CN104843780B - A kind of preparation method of anatase black nano titanium oxide powder - Google Patents
A kind of preparation method of anatase black nano titanium oxide powder Download PDFInfo
- Publication number
- CN104843780B CN104843780B CN201510216852.9A CN201510216852A CN104843780B CN 104843780 B CN104843780 B CN 104843780B CN 201510216852 A CN201510216852 A CN 201510216852A CN 104843780 B CN104843780 B CN 104843780B
- Authority
- CN
- China
- Prior art keywords
- titanium oxide
- solution
- anatase
- preparation
- nano titanium
- 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.)
- Expired - Fee Related
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The preparation method that the invention discloses a kind of anatase black nano titanium oxide powder, by Ti4+Solution and Ti3+Solution is obtained by mixing material liquid；Then in described material liquid, add precipitant, be that under 5～7 conditions, stirring reaction is precipitated thing in pH value；After the filtration of described precipitate, cleaning, carry out roasting, namely obtain anatase black nano titanium oxide powder。Black nano titanium oxide powder product obtained by the present invention is pure Anatase, its Ti3+Content has good controllability。Preparation method of the present invention not only considerably reduces production cost, and preparation technology is simple, polyvinyl chloride, can mass production, it is easy to the realization of industrialization, it is possible to effectively meet the production to black nano titanium oxide and user demand。
Description
Technical field
The present invention relates to technical field of nano material, the preparation method particularly relating to a kind of anatase black nano titanium oxide powder。
Background technology
Titanium dioxide, as important new forms of energy and environment conscious material, can be applicable to the fields such as photocatalysis, solar electrical energy generation, solar energy heating。But, titanium dioxide faces huge challenge in Solar use, main reason is that its light abstraction width separation efficiency narrow, electron-hole pair is low。Titanium dioxide can only absorb in solar spectrum～ultraviolet light of 5%, and the energy of visible ray and near infrared light cannot be utilized；Intrinsic conductivity only has～10-10S/cm, is unfavorable for separation and the transmission of photo-generate electron-hole pair。These problems have had a strong impact on the titanium dioxide extensive use in energy and environment field, thus solar energy cannot be made full use of。Result of study shows, adopts trivalent titanium ion that titanium dioxide carries out auto-dope and can effectively reduce its energy gap, particularly after titanous mixes titanium oxide with finite concentration, titanium oxide can be made to become black so that it is the absorbance of visible ray is reached more than 80%。Black oxidation titanium is owing to having good solar energy wide-spectrum absorption, chemical physical stability and higher carrier concentration and electron transfer performance, such that it is able to meet the requirement of high-efficiency solar。
At present, black oxidation titanium preparation method mainly has: high-temperature hydrogen reduction method, hydrogen plasma reducing process, aluminum reduction method, two step nonmetal doping methods。Wherein, there is complex process, length consuming time, high in cost of production shortcoming in hydrogen reduction method, and there is inflammable and explosive unsafe factor of Denging；Hydrogen plasma reducing process, aluminum reduction method also exist too equipment investment costly, the shortcoming such as energy consumption is high, process conditions are complicated, and aluminum reduction method its to prepare yield few；The shortcoming that black oxidation titanium prepared by two step nonmetal doping methods exists light incomplete absorption。In sum, prior art black oxidation titanium preparation method is still difficult to meet the demand of industrialization, finds a kind of new method easily preparing anatase black oxidation titanium valve, and synthesizing the black oxidation titanium valve of excellent performance with mass is problem anxious to be resolved at present。
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided that a kind of technique is simple, polyvinyl chloride, can the preparation method of anatase black nano titanium oxide powder of mass production, to be effectively improved titanium oxide photochemical catalyst activity, and realize industrialization, thus meet the production to black nano titanium oxide and user demand。
The purpose of the present invention is achieved by the following technical programs:
The preparation method of a kind of anatase black nano titanium oxide powder provided by the invention is: by Ti4+Solution and Ti3+Solution is obtained by mixing material liquid；Then in described material liquid, add precipitant, be that under 5～7 conditions, stirring reaction is precipitated thing in pH value；After the filtration of described precipitate, cleaning, carry out roasting, namely obtain anatase black nano titanium oxide powder。
The present invention can take measure further below: the preparation method of described anatase black nano titanium oxide powder, comprises the following steps:
(1)Ti4+The preparation of solution
Joining in 50～600ml deionized water by 10～60g ammonium titanium fluoride powder, stirring to ammonium titanium fluoride powder is completely dissolved the transparent Ti of formation4+Solution；Or by 10～60gTiCl4It is dissolved in concentrated hydrochloric acid and forms transparent Ti4+Solution；
(2) preparation of material liquid
According to mol ratio Ti3+/Ti4+=1～3, at described Ti4+Solution adds TiCl3Solution stirring mixing 10～60min, obtains material liquid；
(3) precipitation
Adding 20～90g precipitant in described material liquid, stirring and regulate solution system pH value is 5～7, and forms blue precipitate；
(4) precipitate calcining
Described precipitate is filtered, cleans the Cl with scavenger precipitation thing surface adsorption-And F-, then precipitate is carried out in high-purity argon gas atmosphere furnace roasting, sintering temperature is 450～600 DEG C, and temperature retention time is 1～2h, namely obtains anatase black nano titanium oxide powder after its cooling。
Further, precipitant of the present invention is lower fatty acid, it is preferable that propanoic acid or butanoic acid。
In such scheme, anatase black nano titanium oxide powder of the present invention is the nanosphere of the subsphaeroidal granule composition of 20～30nm。
The method have the advantages that
Black nano titanium oxide powder product obtained by the present invention is pure Anatase, its Ti3+Content has good controllability, by adjusting the Ti changed in solution3+/Ti4+Under mol ratio, the addition of precipitant and argon gas atmosphere, sintering temperature just can prepare excellent performance and controlled nanometer black anatase titanium oxide powder。The present invention not only considerably reduces production cost, and preparation technology is simple, polyvinyl chloride, can mass production, it is easy to the realization of industrialization, it is possible to effectively meet the production to black nano titanium oxide and user demand。
Accompanying drawing explanation
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail:
Fig. 1 is the X-ray crystallography of the embodiment of the present invention one, two, three gained anatase black oxidation titanium nano-powder；
Fig. 2 is the FSEM photo of the embodiment of the present invention one, two, three gained anatase black oxidation titanium nano-powder；
Fig. 3 is the TEM photo of the embodiment of the present invention three gained anatase black oxidation titanium nano-powder；
Fig. 4 is the embodiment of the present invention one, two, three gained anatase black oxidation titanium nano-powder and prior art commercialization P25 powder ultraviolet-visible absorption spectroscopy figure；
Fig. 5 is that the embodiment of the present invention three gained anatase black oxidation titanium nano-powder is at visible region degradation of methylene blue light application time and concentration relationship figure；
Fig. 6 is the x-ray photoelectron energy spectrogram of the embodiment of the present invention two gained anatase black oxidation titanium nano-powder。
Detailed description of the invention
Embodiment one:
The preparation method of a kind of anatase black nano titanium oxide powder of the present embodiment, its step is as follows:
(1)Ti4+The preparation of solution
Under room temperature, joining in 200ml deionized water by 20g ammonium titanium fluoride powder, stirring to ammonium titanium fluoride powder is completely dissolved the transparent Ti of formation4+Solution；
(2) preparation of material liquid
According to mol ratio Ti3+/Ti4+=1, at above-mentioned Ti4+Adding concentration in solution is the TiCl of 15%3Solution stirring mixing 10min, obtains material liquid；
(3) precipitation
Adding 40g precipitant propanoic acid in above-mentioned raw materials liquid, stirring and adding 0.1mol/L weak ammonia to solution system pH value is 5, and forms blue precipitate；
(4) precipitate calcining
Above-mentioned precipitate is filtered, and repeatedly cleans with the Cl of scavenger precipitation thing surface adsorption with deionized water-And F-, then precipitate is carried out in high-purity argon gas atmosphere furnace roasting, sintering temperature is 450 DEG C, temperature retention time 1h, namely obtains anatase black nano titanium oxide powder after its cooling。
Embodiment two:
The preparation method of a kind of anatase black nano titanium oxide powder of the present embodiment, its step is as follows:
(1)Ti4+The preparation of solution
Under room temperature, joining in 200ml deionized water by 20g ammonium titanium fluoride powder, stirring to ammonium titanium fluoride powder is completely dissolved the transparent Ti of formation4+Solution；
(2) preparation of material liquid
According to mol ratio Ti3+/Ti4+=2, at above-mentioned Ti4+Adding concentration in solution is the TiCl of 15%3Solution stirring mixing 10min, obtains material liquid；
(3) precipitation
Adding 60g precipitant propanoic acid in above-mentioned raw materials liquid, stirring and adding 0.1mol/L weak ammonia to solution system pH value is 5, and forms blue precipitate；
(4) precipitate calcining
Above-mentioned precipitate is filtered, and repeatedly cleans with the Cl of scavenger precipitation thing surface adsorption with deionized water-And F-, then precipitate is carried out in high-purity argon gas atmosphere furnace roasting, sintering temperature is 500 DEG C, temperature retention time 1h, namely obtains anatase black nano titanium oxide powder after its cooling。
Embodiment three:
The preparation method of a kind of anatase black nano titanium oxide powder of the present embodiment, its step is as follows:
(1)Ti4+The preparation of solution
Under room temperature, joining in 200ml deionized water by 20g ammonium titanium fluoride powder, stirring to ammonium titanium fluoride powder is completely dissolved the transparent Ti of formation4+Solution；
(2) preparation of material liquid
According to mol ratio Ti3+/Ti4+=3, at above-mentioned Ti4+Adding concentration in solution is the TiCl of 15%3Solution stirring mixing 10min, obtains material liquid；
(3) precipitation
Adding 90g precipitant propanoic acid in above-mentioned raw materials liquid, stirring and adding 0.1mol/L weak ammonia to solution system pH value is 5, and forms blue precipitate；
(4) precipitate calcining
Above-mentioned precipitate is filtered, and repeatedly cleans with the Cl of scavenger precipitation thing surface adsorption with deionized water-And F-, then precipitate is carried out in high-purity argon gas atmosphere furnace roasting, sintering temperature is 500 DEG C, temperature retention time 1h, namely obtains anatase black nano titanium oxide powder after its cooling。
Anatase black nano titanium oxide powder prepared by the embodiment of the present invention, as it is shown in figure 1, have good degree of crystallinity, its crystalline phase is pure Anatase, does not contain rutile and brookite；As in figure 2 it is shown, powder body has multilevel hierarchy, titanium oxide is to be assembled into nanosphere (see Fig. 3) by the tiny subsphaeroidal granule of 20～30nm；As shown in Figure 4, product absorbs at visible-range 400～700nm light and reaches more than 84%, illustrates that visible ray is had strong absorbing phenomenon by the black oxidation titanium of preparation；As it is shown in figure 5, product at visible region degradation of methylene blue it is shown that product has certain photocatalytic activity in visible region；As shown in Figure 6, with the Ti2p of white oxide titanium3/2Electron binding energy (458.4eV) is compared, black TiO2-xTi2p3/2Electron binding energy (457.6eV) decreases about 0.8eV, can find after it is carried out peak-fit processing, black TiO2-xContaining substantial amounts of Ti3+, and Ti3+Spectral peak area is about than Ti4+Spectral peak area is twice, this with initial titanium salt in Ti3+/Ti4+Mol ratio is basically identical, illustrates, the Ti in preparing black oxidation titanium powder process, in starting soln3+And not oxidized and and Ti4+Jointly it is built into black oxidation titanium。
Claims (2)
1. the preparation method of an anatase black nano titanium oxide powder, it is characterised in that: by Ti4+Solution and Ti3+Solution is obtained by mixing material liquid；Then in described material liquid, add precipitant, be that under 5～7 conditions, stirring reaction is precipitated thing in pH value；After the filtration of described precipitate, cleaning, carry out roasting, namely obtain anatase black nano titanium oxide powder；Comprise the following steps:
(1)Ti4+The preparation of solution
Joining in 50～600ml deionized water by 10～60g ammonium titanium fluoride powder, stirring to ammonium titanium fluoride powder is completely dissolved the transparent Ti of formation4+Solution；Or by 10～60gTiCl4It is dissolved in concentrated hydrochloric acid and forms transparent Ti4+Solution；
(2) preparation of material liquid
According to mol ratio Ti3+/Ti4+=1～3, at described Ti4+Solution adds TiCl3Solution stirring mixing 10～60min, obtains material liquid；
(3) precipitation
Adding 20～90g precipitant propanoic acid or butanoic acid in described material liquid, stirring and regulate solution system pH value is 5～7, and forms blue precipitate；
(4) precipitate calcining
Described precipitate is filtered, cleans the Cl with scavenger precipitation thing surface adsorption-And F-, then precipitate is carried out in high-purity argon gas atmosphere furnace roasting, sintering temperature is 450～600 DEG C, and temperature retention time is 1～2h, namely obtains anatase black nano titanium oxide powder after its cooling。
2. the preparation method of anatase black nano titanium oxide powder according to claim 1, it is characterised in that: described black nano titanium oxide powder is the nanosphere of the subsphaeroidal granule composition of 20～30nm。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510216852.9A CN104843780B (en) | 2015-04-30 | 2015-04-30 | A kind of preparation method of anatase black nano titanium oxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510216852.9A CN104843780B (en) | 2015-04-30 | 2015-04-30 | A kind of preparation method of anatase black nano titanium oxide powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104843780A CN104843780A (en) | 2015-08-19 |
| CN104843780B true CN104843780B (en) | 2016-06-22 |
Family
ID=53843831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510216852.9A Expired - Fee Related CN104843780B (en) | 2015-04-30 | 2015-04-30 | A kind of preparation method of anatase black nano titanium oxide powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104843780B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109939721B (en) * | 2019-04-16 | 2022-08-09 | 宝鸡文理学院 | Bismuth vanadate porous nanofiber photocatalytic material and preparation method thereof |
| CN110372034A (en) * | 2019-06-14 | 2019-10-25 | 西北大学 | A kind of preparation method of two-dimensional layer black titanium dioxide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102078806A (en) * | 2011-01-06 | 2011-06-01 | 华东师范大学 | Method for preparing doped mesoporous titanium photocatalyst |
| CN103011277A (en) * | 2012-12-25 | 2013-04-03 | 上海交通大学 | Preparation method of Ti<3+>-ion-doped porous titanium dioxide material |
| CN103028386A (en) * | 2012-12-21 | 2013-04-10 | 上海纳米技术及应用国家工程研究中心有限公司 | Ti<3+> and carbon codoped TiO2 photocatalyst with visible-light activity and preparation method of TiO2 photocatalyst |
| CN103130267A (en) * | 2013-02-19 | 2013-06-05 | 上海师范大学 | Preparation method for visible-light response black titanium dioxide photocatalyst |
| CN103285852A (en) * | 2013-04-25 | 2013-09-11 | 上海师范大学 | Ti<3+>-self-doped anatase titanium-oxide photocatalyst with large specific surface area, and synthetic method and applications thereof |
-
2015
- 2015-04-30 CN CN201510216852.9A patent/CN104843780B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102078806A (en) * | 2011-01-06 | 2011-06-01 | 华东师范大学 | Method for preparing doped mesoporous titanium photocatalyst |
| CN103028386A (en) * | 2012-12-21 | 2013-04-10 | 上海纳米技术及应用国家工程研究中心有限公司 | Ti<3+> and carbon codoped TiO2 photocatalyst with visible-light activity and preparation method of TiO2 photocatalyst |
| CN103011277A (en) * | 2012-12-25 | 2013-04-03 | 上海交通大学 | Preparation method of Ti<3+>-ion-doped porous titanium dioxide material |
| CN103130267A (en) * | 2013-02-19 | 2013-06-05 | 上海师范大学 | Preparation method for visible-light response black titanium dioxide photocatalyst |
| CN103285852A (en) * | 2013-04-25 | 2013-09-11 | 上海师范大学 | Ti<3+>-self-doped anatase titanium-oxide photocatalyst with large specific surface area, and synthetic method and applications thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104843780A (en) | 2015-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zheng et al. | Designing 3D magnetic peony flower-like cobalt oxides/g-C3N4 dual Z-scheme photocatalyst for remarkably enhanced sunlight driven photocatalytic redox activity | |
| Guo et al. | Mesocrystalline Ta3N5 superstructures with long-lived charges for improved visible light photocatalytic hydrogen production | |
| CN107138161B (en) | Preparation method of doped black titanium dioxide | |
| Cheng et al. | Characterization and mechanism analysis of Mo–N-co-doped TiO2 nano-photocatalyst and its enhanced visible activity | |
| Yao et al. | Microwave-assisted hydrothermal synthesis of broadband Yb3+/Er3+ co-doped BiOI/Bi2O4 photocatalysts with synergistic effects of upconversion and direct Z-scheme heterojunction | |
| Chaiwichian et al. | Highly efficient visible-light-induced photocatalytic activity of Bi2WO6/BiVO4 heterojunction photocatalysts | |
| Mi et al. | Highly controlled crystallite size and crystallinity of pure and iron-doped anatase-TiO2 nanocrystals by continuous flow supercritical synthesis | |
| CN104209136A (en) | Preparation method of TiO2/porous g-C3N4 composite material | |
| Zhang et al. | Synthesis of Sc and V-doped TiO2 nanoparticles and photodegradation of rhodamine-B | |
| Qin et al. | Construction of multi-shelled Bi2WO6 hollow microspheres with enhanced visible light photo-catalytic performance | |
| CN101116808A (en) | Photocatalysis powder having a negative ion releasing function and method for preparing the same | |
| CN105148949A (en) | Bismuth oxyiodide-bismuth vanadium oxide heterojunction photocatalyst and preparation method thereof | |
| CN103240073B (en) | Zn<2+>-doped BiVO4 visible-light-driven photocatalyst and preparation method thereof | |
| CN105664902A (en) | Trivalent titanium ion self-doped titanium dioxide nanosheet catalyst | |
| CN102001835B (en) | Method for preparing modified glass microspheres | |
| CN103274461B (en) | Method for modulating titanium dioxide crystalline phases by using fluoride ions | |
| Wei et al. | Photothermal catalytic activity and mechanism of LaNixCo1− xO3 (0≦ x≦ 1) perovskites for CO2 reduction to CH4 and CH3OH with H2O | |
| Taziwa et al. | Carbon doped nano-crystalline TiO 2 photo-active thin film for solid state photochemical solar cells | |
| CN104843780B (en) | A kind of preparation method of anatase black nano titanium oxide powder | |
| CN104098134A (en) | Preparation method and application of TiO2 nanotube coated with amorphous layer | |
| CN109879311B (en) | Method for preparing titanium suboxide by reducing titanium-containing complex at normal temperature | |
| CN103613130A (en) | Preparation method of titanium dioxide nanowire-lead sulfide quantum dot composite material | |
| CN103127885A (en) | Sonochemistry preparing method of nitrogen and rare earth element codope nanometer titania crystal | |
| Su et al. | The development of highly crystalline single-phase Bi20TiO32 nanoparticles for light driven oxygen evolution | |
| Pouretedal et al. | Preparation, characterization and catalytic activity of tin dioxide and zero-valent tin nanoparticles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| CB02 | Change of applicant information |
Address after: 333001 Tao Yang Road, Jingdezhen, Jiangxi Province, Jingdezhen Ceramic Institute Applicant after: JINGDEZHEN CERAMIC INSTITUTE Address before: 333001 Tao Yang Road, Jingdezhen, Jiangxi Province, Jingdezhen Ceramic Institute Applicant before: Jingdezhen College of Ceramic Industry |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160622 Termination date: 20210430 |