CN101037226A - Novel Titanium dioxide, preparation method and application thereof - Google Patents
Novel Titanium dioxide, preparation method and application thereof Download PDFInfo
- Publication number
- CN101037226A CN101037226A CN 200710054099 CN200710054099A CN101037226A CN 101037226 A CN101037226 A CN 101037226A CN 200710054099 CN200710054099 CN 200710054099 CN 200710054099 A CN200710054099 A CN 200710054099A CN 101037226 A CN101037226 A CN 101037226A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- preparation
- novel titanium
- novel
- photoelectrochemistry
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002071 nanotube Substances 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 230000004044 response Effects 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 5
- 238000007669 thermal treatment Methods 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract 1
- 230000031700 light absorption Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 abstract 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 239000002002 slurry Substances 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
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a novel titanium dioxide, a preparation method and the application of the same, which is characterized in that: (1)the crystallographic form is anatase structure with a specific surface area of 50~70 m2/g; (2)the crystal lattice contains steady single-electron-trapped oxygen vacancies and Ti3+ crystal lattice defect; (3) a visible light absorption property and a visible light photoluminescent property are possessed; (4)a p-type semiconductor photoelectrochemistry response is presented under the irradiation of visible light, and a n-type semiconductor photoelectrochemistry response is presented under the irradiation of ultraviolet light. The titanium dioxide is prepared by nanotube titanic acid which is subjected to heat treatment for 0.5~72 hours at 400~700 DEG C and then is cooled. The novel titanium dioxide can be used as photoelectric switch material. The present invention has a simple preparation method, a convenient operation, a low cost, and is adapted to mass production.
Description
Technical field
The invention belongs to technical field of nano material, relate to a kind of Novel Titanium dioxide, preparation method and application thereof.
Background technology
Nano titanium oxide has broad application prospects at aspect such as aspect catalysis and the environment protection, and can be applicable to industrial sectors such as daily product, coating, electronics, so nano titanium oxide shows huge market outlook.People are the range of application of expansion titanium dioxide in recent years, attempt obtaining with different preparation methods the titanium dioxide of different crystal forms and pattern.As: utilize the precipitator method with TiCl
4For presoma is prepared globular anatase titanium dioxide [J.AM.Ceram.Soc.1997,80:743-749] by pure pyrolysis method.Utilize the mixed crystal that can prepare anatase octahedrite and rutile of oxidation reduction process preparation, specific surface is 80m
2/ g[Mater Lett.1998,34:290-293], the titanium dioxide with special property of development of new becomes the focus of people's research.The nanotube metatitanic acid is as a kind of novel monodimension nanometer material, because it has nano tubular structure, and bigger specific surface area, people are synthetic to it, big quantity research has been carried out in structure, character and application.In the preparation method of existing titanium dioxide, also do not utilize the nanotube metatitanic acid to have the report of special light electrical property titanium dioxide by the thermal treatment preparation.
Summary of the invention
The purpose of this invention is to provide a kind of novel titanium dioxide.
Further aim of the present invention provides the preparation method of the Novel Titanium dioxide that a kind of technology is simple, easy to operate, cost is low, be suitable for producing in enormous quantities.
Another object of the present invention provides the application of a kind of Novel Titanium dioxide on the preparation photoelectric switch material.
For achieving the above object, the present invention by the following technical solutions: a kind of Novel Titanium dioxide,
(1), crystal formation is anatase structured, specific surface area is 50～70m
2/ g;
(2), contain stable constraint single electron oxygen room and Ti in the lattice
3+Lattice imperfection;
(3), has visible absorption and visible fluorescence character;
(4), under radiation of visible light, show p N-type semiconductorN photoelectrochemistry response, under UV-irradiation, show as the response of n N-type semiconductorN photoelectrochemistry.
The preparation method of Novel Titanium dioxide: be warming up to 400～700 ℃ according to the constant temperature rise rate, the nanotube metatitanic acid is heat-treated 0.5～72h, cooling promptly gets product.
The described naturally cooling that is cooled to.
Thermal treatment temp is preferably 500～600 ℃, and heat treatment time is preferably 2～8h.
Novel Titanium dioxide can be used on the preparation photoelectric switch material.
The preparation method of nanotube metatitanic acid:
Titanium dioxide or metatitanic acid slurry are mixed with strong base solution, in the oil bath under 70～150 ℃ temperature reflux 5～60 hours, cooling-sedimentation, incline and supernatant liquor, being washed with distilled water to pH value is 6～8, the product that filtration obtains soaked in the dilute solution of strong acid 5～72 hours, promptly obtained the nanotube metatitanic acid.
The present invention is to be the thermal treatment presoma with the nanotube metatitanic acid, 400～700 ℃ of following thermal treatments 0.5～72 hour, prepares a kind of novel anatase titanium dioxide by naturally cooling then, and this titanium dioxide specific surface area is big, and specific surface area is 50～70m
2/ g, crystal formation is an anatase crystal, and contains a large amount of stable lattice imperfections in the titanium dioxide crystal lattice: constraint single electron oxygen room (single-electron-trappedoxygen vacancy, SETOV) and Ti
3+, just because of containing stable SETOV and Ti
3+Lattice imperfection, new Ti O of the present invention
2(anatase) demonstrate some special photoelectric properties: promptly have visible absorption and visible fluorescence character, under visible light, show as the photoelectrochemistry response of p N-type semiconductorN under the irradiation, and, therefore can be used as photoelectric switch material in the next photoelectrochemistry response that shows as the n N-type semiconductorN of UV-irradiation; Preparation technology of the present invention is simple, easy to operate, cost is low, is suitable for producing in enormous quantities.
Description of drawings
Fig. 1 is X-ray powder diffraction (XRD) figure of embodiment 2;
Fig. 2 is high-resolution-ration transmission electric-lens (HRTEM) figure of embodiment 2;
Fig. 3 is electron paramagnetic resonance (ESR) figure of embodiment 2;
Fig. 4 is the ultraviolet-visible diffused reflection spectrum of embodiment 2;
Fig. 5 is the fluorescence spectrum of embodiment 2;
Fig. 6 is X-ray powder diffraction (XRD) figure of embodiment 3;
Fig. 7 is X-ray powder diffraction (XRD) figure of embodiment 4;
Fig. 8 is the photoelectric current-bias voltage figure of titanium dioxide of the present invention under radiation of visible light;
Fig. 9 is the photoelectric current-bias voltage figure of titanium dioxide of the present invention under UV-irradiation;
Figure 10 for titanium dioxide of the present invention keep bias voltage be-during 0.4ev, the photoelectricity behavior outcome of the variable semi-conductor Novel Titanium dioxide of n/p type.
The XRD analysis instrument is X ' pert pro type x-ray diffractometer (XRD, Dutch Philips Company), adopt CuK α line excitaton source, λ=0.15418366nm, voltage 40kV, electric current 40mA, sample Product can be powder and place the pressing of sample stage groove or sample dispersion to drip on slide in acetone, dry in the air Become film, direct-detection after doing.
It is JEM-2010 type high-resolution-ration transmission electric-lens that HRTEM analyzes instrument.
It is Switzerland ESP300E electron spin resonanceapparatus that ESR analyzes used instrument.
It is Japanese Shimadzu U3010 ultraviolet-visible scattered reflection instrument that UV-Vis analyzes used instrument.
The used instrument of spectrofluorimetry is SPEX F212 XRF.
The photoelectrochemical behaviour evaluation is finished at DJS-292 type potentiostat, and visible light source is the xenon lamp of 500W, and by the edge filter of infrared-filtered device and 420nm, measuring light intensity through light intensity meter is 0.6 mW/cm2, ultraviolet source is the black light lamp of 8W, measuring light intensity through light intensity meter is 0.7mW/cm2。
Embodiment
Embodiment 1, it is in the polytetrafluoroethylcontainer container in 40% the NaOH solution that 3g titanium dioxide (P25 type) is slowly joined 300ml concentration, place oil bath to heat up 118 ℃, reflux 24h, cooling-sedimentation, inclining supernatant liquor, be washed with distilled water to PH=8.0, filter, use the salt acid soak 5 hours of 0.1mol/L then, filter, wash, be drying to obtain presoma nanotube metatitanic acid.
As shown in Figure 1, to turn out to be product of the present invention be anatase structured to X-ray diffraction analysis; As shown in Figure 2, high-resolution-ration transmission electric-lens (HRTEM) is analyzed in the lattice turn out to be product of the present invention and is contained a large amount of lattice imperfections; As shown in Figure 3, the electron paramagnetic resonance analysis confirms to contain stable constraint single electron oxygen room and Ti in the product lattice of the present invention
3+Lattice imperfection; UV, visible light diffused reflection spectrum and fluorescence spectrum shown in Figure 5 show that this Novel Titanium dioxide has visible absorption and visible fluorescence as shown in Figure 4.
Shown in Fig. 8,9, with P25 (n N-type semiconductorN) as reference, at visible light (λ 〉=420nm, E
PhotonUnder=2.95eV) the irradiation, Novel Titanium dioxide shows as the p N-type semiconductorN, at (λ 〉=365nm, the E of UV-light
PhotonUnder=3.40eV) the irradiation, novel sharp titanium dioxide shows as the n N-type semiconductorN, and the semiconductor type of novel anatase octahedrite can be by light guide ,+0.1V＞V
BiasBeing the p type under visible light during＞-0.7V, is the n type under UV-light.
As shown in figure 10, at fixed bias V
BiasDuring=-0.4V, the variable semi-conductive photoelectrochemistry behavior of n/p type.As can be seen from the figure under visible light radiation, the mensuration electric current reaches a stable negative value through 40s, and the increment of electric current is for negative, and what show demonstration this moment is the behavior of p N-type semiconductorN, keep closing visible light source suddenly behind the 2-3min, the electric current of dark attitude is got back to the level before the illumination again.When UV-light is shone working electrode, electric current reach very soon one stable on the occasion of, the increment of electric current (is photoelectric current I
PhotoValue) for just, show the time n N-type semiconductorN behavior that shows this moment, keep closing visible light source suddenly behind the 2-3min, the electric current of dark attitude is got back to the level before the illumination again.Therefore, this special type material can be used for the photoswitc material.
Claims (5)
1, a kind of Novel Titanium dioxide is characterized in that,
(1), crystal formation is anatase structured, specific surface area is 50～70m
2/ g;
(2), contain stable constraint single electron oxygen room and Ti in the lattice
3+Lattice imperfection;
(3), has visible absorption and visible fluorescence character;
(4), under radiation of visible light, show p N-type semiconductorN photoelectrochemistry response, under UV-irradiation, show as the response of n N-type semiconductorN photoelectrochemistry.
2, the preparation method of Novel Titanium dioxide is characterized in that, is warming up to 400～700 ℃ according to the constant temperature rise rate, and the nanotube metatitanic acid is heat-treated 0.5～72h, and cooling promptly gets product.
3, as the preparation method of Novel Titanium dioxide as described in claims 2, it is characterized in that the described naturally cooling that is cooled to.
4, as the preparation method of Novel Titanium dioxide as described in claims 3, it is characterized in that thermal treatment temp is 500～600 ℃, heat treatment time is 2～8h.
5, the application of Novel Titanium dioxide on the preparation photoelectric switch material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710054099 CN101037226A (en) | 2007-03-23 | 2007-03-23 | Novel Titanium dioxide, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710054099 CN101037226A (en) | 2007-03-23 | 2007-03-23 | Novel Titanium dioxide, preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101037226A true CN101037226A (en) | 2007-09-19 |
Family
ID=38888434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710054099 Pending CN101037226A (en) | 2007-03-23 | 2007-03-23 | Novel Titanium dioxide, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101037226A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279762B (en) * | 2008-05-26 | 2010-06-02 | 武汉理工大学 | A kind of preparation method of spindle-shaped anatase TiO2 nanocrystal material |
| CN103334142A (en) * | 2013-06-17 | 2013-10-02 | 华中科技大学 | A self-doping modified high-conductivity TiO2 nanotube array preparation method |
| CN103626225A (en) * | 2013-10-25 | 2014-03-12 | 河南大学 | Anatase titanium dioxide nanocrystal containing single-electron-trapped oxygen vacancies and with exposed {001} face and preparation method thereof |
| CN106582593A (en) * | 2016-12-15 | 2017-04-26 | 河南师范大学 | Method for synthesizing rutile phase titania photocatalyst containing electron-trapped oxygen vacancies |
| CN110038560A (en) * | 2019-04-28 | 2019-07-23 | 河南大学 | A kind of sea urchin shape hollow platinum/titanium dioxide nano material, preparation method and application of oxygen-containing vacancy |
-
2007
- 2007-03-23 CN CN 200710054099 patent/CN101037226A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279762B (en) * | 2008-05-26 | 2010-06-02 | 武汉理工大学 | A kind of preparation method of spindle-shaped anatase TiO2 nanocrystal material |
| CN103334142A (en) * | 2013-06-17 | 2013-10-02 | 华中科技大学 | A self-doping modified high-conductivity TiO2 nanotube array preparation method |
| CN103626225A (en) * | 2013-10-25 | 2014-03-12 | 河南大学 | Anatase titanium dioxide nanocrystal containing single-electron-trapped oxygen vacancies and with exposed {001} face and preparation method thereof |
| CN103626225B (en) * | 2013-10-25 | 2015-08-26 | 河南大学 | A kind of expose that { 001} face anatase titania is nanocrystalline and preparation method thereof containing constraint single electron Lacking oxygen |
| CN106582593A (en) * | 2016-12-15 | 2017-04-26 | 河南师范大学 | Method for synthesizing rutile phase titania photocatalyst containing electron-trapped oxygen vacancies |
| CN106582593B (en) * | 2016-12-15 | 2020-04-28 | 河南师范大学 | A kind of synthetic method of rutile phase titanium dioxide photocatalyst containing bound electron oxygen vacancies |
| CN110038560A (en) * | 2019-04-28 | 2019-07-23 | 河南大学 | A kind of sea urchin shape hollow platinum/titanium dioxide nano material, preparation method and application of oxygen-containing vacancy |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ramakrishnan et al. | Size controlled synthesis of TiO2 nanoparticles by modified solvothermal method towards effective photo catalytic and photovoltaic applications | |
| Ranjith et al. | Effective shell wall thickness of vertically aligned ZnO-ZnS core-shell nanorod arrays on visible photocatalytic and photo sensing properties | |
| Rahman Khan et al. | Simple fabrication of PVA–ZnS composite films with superior photocatalytic performance: enhanced luminescence property, morphology, and thermal stability | |
| Patrocinio et al. | Layer-by-layer TiO2/WO3 thin films as efficient photocatalytic self-cleaning surfaces | |
| Zare et al. | Evolution of rough-surface geometry and crystalline structures of aligned TiO2 nanotubes for photoelectrochemical water splitting | |
| Nayak et al. | Facile green synthesis of WO3· H2O nanoplates and WO3 nanowires with enhanced photoelectrochemical performance | |
| Mali et al. | Eosin-Y and N3-Dye sensitized solar cells (DSSCs) based on novel nanocoral TiO2: A comparative study | |
| Zhang et al. | Particle-size-dependent distribution of carboxylate adsorption sites on TiO2 nanoparticle surfaces: insights into the surface modification of nanostructured TiO2 electrodes | |
| Saleem et al. | Synthesis, characterization, and performance evaluation of pristine and cerium‐doped WO3 nanoparticles for photodegradation of methylene blue via solar irradiation | |
| CN114772635B (en) | Preparation method of titanium dioxide nano cone array/indium zinc sulfide photocatalyst containing sulfur vacancies | |
| Kokate et al. | CdS sensitized cadmium doped ZnO solar cell: Fabrication and characterizations | |
| Patil et al. | Synthesis of photosensitive nanograined TiO2 thin films by SILAR method | |
| Chaudhari et al. | Effect of annealing on the photocatalytic activity of chemically prepared TiO2 thin films under visible light | |
| Rajan et al. | Ameliorating the photovoltaic conversion efficiency of ZnO nanorod based dye-sensitized solar cells by strontium doping | |
| CN101037226A (en) | Novel Titanium dioxide, preparation method and application thereof | |
| Govindan et al. | One-pot microwave synthesis of SnSe and Lanthanum doped SnSe nanostructure with direct Z scheme pattern for excellent photodegradation of organic pollutants | |
| Chen et al. | Preparation and Characterization of Pure Rutile TiO2 Nanoparticles for Photocatalytic Study and Thin Films for Dye‐Sensitized Solar Cells | |
| Liu et al. | Construction of ternary hollow TiO2-ZnS@ ZnO heterostructure with enhanced visible-light photoactivity | |
| Wang et al. | Hierarchical Ag/AgCl-TiO2 hollow spheres with enhanced visible-light photocatalytic activity | |
| Yao et al. | TiO2-coated copper zinc tin sulfide photocatalyst for efficient photocatalytic decolourization of dye-containing wastewater | |
| Mrabet et al. | Mechanism of wettability conversion on sprayed Zn2SnO4 thin films surfaces modified by thermal annealing in air | |
| Chakraborty et al. | Self-powered broadband photodetection with mixed-phase black TiO2-assisted output boosting of a biobased triboelectric nanogenerator | |
| Guitoume et al. | Structural, optical and photoelectrochemical properties of TiO2 films decorated with plasmonic silver nanoparticles | |
| Bhat et al. | Hydrothermal synthesis of one-dimensional, rutile TiO2 nanograss arrays for photoelectrochemical solar cell | |
| Desai et al. | Influence of deposition temperature on the optical, structural, morphological, compositional and photoelectrochemical properties of TiO2 thin films |
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 |