained precursor liquid, and plated film, calcining promptly obtain nano tungsten trioxide thin film.Fig. 4 is the FESEM figure of the nano tungsten trioxide thin film that makes.
Embodiment 5
Present embodiment is similar to embodiment 1, and difference is: step 2) take by weighing 3.2g[NH 4] 10H 2[W 2O 7] 6Be dissolved in the 20ml secondary deionized water, add 2.5g Macrogol 2000 0, stirring, water-bath are left standstill and are obtained precursor liquid, and plated film, calcining promptly obtain nano tungsten trioxide thin film.Fig. 5 is the FESEM figure of the nano tungsten trioxide thin film that makes.
Embodiment 6
Present embodiment is similar to embodiment 1, and difference is: graphite base is adopted in the substrate of step 3).Fig. 6 and Fig. 8 are respectively the FESEM figure and the X diffracting spectrum of the nano tungsten trioxide thin film that makes.
It should be noted last that: above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although the present invention is had been described in detail with reference to above-mentioned, those of ordinary skill in the art is to be understood that: still can make amendment or replacement on an equal basis to the present invention, and not breaking away from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.

Claims (8)

1. a nano tungsten trioxide thin film preparation method comprises precursor liquid preparation, base coated film, high-temperature calcination, it is characterized in that, and be that the water-soluble poly tungstate of the 2wt-50wt% aqueous solution adds the 10-50wt% dispersion agent with concentration, make the tungstic oxide precursor liquid.
2. a kind of nano tungsten trioxide thin film preparation method according to claim 1, it is characterized in that described water-soluble poly tungstate is [NH4] 6W7O246H2O, [NH4] 6[W12O39], [NH4] 10H2[W2O7] 6 and [NH4] 6H2W12OnH2O wherein at least a.
3. a kind of nano tungsten trioxide thin film preparation method according to claim 1 is characterized in that described dispersion agent is polyoxyethylene glycol, polyvinyl alcohol, Terpineol 350 or polyoxyethylene-poly-oxypropylene polyoxyethylene.
4. a kind of nano tungsten trioxide thin film preparation method according to claim 3 is characterized in that the molecular weight of described polyoxyethylene glycol comprises 200-20000.
5. a kind of nano tungsten trioxide thin film preparation method according to claim 1 is characterized in that, adds to be no more than 20wt% properties-correcting agent in the described water-soluble poly tungstate aqueous solution.
6. a kind of nano tungsten trioxide thin film preparation method according to claim 5 is characterized in that described properties-correcting agent is citric acid, Triton X-100, oleic acid or methyl ethyl diketone.
7. a kind of nano tungsten trioxide thin film preparation method according to claim 1 is characterized in that, preparation is during precursor liquid, add various raw materials after, magnetic force continues to stir 3-5h, at 70-90 ℃ of water-bath 1.5-3h, obtains transparent precursor liquid again.
8. a kind of nano tungsten trioxide thin film preparation method according to claim 1 is characterized in that described plated film substrate is aluminium, stainless steel, glass, graphite or silicon chip.
CN200910311691A 2009-12-17 2009-12-17 Method for preparing nano tungsten trioxide thin film Pending CN101734866A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200910311691A CN101734866A (en) 2009-12-17 2009-12-17 Method for preparing nano tungsten trioxide thin film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200910311691A CN101734866A (en) 2009-12-17 2009-12-17 Method for preparing nano tungsten trioxide thin film

Publications (1)

Publication Number Publication Date
CN101734866A true CN101734866A (en) 2010-06-16

Family

ID=42458968

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200910311691A Pending CN101734866A (en) 2009-12-17 2009-12-17 Method for preparing nano tungsten trioxide thin film

Country Status (1)

Country Link
CN (1) CN101734866A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102674463A (en) * 2012-05-21 2012-09-19 上海交通大学 Tungsten-base tungsten trioxide nano film, and preparation method and application thereof
US8821967B2 (en) 2010-10-04 2014-09-02 National Cheng Kung University Method for manufacturing an oxide thin film
CN105056938A (en) * 2015-08-27 2015-11-18 盐城工学院 Method for improving photocatalytic activity of tungsten trioxide film
CN106024195A (en) * 2016-05-20 2016-10-12 陕西国际商贸学院 Preparation method for tungsten nanodots with controllable dimensions
CN108465475A (en) * 2018-04-04 2018-08-31 东莞市石鼓污水处理有限公司 A kind of preparation method of WO3-ZrO2 photocatalysis sewages processing composite membrane
CN115432939A (en) * 2022-03-22 2022-12-06 苏州科技大学 High-performance tungsten trioxide/bismuth tungstate film and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8821967B2 (en) 2010-10-04 2014-09-02 National Cheng Kung University Method for manufacturing an oxide thin film
CN102674463A (en) * 2012-05-21 2012-09-19 上海交通大学 Tungsten-base tungsten trioxide nano film, and preparation method and application thereof
CN105056938A (en) * 2015-08-27 2015-11-18 盐城工学院 Method for improving photocatalytic activity of tungsten trioxide film
CN106024195A (en) * 2016-05-20 2016-10-12 陕西国际商贸学院 Preparation method for tungsten nanodots with controllable dimensions
CN108465475A (en) * 2018-04-04 2018-08-31 东莞市石鼓污水处理有限公司 A kind of preparation method of WO3-ZrO2 photocatalysis sewages processing composite membrane
CN115432939A (en) * 2022-03-22 2022-12-06 苏州科技大学 High-performance tungsten trioxide/bismuth tungstate film and preparation method thereof
CN115432939B (en) * 2022-03-22 2024-04-09 苏州科技大学 High-performance tungsten trioxide/bismuth tungstate film and preparation method thereof

Similar Documents

Publication Publication Date Title
Xu et al. Au nanoparticles modified branched TiO2 nanorod array arranged with ultrathin nanorods for enhanced photoelectrochemical water splitting
Yu et al. ZnS/ZnO heteronanostructure as photoanode to enhance the conversion efficiency of dye-sensitized solar cells
CN108103525B (en) N doping carbon dots modify tungstic acid complex light electrode and preparation method thereof and decompose the application in water in photoelectrocatalysis
Phuan et al. Effects of annealing temperature on the physicochemical, optical and photoelectrochemical properties of nanostructured hematite thin films prepared via electrodeposition method
CN109402656B (en) Preparation method of cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode
CN106848494B (en) A kind of simple preparation method of carbon auto-dope nano carbon nitride film electrode
Liu et al. Composite photoanodes of Zn2SnO4 nanoparticles modified SnO2 hierarchical microspheres for dye-sensitized solar cells
CN105039938B (en) The method that a kind of list source presoma prepares the optoelectronic pole of α-ferric oxide film
Ge et al. Photocathodic protection of 304 stainless steel by MnS/TiO2 nanotube films under simulated solar light
CN108579765B (en) Preparation of copper sulfide/bismuth vanadate double-layer film composite material and application of copper sulfide/bismuth vanadate double-layer film composite material as photoelectric anode
CN104941614A (en) Method for preparing black titanium dioxide by contact type reduction method
CN102220615B (en) Method for preparing CdS/ZnO nanotube array photoelectrode
CN101734866A (en) Method for preparing nano tungsten trioxide thin film
CN105498773A (en) Preparation method for doped iron oxide nanorod catalyst
Song et al. Enhanced visible-light response and conductivity of the TiO2/reduced graphene oxide/Sb2S3 heterojunction for photoelectrochemical water oxidation
CN105261483B (en) Cu2ZnSnS4It is sensitized TiO2Light anode and its in-situ preparation method and application
Shin et al. Highly transparent dual-sensitized titanium dioxide nanotube arrays for spontaneous solar water splitting tandem configuration
Cao et al. Zn0. 5Cd0. 5S nanoparticles modified TiO2 nanotube arrays with efficient charge separation and enhanced light harvesting for boosting visible-light-driven photoelectrochemical performance
Xin et al. Construction of BiVO4 nanosheets@ WO3 arrays heterojunction photoanodes by versatile phase transformation strategy
CN106637285B (en) Cu2The TiO 2 nanotubes modified optoelectronic pole of O quantum dot and its preparation and application
CN110965073B (en) WO containing defects3Preparation method of photoelectrode
Kong et al. Controlled synthesis of various SrTiO3 morphologies and their effects on photoelectrochemical cathodic protection performance
Gao et al. ZnO/TiO2 core–shell heterojunction for CdS and PbS quantum dot-cosensitized solar cells
Guo et al. A simplified successive ionic layer adsorption and reaction (s-SILAR) method for growth of porous BiVO4 thin films for photoelectrochemical water oxidation
Saleem et al. Solution-derived ZnO nanoflowers based photoelectrodes for dye-sensitized solar cells

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Open date: 20100616