CN104071831A - Titanium dioxide nanowire arrays simultaneously subjected to etching and tungsten doping as well as preparation method and application of titanium dioxide nanowire arrays - Google Patents
Titanium dioxide nanowire arrays simultaneously subjected to etching and tungsten doping as well as preparation method and application of titanium dioxide nanowire arrays Download PDFInfo
- Publication number
- CN104071831A CN104071831A CN201410288305.7A CN201410288305A CN104071831A CN 104071831 A CN104071831 A CN 104071831A CN 201410288305 A CN201410288305 A CN 201410288305A CN 104071831 A CN104071831 A CN 104071831A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- preparation
- etching
- nanowire arrays
- dioxide nanowire
- 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
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of solar cells and particularly relates to titanium dioxide nanowire arrays simultaneously subjected to etching and tungsten doping as well as a preparation method and an application of titanium dioxide nanowire arrays. The preparation method comprises the steps of enabling titanium dioxide nanowire arrays to grow on a conductive glass substrate containing fluorinated tin oxide (FTO) and the like under a hydrothermal system and then simultaneously carrying out etching and tungsten doping on the titanium dioxide nanowire arrays in hydroxylamine hydrochloride, sodium sulfide and sodium tungstate aqueous solutions, wherein tetra-n-butyl titanate and the like are taken as titanium sources, water is taken as a solvent and the rate of the hydrolysis reaction is adjusted by concentrated hydrochloric acid. According to the preparation method disclosed by the invention, by virtue of the etching process of titanium dioxide nanowire arrays under weakly alkaline conditions, the efficient tungsten doping is realized, the absorption efficiency of the solar cell to light is improved and a one-step process of hydrogen generation by virtue of efficient photolysis of water and the generation of photocurrent by virtue of photoelectric conversion is achieved. The titanium dioxide nanowire arrays disclosed by the invention have the advantages of wide range of sources of raw materials, simple preparation method, environment friendliness and low cost and are conducive to being popularized and applied.
Description
Technical field
The invention belongs to technical field of solar batteries, be specifically related to a kind of etching simultaneously and tungsten doped titanium dioxide nano line array and preparation method thereof and the application in solar cell.
Background technology
In recent years, along with the energy dilemma that the exhaustion of global fossil oil brings, people day by day increase for finding sustainable demand that can new forms of energy.Sun power, as a kind of sustainable development source of cleanliness without any pollution, efficiently utilizes sun power to attract whole world investigator's concern.General using solar energy resources can be divided into two large classes: a class is solar cell, by solar energy converting, is utilization of power, but because the electric energy of solar cell needs to use in time, can not standing storage, thereby can there is in actual use the problems such as grid-connected, energy storage; Another kind of is photogalvanic cell, by solar energy converting, is chemical energy utilization, and as decomposing water with solar energy hydrogen manufacturing, this kind of energy, without further conversion, can directly store life-time service.
Titanium dioxide is as a kind of semiconductor energy gap Structure and stability, thereby is widely studied photodissociation is waterborne, but titanium dioxide exists the excessive problem of band gap, can only absorb the light of ultraviolet region, sun power utilising efficiency is too low, need to dwindle band gap by doping, strengthens photoabsorption.Adulterating method generally has two classes: front synthesizing blender and aftertreatment doping.Front synthesizing blender need to add dopant presoma when synthetic, and this class doping is generally more even, but may have impact to the appearance structure of material.Aftertreatment doping can keep the intrinsic pattern of material, generally needs high temperature annealing, but a lot of material and substrate cannot be born pyroprocessing.The present invention utilizes titanium dioxide etching process at a lower temperature, has carried out the hydro-thermal aftertreatment tungsten doping under lesser temps, have adulterating method simple and convenient, adulterate a little effectively, conveniently use on a large scale.
Summary of the invention
The object of this invention is to provide and a kind ofly there is efficient photolysis water hydrogen, and etching and tungsten doped titanium dioxide nano line array and its preparation method and application when producing photoelectric current.
The preparation method of while etching provided by the invention and tungsten doped titanium dioxide nano line array, concrete steps are:
(1) water is mixed to 0.1 – with concentrated acid after 0.5 hour, add wherein titanium source, under whipped state, react 5 – 10 min; Then transfer in reactor, the substrate front surface of suitable size is put into still down, under 140 180 ℃ of – conditions, react 4 – 20 hours;
(2) product above-mentioned steps being made is rinsed well, is dried up, and roasting 1 – 2 hours under 550 ℃ of temperature condition of 450 – in air atmosphere, obtains pure titinium dioxide nano-wire array;
(3) pure titinium dioxide nano-wire array above-mentioned steps being made is placed in oxammonium hydrochloride, sodium sulphite and the sodium wolframate aqueous solution, reacts 2-10 hour under 150-200 ℃ of condition, can obtain etching and tungsten doped titanium dioxide nano line array simultaneously.
In the present invention, described titanium source can be one or more in titanyl sulfate, titanium sulfate, titanium tetrachloride, titanium tetraisopropylate, n-butyl titanium, tetrem amido titanium, four Propylamino titaniums or four butylamine base titaniums.
In the present invention, described concentrated acid can be concentrated hydrochloric acid or nitric acid.
In the present invention, described substrate can be silicon chip or the slide that FTO glass or spin coating have titanium dioxide crystal seed.
In the present invention, second step hydrothermal solution is oxammonium hydrochloride, sodium sulphite and the sodium wolframate aqueous solution; Etching and tungsten doping simultaneously during second step hydro-thermal.
In the present invention, etching and tungsten doped titanium dioxide nano line array can utilize the hydrogen manufacturing simultaneously of sun power photodissociation water generates photoelectric current simultaneously.
Nano-wire array of the present invention can be applicable to solar cell: take while etching and tungsten doped titanium dioxide nano line array is working electrode, Ag/AgCl electrode is reference electrode, platinum filament is to electrode, the sodium hydroxide of 0.1 – 1 M or potassium hydroxide solution are reaction soln, irradiating light intensity is a sunlight, and irradiating sectional area is to regulate according to the size of working electrode.
The present invention simultaneously etching and the titania-doped array of tungsten is to adopt hydrothermal method preparation, and etching and tungsten doped titanium dioxide nano line array, realize the performance that efficient photolysis water hydrogen produces photoelectric current simultaneously by under lesser temps time.It is simple that while etching and tungsten doped titanium dioxide nano line array have manufacture craft, cost is low, good stability, the high also environment amenable feature of electricity conversion, being applicable to big area produces, upper significant for solar cell research, at new energy field, also there is good application prospect.
Accompanying drawing explanation
Fig. 1: a – c is the SEM photo of pure titinium dioxide nano-wire array; D-f is the SEM photo of while etching and tungsten doped titanium dioxide nano line array.
Fig. 2: a is while etching and titania-doped photoelectric current curve (solid line) and the dark current curve (dotted line) of tungsten; B is the time m-photoelectric current curve under 0.23 V vs Ag/AgCl condition.
Fig. 3 is while etching and tungsten doped titanium dioxide nano line array preparation principle diagram.
Embodiment
Below, by following examples, the invention will be further described, and it will contribute to understand the present invention, but not limit content of the present invention.
First substrate FTO glass is placed in to the reactor of 50 ml, face down, gets 15 ml water and mixes with 13 ml concentrated hydrochloric acids, then to adding 0.35 ml tetra-n-butyl titanate in it.Treat solution stirring 5 – 10 minutes, after mixing, pour in reactor, under 150 ℃ of conditions, react 12 hours.After reaction finishes, substrate is taken out and cleans and dry up.Then, substrate is placed in tube furnace under 450 ℃ of conditions to roasting 2 hours.Finally, under argon shield, be down to room temperature, the SEM photo of resulting pure titinium dioxide nano-wire array is as shown in Fig. 1 a-c.Pure titinium dioxide nano-wire array is continued to be placed in to the reactor of 50 ml, the 30 mL aqueous solution that add 0.725 g oxammonium hydrochloride, 1.2 g nine hydrated sodium sulfides and 1.852 g sodium wolframates, under 180 ℃ of conditions, react 10 hours, can obtain etching and tungsten doped titanium dioxide nano line array simultaneously, the SEM photo of resulting while etching and the titania-doped titanium dioxide nanowire array of tungsten is as shown in Fig. 1 d-f.
As shown in Figure 3, take while etching and tungsten doped titanium dioxide nano line array is working electrode, and Ag/AgCl electrode is reference electrode, and platinum filament is to electrode, and the sodium hydroxide solution of 1 M is reaction soln, and irradiating light intensity is a sunlight, and irradiated area is 1 cm
2.Under 0.25 V condition, survey its photoelectricity flow valuve, can find photoelectric current be about 1.53 mA(as Fig. 2 a).When sweep time, surpass 15000 seconds, photoelectricity flow valuve still keeps stable (as Fig. 2 b).
Claims (6)
1. the preparation method of etching and tungsten doped titanium dioxide nano line array simultaneously, is characterized in that concrete steps are:
(1) water is mixed to 0.1 – with concentrated acid after 0.5 hour, add wherein titanium source, under whipped state, react 5 – 10 min, then transfer in reactor, substrate front surface is put into still down, under 140 180 ℃ of – conditions, react 4 – 20 hours;
(2) product above-mentioned steps being made is rinsed well, is dried up, and roasting 1 – 2 hours under 550 ℃ of temperature condition of 450 – in air atmosphere, obtains pure titinium dioxide nano-wire array;
(3) pure titinium dioxide nano-wire array above-mentioned steps being made is placed in oxammonium hydrochloride, sodium sulphite and the sodium wolframate aqueous solution, reacts 2-10 hour under 150-200 ℃ of condition, obtains etching and tungsten doped titanium dioxide nano line array simultaneously.
2. preparation method as claimed in claim 1, is characterized in that described concentrated acid is concentrated hydrochloric acid or nitric acid.
3. preparation method as claimed in claim 1, is characterized in that described titanium source is one or more in titanyl sulfate, titanium sulfate, titanium tetrachloride, titanium tetraisopropylate, n-butyl titanium, tetrem amido titanium, four Propylamino titaniums or four butylamine base titaniums.
4. the preparation method as described in claim 1,2 or 3, it is characterized in that described substrate is FTO glass, or spin coating has silicon chip or the slide of titanium dioxide crystal seed.
5. etching and tungsten doped titanium dioxide nano line array when being prepared by one of claim 1-4 preparation method, can utilize the hydrogen manufacturing simultaneously of sun power photodissociation water generates photoelectric current.
6. while etching as claimed in claim 5 and the application of tungsten doped titanium dioxide nano line array in preparing solar cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410288305.7A CN104071831A (en) | 2014-06-25 | 2014-06-25 | Titanium dioxide nanowire arrays simultaneously subjected to etching and tungsten doping as well as preparation method and application of titanium dioxide nanowire arrays |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410288305.7A CN104071831A (en) | 2014-06-25 | 2014-06-25 | Titanium dioxide nanowire arrays simultaneously subjected to etching and tungsten doping as well as preparation method and application of titanium dioxide nanowire arrays |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104071831A true CN104071831A (en) | 2014-10-01 |
Family
ID=51593495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410288305.7A Pending CN104071831A (en) | 2014-06-25 | 2014-06-25 | Titanium dioxide nanowire arrays simultaneously subjected to etching and tungsten doping as well as preparation method and application of titanium dioxide nanowire arrays |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104071831A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112481634A (en) * | 2020-10-08 | 2021-03-12 | 江苏大学 | Ternary composite TiO2Preparation method and application of-STO-CdS NRs photoelectrode |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101109096A (en) * | 2007-06-22 | 2008-01-23 | 湖南大学 | Method for producing titanium dioxide nano tube array with molybdenum tungsten doped anodizing method |
| CN101792117A (en) * | 2010-02-23 | 2010-08-04 | 武汉理工大学 | Method for preparing tungsten-doped anatase type nano titanium dioxide composite powder |
| CN102157268A (en) * | 2010-11-23 | 2011-08-17 | 复旦大学 | Tungsten-doped nanocrystalline titanium dioxide semiconductor film as well as preparation method and application thereof |
| CN102509625A (en) * | 2011-11-14 | 2012-06-20 | 复旦大学 | In-situ preparation method for photoanode of silicon-tungsten and TiO2 codoped nanotube film |
-
2014
- 2014-06-25 CN CN201410288305.7A patent/CN104071831A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101109096A (en) * | 2007-06-22 | 2008-01-23 | 湖南大学 | Method for producing titanium dioxide nano tube array with molybdenum tungsten doped anodizing method |
| CN101792117A (en) * | 2010-02-23 | 2010-08-04 | 武汉理工大学 | Method for preparing tungsten-doped anatase type nano titanium dioxide composite powder |
| CN102157268A (en) * | 2010-11-23 | 2011-08-17 | 复旦大学 | Tungsten-doped nanocrystalline titanium dioxide semiconductor film as well as preparation method and application thereof |
| CN102509625A (en) * | 2011-11-14 | 2012-06-20 | 复旦大学 | In-situ preparation method for photoanode of silicon-tungsten and TiO2 codoped nanotube film |
Non-Patent Citations (1)
| Title |
|---|
| YONGCHENG WANG ET AL.: ""Simultaneous Etching and Doping of TiO2 Nanowire Arrays for Enhanced Photoelectrochemical Performance"", 《ACSNANO》, vol. 7, no. 10, 18 September 2013 (2013-09-18) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112481634A (en) * | 2020-10-08 | 2021-03-12 | 江苏大学 | Ternary composite TiO2Preparation method and application of-STO-CdS NRs photoelectrode |
| CN112481634B (en) * | 2020-10-08 | 2021-12-21 | 江苏大学 | Ternary composite TiO2Preparation method and application of-STO-CdS NRs photoelectrode |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zeng et al. | A low-cost photoelectrochemical tandem cell for highly-stable and efficient solar water splitting | |
| Pan et al. | The photovoltaic conversion enhancement of NiO/Tm: CeO2/SnO2 transparent pn junction device with dual-functional Tm: CeO2 quantum dots | |
| CN100517772C (en) | An electrode of quantum dot sensitization solar battery and the corresponding preparation method | |
| Chandrasekaran et al. | Nanostructured silicon photoelectrodes for solar water electrolysis | |
| CN102122580B (en) | Method for preparing modified titanium dioxide nanotube dye-sensitized photoanode thin film | |
| CN101857382B (en) | Method for preparing sheet-shaped bismuth oxyiodide (BiOI) nano-film electrode | |
| KR100928302B1 (en) | Method for manufacturing solar cell of tricrystalline silicon using surfactant and acid solution wet etching method | |
| CN106637287B (en) | A method of preparing tantalic acid lanthanum oxynitride efficiency light electrode | |
| CN103871750B (en) | Anatase TiO2 nanometer tree array and application of anatase TiO2 nanometer tree array to solar cell preparation | |
| US20130276873A1 (en) | High level injection systems | |
| CN105568313B (en) | Branched semiconductor nano heterojunction photovoltaic pole materials of 3D and preparation method thereof | |
| Uthirakumar | Fabrication of ZnO based dye sensitized solar cells | |
| CN103779102B (en) | Low-temperature in-site builds BiOI/Bi2s3hetero-junction thin-film and flexible optoelectronic chemistry solar cell device | |
| CN106128772B (en) | A kind of preparation method of vulcanized lead quantum dot photovoltaic battery | |
| CN106169537A (en) | A kind of preparation method of solaode | |
| CN106319556A (en) | Preparation method for producing hydrogen electrode through efficient photoelectrocatalysis and application thereof | |
| CN109289890A (en) | Efficient self-supporting titanium nitride/nitrogen-doped titanium dioxide light electro catalytic electrode material and preparation method | |
| Saputrina et al. | Performances of dye-sensitized solar cell (DSSC) with working electrode of aluminum-doped ZnO nanorods | |
| CN105261483A (en) | Cu2ZnSnS4 sensitized TiO2 photo anode and in-situ preparation method and application thereof | |
| CN106848064A (en) | High stability perovskite solar cell and preparation method based on titanium dioxide indium sulphur quantum dot core shell structure | |
| CN113293404B (en) | Heterojunction photo-anode material and preparation method and application thereof | |
| CN101894678B (en) | Spongy quantum dot solar cell and preparation method thereof | |
| CN105470393A (en) | Water-electrolytic hydrogen making integrated device for perovskite solar cell and manufacturing method for integrated device | |
| CN105568309A (en) | Preparation method for photoelectrode of photoelectrochemical cell | |
| CN107268020A (en) | A kind of Ta3N5The preparation method and Ta of film3N5The application of film |
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 |
Application publication date: 20141001 |