CN102600819A - Porous titanium dioxide photocatalyst film and preparation method thereof - Google Patents
Porous titanium dioxide photocatalyst film and preparation method thereof Download PDFInfo
- Publication number
- CN102600819A CN102600819A CN2012100503849A CN201210050384A CN102600819A CN 102600819 A CN102600819 A CN 102600819A CN 2012100503849 A CN2012100503849 A CN 2012100503849A CN 201210050384 A CN201210050384 A CN 201210050384A CN 102600819 A CN102600819 A CN 102600819A
- Authority
- CN
- China
- Prior art keywords
- film
- titanium dioxide
- preparation
- ionic liquid
- concentration
- 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.)
- Granted
Links
Images
Landscapes
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a porous titanium dioxide photocatalyst film and a preparation method thereof. A substrate participates in an oxidizing reaction, an ionic liquid is taken as a template agent, and the reaction speed is controlled, so that a pure anatase phase titanium oxide film can be directly obtained on the surface of a titanium sheet. The preparation method comprises the following steps of: preparing a mixed solution of a hydrogen peroxide solution and an ionic liquid, i.e., 1-butyl-3-methylimidazolium tetrafluoroborate; soaking a metal titanium sheet into a reaction liquid for reacting in a baking oven of 80 DEG C for couple hours; and taking the reacted titanium sheet out, and baking to obtain a titanium dioxide film. The preparation method has the advantages of readily-available raw materials, simple process, easiness for controlling conditions, short preparing period and easiness for amplifying on a large scale. The prepared pure anatase structure titanium dioxide film high the advantages of high crystallinity, high purity, firm combination with the substrate, high stability and repeatability.
Description
Technical field
The invention belongs to the preparing technical field of semiconductor light-catalyst, be specifically related to a kind of porous titanium dioxide photocatalysis film and preparation method thereof.
Background technology
The high speed development of world industry provides when enriching material life to people, has also brought many environmental problems.The discharging of the three wastes in the commercial production (waste water, waste residue, waste gas) destroys the ecological balance, contaminated environment, and people's healthy living in serious threat.Wherein, waste water from dyestuff is one of industrial wastewater of present difficult degradation, and the dyeing waste water discharge capacity accounts for 1/10th of industrial wastewater total release, and environmental pollution is comparatively serious, and its color and luster is dark, and toxicity is big, and carcinogenic is arranged, serious harm ecological environment.
The conductor photocatalysis technology is multiple hazardous contaminant because powerful oxidability can be degraded, simultaneously, and its environmental friendliness; Solar energy capable of using; Characteristics such as reaction condition is gentle, and cost is low make it have extremely wide application prospect, receive the extensive concern of Chinese scholars day by day.Wherein, TiO
2Material is high because of photocatalytic activity, and stable in properties is nontoxic and material is cheap, becomes the current photochemical catalyst that has application potential most.Compare TiO with the powder catalyst
2Photocatalysis film can be avoided the loss and the energy waste that cause because of catalyst and separating of reactant when practical application, thereby has better application and be worth.But existing thin film of titanium oxide technology of preparing still exists preparation technology complicated, and scale is difficult amplifies, and degree of crystallinity is lower, and film combines shortcomings such as firmness is relatively poor with substrate.
Summary of the invention
The objective of the invention is to provides a kind of porous titanium dioxide photocatalysis film and preparation method and application simple, with low cost thereof to the existing in prior technology defective and the market demand.
The preparation method of porous titanium dioxide photocatalysis film of the present invention comprises the steps:
The bright and clean titanium sheet of polishing is immersed in the mixed solution of hydrogen peroxide solution and ionic liquid 1-butyl-3-methyl-tetrafluoroborate composition; The concentration of hydrogen peroxide solution is 10～15wt% in the mixed solution; The concentration of ionic liquid 1-butyl-3-methyl-tetrafluoroborate is 0.1～0.5wt%; Keep 8～10h at 80 ℃～100 ℃ constant temperature, clean, the oven dry back is at 450 ℃～500 ℃ following roasting 1～1.1h.
The concentration of hydrogen peroxide solution is preferably 15wt% in the mixed solution, and the concentration of ionic liquid 1-butyl-3-methyl-tetrafluoroborate is preferably 0.2wt%.
Can obtain porous titanium dioxide photocatalysis film of the present invention through technique scheme, film and the substrate of titanium sheet combine, and are the flower-shaped micro-sphere structure of porous, and its crystal formation is a Detitanium-ore-type.
Principle of the present invention is to utilize ion liquid template action and effectively controls reaction rate; Participate in oxidation reaction through substrate and directly obtain pure anatase titanium dioxide film at titanium plate surface, its microstructure is porous bouquet shape titanium dioxide and substrate be combined into.
The present invention compared with prior art, have the following advantages and outstanding effect: chemical reagent used in the present invention is common agents, cheap and easy to get; Preparation technology is simple, easy to operate, easy control of structure; Prepared titanium deoxid film combines with substrate firmly, and catalytic efficiency is high, has stable photocatalytic activity, long service life.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1 prepared sample.
Fig. 2 is the stereoscan photograph of embodiment 1 prepared sample.
Fig. 3 is embodiment 1 and embodiment 8 prepared samples UV-vis DRS collection of illustrative plates relatively.
Fig. 4 is that the photocatalytic activity of the prepared oxidation titanium film of embodiment 1-9 compares.
The life test result of the sample that Fig. 5 makes for embodiment 1.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
Following examples gained sample carries out structural characterization through following means: the X ray diffracting spectrum that adopts Rigaku D/Max-RB type X-ray diffractometer to measure carries out the structures of samples analysis; Adopt the appearance structure of the stereoscan photograph analytic sample of JEOLJSM-6380LV type ESEM acquisition; Adopt MC-2530 type ultraviolet-visible diffuse reflection spectrum (UV-vis DRS) to analyze absorbing properties.
Embodiment 1
To be of a size of 42cm with sand paper
2Titanium plate surface polish smooth, remove surface oxide layer; Use the ethanol and the aqueous isopropanol supersound washing of 1: 1 volume ratio, use the deionized water supersound washing then, use N at last
2Purge to dry.
Titanium sheet after the processing is soaked in the H of 50mL 15wt%
2O
2With (concentration of hydrogen peroxide solution is 15.0wt% in the mixed solution in the mixed solution of 0.10mL ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate; The concentration of ionic liquid 1-butyl-3-methyl-tetrafluoroborate is 0.2wt%), place baking oven to react 8h down at 80 ℃.Reacted titanium sheet behind deionized water rinsing 3 times in 100 ℃ of oven dry down, afterwards at 450 ℃ of following roasting 1h, target product.
Fig. 1 is the X-ray diffracting spectrum of the prepared sample of present embodiment, can confirm that from collection of illustrative plates the film of gained sample surfaces is Detitanium-ore-type TiO
2
Fig. 2 is the SEM photo of the prepared sample of present embodiment, it is thus clear that the film of gained sample surfaces is the loose structure with flower-shaped microballoon, microsphere diameter is about 300nm from photo.
Embodiment 2
Change the ionic liquid consumption into 0.05mL, all the other contents and embodiment 1 said identical (concentration of hydrogen peroxide solution is 15.0wt% in the mixed solution, and the concentration of ionic liquid 1-butyl-3-methyl-tetrafluoroborate is 0.1wt%).Can confirm that by the X-ray diffracting spectrum of the prepared sample of present embodiment the film of gained sample surfaces is Detitanium-ore-type TiO
2, can know that by the SEM photo it is the random laminated structure of porous.
Embodiment 3
Change the ionic liquid consumption into 0.15mL, all the other contents and embodiment 1 said identical (concentration of hydrogen peroxide solution is 15.0wt% in the mixed solution, and the concentration of ionic liquid 1-butyl-3-methyl-tetrafluoroborate is 0.4wt%).Can confirm that by the X-ray diffracting spectrum of the prepared sample of present embodiment the film of gained sample surfaces is Detitanium-ore-type TiO
2, can know that by the SEM photo it is the loose structure with flower-shaped microballoon, microsphere diameter is about 1 μ m.
Embodiment 4
Change the ionic liquid consumption into 0.20mL, all the other contents and embodiment 1 said identical (concentration of hydrogen peroxide solution is 15.0wt% in the mixed solution, and the concentration of ionic liquid 1-butyl-3-methyl-tetrafluoroborate is 0.5wt%).Can confirm that by the X-ray diffracting spectrum of the prepared sample of present embodiment the film of gained sample surfaces is Detitanium-ore-type TiO
2, can know that by the SEM photo it is the loose structure with flower-shaped microballoon, microsphere diameter is about 2 μ m.
Embodiment 5
To the reaction time change 4h into, all the other contents are said identical with embodiment 1.Can confirm that by the X-ray diffracting spectrum of the prepared sample of present embodiment the film of gained sample surfaces is Detitanium-ore-type TiO
2, can know that by the SEM photo it is a loose structure, does not have flower-shaped microballoon.
Embodiment 6
To the reaction time change 6h into, all the other contents are said identical with embodiment 1.Can confirm that by the X-ray diffracting spectrum of the prepared sample of present embodiment the film of gained sample surfaces is Detitanium-ore-type TiO
2, can know that by the SEM photo it is a loose structure, does not have flower-shaped microballoon.
Embodiment 7
To the reaction time change 10h into, all the other contents are said identical with embodiment 1.Can confirm that by the X-ray diffracting spectrum of the prepared sample of present embodiment the film of gained sample surfaces is Detitanium-ore-type TiO
2, can know that by the SEM photo it is the loose structure with flower-shaped microballoon.
Do not add ionic liquid, all the other contents are said identical with embodiment 1.Can confirm that by the X-ray diffracting spectrum of the prepared sample of present embodiment the film of gained sample surfaces is Detitanium-ore-type TiO
2, can know that by the SEM photo it is the random laminated structure of porous.
Fig. 3 is embodiment 1 and embodiment 8 prepared samples UV-vis DRS collection of illustrative plates relatively, can know that by figure the titanium deoxid film with bouquet structure of embodiment 1 does not add the optical absorption intensity of the prepared sample that obtains of ionic liquid in the ultra-violet (UV) band than present embodiment and is significantly improved.
The photocatalysis performance of above-mentioned each embodiment gained sample:
Get the rhodamine B solution that resulting thin film of titanium oxide among the foregoing description 1-8 places the 10mg/L of 55mL, make the surface area of Ti sheet 43% be dipped under the liquid level, residual surface is exposed in the air, places disk reactor then.
The 8W uviol lamp that with the characteristic wavelength is 365nm be light source irradiation in Ti sheet surface, with the distance of Ti sheet be 4.0cm; Titanium sheet rotating speed is 90rpm, and reaction temperature is 30 ℃, and absorption reaches and carry out photocatalytic activity after the adsorption equilibrium and measure half an hour in the dark, and the reaction time is 3h.
The reaction back is measured the change in concentration of rhodamine B and is calculated degradation rate thus at 553nm with the UV spectrophotometer.Be less than 5% rhodamine B decomposition owing to after reacting 3 hours under unglazed photograph or the catalyst-free condition, only have, therefore can ignore the error that causes thus.
Fig. 4 is that the photocatalytic activity of the prepared titanium deoxid film of embodiment 1-8 can compare.Can be known that by Fig. 4 the resulting sample of various embodiments of the present invention all has good photocatalytic activity, adding the film sample activity for preparing behind the ionic liquid is the best with embodiment 1 all, and all is higher than and does not add ion liquid embodiment 8.
Adopt embodiment 1 gained sample to carry out life experiment:
By the photocatalysis performance of above-mentioned steps test implementation example 1 gained sample, difference is that the reaction time is 4h, writes down the change in concentration situation of the rhodamine B of each hour.After reaction is accomplished the Ti sheet taken out and with after the washed with de-ionized water 3 times in 100 ℃ of oven dry 12h, repeat above-mentioned reaction, 10 times altogether.
The life test result is as shown in Figure 5, can find out that the product of gained of the present invention has stable photocatalytic activity.
The foregoing description is interpreted as only being used to the present invention is described and is not used in restriction protection scope of the present invention.After the content of having read the present invention's record, those skilled in the art can do various changes or modification to the present invention, and these equivalences change and modify and fall into claim of the present invention institute restricted portion equally.
Claims (5)
1. a porous titanium dioxide photocatalysis film is characterized in that, film and the substrate of titanium sheet combine, and the surface is the flower-shaped micro-sphere structure of porous, and its crystal formation is a Detitanium-ore-type.
2. the preparation method of the described porous titanium dioxide thin-film of claim 1; It is characterized in that the bright and clean titanium sheet of polishing is immersed in the mixed solution of hydrogen peroxide solution and ionic liquid 1-butyl-3-methyl-tetrafluoroborate composition, the concentration of hydrogen peroxide solution is 10～15wt% in the mixed solution; The concentration of ionic liquid 1-butyl-3-methyl-tetrafluoroborate is 0.1～0.5wt%; Keep 8～10h at 80 ℃～100 ℃ constant temperature, clean, the oven dry back is at 450 ℃～500 ℃ following roasting 1～1.1h.
3. the preparation method of the described porous titanium dioxide thin-film of claim 2 is characterized in that, the concentration of hydrogen peroxide solution is 15wt% in the mixed solution, and the concentration of ionic liquid 1-butyl-3-methyl-tetrafluoroborate is 0.2wt%.
4. the described porous titanium dioxide photocatalysis film of claim 1 is applied to the degraded of organic pollution.
5. the described porous titanium dioxide photocatalysis film of claim 4 is applied to the degraded of rhodamine B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210050384 CN102600819B (en) | 2012-02-29 | 2012-02-29 | Porous titanium dioxide photocatalyst film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210050384 CN102600819B (en) | 2012-02-29 | 2012-02-29 | Porous titanium dioxide photocatalyst film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102600819A true CN102600819A (en) | 2012-07-25 |
| CN102600819B CN102600819B (en) | 2013-12-25 |
Family
ID=46518808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210050384 Expired - Fee Related CN102600819B (en) | 2012-02-29 | 2012-02-29 | Porous titanium dioxide photocatalyst film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102600819B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657620A (en) * | 2013-11-19 | 2014-03-26 | 浙江大学 | Preparation method for anatase type microporous titanium dioxide material for purifying indoor air |
| CN108479857A (en) * | 2018-04-14 | 2018-09-04 | 扬州工业职业技术学院 | A kind of preparation method of the polyaniline/titanium dioxide composite material of Ionic Liquid Modified |
| CN114405292A (en) * | 2022-03-01 | 2022-04-29 | 苏州仕净科技股份有限公司 | Novel composite nanofiltration membrane modified by ionic liquid and preparation method and application thereof |
| CN114632504A (en) * | 2022-03-14 | 2022-06-17 | 徐州市正峰锌业有限公司 | Preparation method of blast furnace ash photocatalytic material and wastewater treatment application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003200058A (en) * | 2002-01-11 | 2003-07-15 | Ulvac Japan Ltd | Method for forming photocatalyst film |
| CN102071409A (en) * | 2010-11-19 | 2011-05-25 | 长春理工大学 | TiO2 nanoparticle porous film and preparation method thereof |
-
2012
- 2012-02-29 CN CN 201210050384 patent/CN102600819B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003200058A (en) * | 2002-01-11 | 2003-07-15 | Ulvac Japan Ltd | Method for forming photocatalyst film |
| CN102071409A (en) * | 2010-11-19 | 2011-05-25 | 长春理工大学 | TiO2 nanoparticle porous film and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JIN-MING WU, ET AL.: "Porous titania films prepared from interactions of titanium with hydrogen peroxide solution", 《SCRIPTA MATERIALIA》 * |
| QUANJUN XIANG, ET AL.: "Tunable photocatalytic selectivity of TiO2 films consisted of flower-like microspheres with exposed {001} facets", 《CHEMICAL COMMUNICATIONS》 * |
| YONG ZHOU, ET AL.: "Synthesis of very small TiO2 nanocrystals in a room-temperature ionic liquid and their self-assembly toward mesoporous spherical aggregates", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657620A (en) * | 2013-11-19 | 2014-03-26 | 浙江大学 | Preparation method for anatase type microporous titanium dioxide material for purifying indoor air |
| CN103657620B (en) * | 2013-11-19 | 2015-09-30 | 浙江大学 | A kind of anatase titanium dioxide microporous titania materials preparation method purified the air of a room |
| CN108479857A (en) * | 2018-04-14 | 2018-09-04 | 扬州工业职业技术学院 | A kind of preparation method of the polyaniline/titanium dioxide composite material of Ionic Liquid Modified |
| CN108479857B (en) * | 2018-04-14 | 2021-04-27 | 扬州工业职业技术学院 | Preparation method of ionic liquid modified polyaniline/titanium dioxide composite material |
| CN114405292A (en) * | 2022-03-01 | 2022-04-29 | 苏州仕净科技股份有限公司 | Novel composite nanofiltration membrane modified by ionic liquid and preparation method and application thereof |
| CN114405292B (en) * | 2022-03-01 | 2023-10-27 | 苏州仕净科技股份有限公司 | Composite nanofiltration membrane modified by ionic liquid and preparation method and application thereof |
| CN114632504A (en) * | 2022-03-14 | 2022-06-17 | 徐州市正峰锌业有限公司 | Preparation method of blast furnace ash photocatalytic material and wastewater treatment application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102600819B (en) | 2013-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nogueira et al. | Improved visible light photoactivity of CuBi2O4/CuO heterojunctions for photodegradation of methylene blue and metronidazole | |
| Tian et al. | Hydrothermal synthesis of m-BiVO4/t-BiVO4 heterostructure for organic pollutants degradation: Insight into the photocatalytic mechanism of exposed facets from crystalline phase controlling | |
| Rao et al. | Defect chemistry of Er3+-doped TiO2 and its photocatalytic activity for the degradation of flowing gas-phase VOCs | |
| CN101791558B (en) | Bismuth ferrite microsphere photocatalyst with hollow structure and preparation method thereof | |
| Zhao et al. | Noble metal-free Bi nanoparticles supported on TiO 2 with plasmon-enhanced visible light photocatalytic air purification | |
| Zhu et al. | Insight into the role of Ti3+ in photocatalytic performance of shuriken-shaped BiVO4/TiO2− x heterojunction | |
| Gao et al. | One-pot synthesis of Ag/r-GO/TiO 2 nanocomposites with high solar absorption and enhanced anti-recombination in photocatalytic applications | |
| Wang et al. | A highly efficient visible-light-activated photocatalyst based on bismuth-and sulfur-codoped TiO2 | |
| She et al. | Controllable synthesis of CeO 2/gC 3 N 4 composites and their applications in the environment | |
| Danwittayakul et al. | Efficient solar photocatalytic degradation of textile wastewater using ZnO/ZTO composites | |
| Nezamzadeh-Ejhieh et al. | Solar photodecolorization of methylene blue by CuO/X zeolite as a heterogeneous catalyst | |
| Peng et al. | Room temperature synthesis of Ti–MCM-48 and Ti–MCM-41 mesoporous materials and their performance on photocatalytic splitting of water | |
| Wang et al. | Ordered mesoporous TiO 2 with exposed (001) facets and enhanced activity in photocatalytic selective oxidation of alcohols | |
| Sapawe et al. | Isomorphous substitution of Zr in the framework of aluminosilicate HY by an electrochemical method: Evaluation by methylene blue decolorization | |
| Bi et al. | Improved photocatalytic activity of WO3 through clustered Fe2O3 for organic degradation in the presence of H2O2 | |
| Shi et al. | Few layered BiOBr with expanded interlayer spacing and oxygen vacancies for efficient decomposition of real oil field produced wastewater | |
| Xu et al. | Enhanced photocatalytic activity of Ag3VO4 loaded with rare-earth elements under visible-light irradiation | |
| Ismail et al. | Metal‐Free Porphyrin‐Sensitized Mesoporous Titania Films For Visible‐Light Indoor Air Oxidation | |
| Zhou et al. | Fabrication and photoelectrocatalytic properties of nanocrystalline monoclinic BiVO4 thin-film electrode | |
| Li et al. | Preparation of visible light-driven SnS2/TiO2 nanocomposite photocatalyst for the reduction of aqueous Cr (VI) | |
| Sun et al. | Facile synthesis of oxygen defective yolk–shell BiO 2− x for visible-light-driven photocatalytic inactivation of Escherichia coli | |
| Feng et al. | Postillumination activity in a single-phase photocatalyst of Mo-doped TiO2 nanotube array from its photocatalytic “memory” | |
| Xia et al. | Photocatalytic degradation of dyes over cobalt doped mesoporous SBA-15 under sunlight | |
| CN102380367B (en) | Control synthetic method of high-visible-light-activity mixed crystal type BiVO4 photocatalysts | |
| Lee et al. | Photocatalytic characteristics of boron and nitrogen doped titania film synthesized by micro-arc oxidation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131225 Termination date: 20170229 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |