CN101264928A - Preparation of high photocatalysis activity titanium dioxide nano-stick by non-hydrosol-gel method and surface thereof functionalization - Google Patents
Preparation of high photocatalysis activity titanium dioxide nano-stick by non-hydrosol-gel method and surface thereof functionalization Download PDFInfo
- Publication number
- CN101264928A CN101264928A CNA2008100474318A CN200810047431A CN101264928A CN 101264928 A CN101264928 A CN 101264928A CN A2008100474318 A CNA2008100474318 A CN A2008100474318A CN 200810047431 A CN200810047431 A CN 200810047431A CN 101264928 A CN101264928 A CN 101264928A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- titanium
- rod
- hydrosol
- dioxide nano
- 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
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention provides a non-hydrosol-gel preparation method of titanium-dioxide nanorods, which can realize the online functionlization of the titanium-dioxide nanorods. The invention uses phenyl carbinol as the reaction media, and titanium tetrachloride directly dissolves in the phenyl carbinol. By the hydrolyzation of the titanium tetrachloride in phenyl carbinol under low temperature, the high activity titanium-dioxide nanorods are compounded at once. The functionlization reagent, which is added into the reaction system, realizes the online functionlization of the titanium-dioxide nanorods, which improves the photo-catalysis activity of the titanium-dioxide nanorods. The non-hydrosol-gel preparation method has the advantages that: the method is sample; the preparation process runs under the temperature of 40 to 100 centidegrees; the granularity of the titanium-dioxide, produced by the method, is homogeneously distributed; the crystal structure is uniform anatase ; the technical process is easy to controlled; the product quality is stable; the non-hydrosol-gel preparation method is suit for mass production.
Description
Technical field
The invention belongs to technical field of nano material, relate generally to the preparation of titanium dioxide nano-rod and surface-functionalized.
Background technology
Titanium dioxide is commonly called as titanium white, is the more function fine inorganic material of research, is important pottery, semi-conductor and catalytic material.Titanium dioxide then because of special performances such as its good weathering resistance, chemical resistance, higher chemical stability, thermostability, nontoxicity, photosensitivity, can be used as the raw material of producing high grade paint, catalyzer and fine ceramics such as support of the catalyst, makeup, UV light absorber, special glass and electronic ceramics, structural ceramics etc.Anatase titanium dioxide has very strong photocatalytic activity, is widely used in the improvement of waste water and pollutent.
The catalytic activity of titanium dioxide is not only relevant with its crystal configuration, and with its grain-size much relations is arranged.Compare with the titanium dioxide of micro-meter scale, the catalytic activity of the titanium dioxide of nanoscale improves a lot.Most studies and patent concentrate on the preparation of titanium dioxide nanoparticle at present, and less relatively about the research of one dimension Nano structure titanium dioxide.1-dimention nano titanium dioxide is owing to the surface imperfection that has bigger specific surface and enrich, thereby the ratio nano particle has higher catalytic activity.Among the preparation method about titanium dioxide nano-rod, that mainly adopt is hydrothermal method (Jun-Nan Nian and Hsisheng Teng J.Phys.Chem.B 2006,110,4193-4198), solvent-thermal method (Xiangping Huang, Chunxu Pan, Journal of Crystal Growth 2007,306,117-122; CN1699636A), amine-decomposing method (CN1986908A).Hydrothermal method and solvent-thermal method all carry out under high temperature and high pressure in these methods, and reaction yield is subject to the restriction of equipment, are difficult for expanding the scale of production.Other preparation method's flow process complexity, and preparation process also need just can obtain pure Detitanium-ore-type crystalline structure through pyroreaction or calcining.
Utilize titanium tetrachloride and phenylcarbinol direct reaction to prepare titanium dioxide nano-rod among the present invention, Shang Weijian has other pertinent literature report.And be reflected under normal pressure and the low temperature and carry out, obtain titanium dioxide nano-rod and have pure Detitanium-ore-type crystalline structure.
Summary of the invention
The object of the present invention is to provide a kind of non-aqueous sol-preparing gel titanium dioxide nano-rod and surface-functionalized method thereof, this method is carried out under normal pressure and low temperature, the variety of raw material that uses is few, the product separate easily that obtains, cost is lower, and energy consumption is low, the product purity height, steady quality, equipment and technology is simple, is convenient to scale operation
The method of a kind of non-aqueous sol-preparing gel titanium dioxide nano-rod is characterized in that may further comprise the steps:
In described step 2, described time of repose is 60～80 hours.
In described step 1, titanium tetrachloride is progressively added in the phenylcarbinol that contains the L-oxyproline, forming titanium content is 0.1～0.7 mol, the concentration of L-oxyproline is the white emulsion of 0.05～0.12 mol, through described step 2 and step 3 operation, promptly get the anatase titanium dioxide nanometer rod that the L-oxyproline is modified then.
Effect of the present invention and advantage:
Preparation process of the present invention is all carried out under normal pressure and 60～100 ℃ of temperature, the variety of raw material that uses is few, and do not need just can obtain pure Detitanium-ore-type crystalline structure through pyroreaction, the product separate easily, cost is lower, and energy consumption is low, the product purity height, steady quality, equipment and technology is simple, is convenient to scale operation.
Further the present invention will be described below in conjunction with drawings and Examples.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of corresponding embodiment 1 gained titanium dioxide nano-rod powder;
Fig. 2 is the X ray diffracting spectrum of the titanium dioxide nano-rod powder of corresponding embodiment 2 gained L-oxyprolines modification;
Fig. 3 is the transmission electron microscope figure photo (a) and the high resolution transmission electron microscope figure photo (b) of present embodiment 1 gained powder;
Fig. 4 is under the different time simulated solar rayed, degrade the respectively effect of rhodamine B of titanium dioxide nano-rod (embodiment 1), surface-functionalized nanometer rod (embodiment 2) and commercially available Degussa P25.
The characteristic peak of (Fig. 1, Fig. 2) and standard diffracting spectrum (TiO in the diffracting spectrum
2PDF 71-1169) peak value coincide, and illustrates that product is an anatase titanium dioxide.Sample is observed (see figure 3) through high resolution transmission electron microscope (JEM-2010), and the diameter of nanometer rod is about 3 nanometers, and length is about 10 nanometers.Fig. 4 shows under the simulated solar optical condition, behind rhodamine B under the different time radiation of visible light (RhB) aqueous solution, and the technology of the ratio of concentration of rhodamine B and initial difficulty and irradiation time in the solution.Test condition is: the 100 milliliters of solution that contain 5 mg/litre RhB of packing in reaction vessel, add 0.1 gram specimen then, pre-earlier stirring of solution reached adsorption equilibrium in 1 hour, apply 500 watts of tungsten lamp irradiations then, solution is consistent to be in whipped state and to remain on 25 degree simultaneously, and the concentration of RhB is determined by U-3310 (HITACHI) UV, visible light extinction photometer measurement absorption peak strength in the solution.As can be seen, the prepared sample of the present invention all has higher catalyzed degradation activity than Degussa P25, and wherein the titanium dioxide nano-rod catalytic activity of process L-oxyproline modification has higher catalytic activity than the nanometer rod of unmodified.
Embodiment
Under vigorous stirring, titanium tetrachloride progressively added form solution in the phenylcarbinol, wherein titanium content is 0.4 mol, subsequently white emulsion was left standstill 70 hours in 80 ℃ of atmosphere, make the titanium dioxide hydrolysis complete, reaction finishes by the centrifugal white precipitate that obtains, behind chloroform washing institute white precipitate, 50 ℃ of oven dry down, obtain white anatase titanium dioxide nanometer rod then.
Get a certain amount of phenylcarbinol, adding L-oxyproline and stirring are dissolved it fully, and the concentration of L-oxyproline is 0.05 mol.Then under vigorous stirring, titanium tetrachloride is progressively added the white emulsion of formation in the above phenylcarbinol mixed solution, wherein titanium content is 0.7 mol, subsequently white emulsion was left standstill 80 hours in 60 ℃ of atmosphere, make the titanium dioxide hydrolysis complete, reaction finishes by the centrifugal white precipitate that obtains, behind chloroform washing institute white precipitate, oven dry under 50 degree obtains the white anatase titanium dioxide nanometer rod that the L-oxyproline is modified then.
Under vigorous stirring, titanium tetrachloride is progressively added the white emulsion of formation in the phenylcarbinol, wherein titanium content is 0.7 mol, subsequently white emulsion was left standstill 60 hours in 100 ℃ of atmosphere, make the titanium dioxide hydrolysis complete, reaction finishes by the centrifugal white precipitate that obtains, behind chloroform washing institute white precipitate, oven dry under 50 degree obtains white anatase titanium dioxide nanometer rod then.
Embodiment 4
Get a certain amount of phenylcarbinol, adding L-oxyproline and stirring are dissolved it fully, and the concentration of L-oxyproline is 0.12 mol.Then under vigorous stirring, titanium tetrachloride is progressively added the white emulsion of formation in above phenylcarbinol and the L-oxyproline mixed solution, wherein titanium content is 0.1 mol, subsequently white emulsion was left standstill 80 hours in 100 ℃ of atmosphere, make the titanium dioxide hydrolysis complete, reaction finishes by the centrifugal white precipitate that obtains, behind chloroform washing institute white precipitate, oven dry under 50 degree obtains the white anatase titanium dioxide nanometer rod that the L-oxyproline is modified then.
Claims (3)
1. the method for non-aqueous sol-preparing gel titanium dioxide nano-rod is characterized in that may further comprise the steps:
Step 1, under vigorous stirring, titanium tetrachloride is progressively added in the phenylcarbinol, forming titanium content is 0.1～0.7 mol white emulsion;
Step 2, the white emulsion that step 1 is obtained leave standstill in 60～100 ℃ of atmosphere, make the titanium dioxide hydrolysis complete;
Step 3, the white emulsion that step 2 hydrolysis is obtained are centrifugal, and the white precipitate that obtains promptly gets the anatase titanium dioxide nanometer rod with chloroform washing back oven dry.
2. the method for non-aqueous sol according to claim 1-preparing gel titanium dioxide nano-rod is characterized in that in the described step 2 that described time of repose is 60～80 hours.
3. the method for non-aqueous sol according to claim 1-preparing gel titanium dioxide nano-rod, it is characterized in that in the described step 1, titanium tetrachloride is progressively added in the phenylcarbinol that contains the L-oxyproline, forming titanium content is 0.1～0.7 mol, the concentration of L-oxyproline is 0.05～0.12 mol white emulsion, through described step 2 and step 3 operation, promptly get the anatase titanium dioxide nanometer rod that the L-oxyproline is modified then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810047431A CN100591620C (en) | 2008-04-23 | 2008-04-23 | Preparation of high photocatalysis activity titanium dioxide nano-stick by non-hydrosol-gel method and surface functionalization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810047431A CN100591620C (en) | 2008-04-23 | 2008-04-23 | Preparation of high photocatalysis activity titanium dioxide nano-stick by non-hydrosol-gel method and surface functionalization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101264928A true CN101264928A (en) | 2008-09-17 |
| CN100591620C CN100591620C (en) | 2010-02-24 |
Family
ID=39987653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810047431A Expired - Fee Related CN100591620C (en) | 2008-04-23 | 2008-04-23 | Preparation of high photocatalysis activity titanium dioxide nano-stick by non-hydrosol-gel method and surface functionalization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100591620C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830501B (en) * | 2009-03-13 | 2012-09-05 | 复旦大学 | Method for preparing soluble anatase titanium dioxide |
| CN102757092A (en) * | 2012-07-31 | 2012-10-31 | 常州大学 | L-tryptophan molecular imprinted TiO2 powder and preparation method thereof |
| CN103771504A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Synthetic method of titanium dioxide photocatalyst |
| CN105664808A (en) * | 2016-01-13 | 2016-06-15 | 云南大学 | Method for preparing stable nano anatase titanium dioxide alcohol phase sol at low temperature |
| WO2019001026A1 (en) * | 2017-06-28 | 2019-01-03 | Tcl集团股份有限公司 | Preparation method for metal oxide nanoparticle film and electrical component |
| CN110668538A (en) * | 2019-09-20 | 2020-01-10 | 济南大学 | Preparation method of titanium polychloride |
-
2008
- 2008-04-23 CN CN200810047431A patent/CN100591620C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830501B (en) * | 2009-03-13 | 2012-09-05 | 复旦大学 | Method for preparing soluble anatase titanium dioxide |
| CN102757092A (en) * | 2012-07-31 | 2012-10-31 | 常州大学 | L-tryptophan molecular imprinted TiO2 powder and preparation method thereof |
| CN102757092B (en) * | 2012-07-31 | 2014-05-21 | 常州大学 | L-tryptophan molecular imprinted TiO2 powder and preparation method thereof |
| CN103771504A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Synthetic method of titanium dioxide photocatalyst |
| CN103771504B (en) * | 2012-10-24 | 2015-07-22 | 中国石油化工股份有限公司 | Synthetic method of titanium dioxide photocatalyst |
| CN105664808A (en) * | 2016-01-13 | 2016-06-15 | 云南大学 | Method for preparing stable nano anatase titanium dioxide alcohol phase sol at low temperature |
| WO2019001026A1 (en) * | 2017-06-28 | 2019-01-03 | Tcl集团股份有限公司 | Preparation method for metal oxide nanoparticle film and electrical component |
| US11851343B2 (en) | 2017-06-28 | 2023-12-26 | Tcl Technology Group Corporation | Preparation method for metal oxide nanoparticle film and electrical component |
| CN110668538A (en) * | 2019-09-20 | 2020-01-10 | 济南大学 | Preparation method of titanium polychloride |
| CN110668538B (en) * | 2019-09-20 | 2021-10-22 | 济南大学 | Preparation method of titanium polychloride |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100591620C (en) | 2010-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102350334B (en) | Graphene/mesoporous titanium dioxide visible light catalyst and preparation method | |
| CN104084186B (en) | A kind of Graphene/optically catalytic TiO 2 matrix material and its preparation method | |
| CN100591620C (en) | Preparation of high photocatalysis activity titanium dioxide nano-stick by non-hydrosol-gel method and surface functionalization | |
| Mousavi et al. | Green synthesis of ZnO hollow sphere nanostructures by a facile route at room temperature with efficient photocatalytic dye degradation properties | |
| Shahmirzaee et al. | In situ crystallization of ZnAl 2 O 4/ZnO nanocomposite on alumina granule for photocatalytic purification of wastewater | |
| CN104069844A (en) | Grading three-dimensional porous graphene/titanium dioxide photocatalyst and preparation method thereof | |
| Wei et al. | Influence of surfactant on the morphology and photocatalytic activity of anatase TiO2 by solvothermal synthesis | |
| Cai et al. | Biotemplating synthesis of graphitic carbon-coated TiO2 and its application as efficient visible-light-driven photocatalyst for Cr6+ remove | |
| CN106044743A (en) | Preparation method and application of water-soluble carbon quantum dots based on eggshell membranes | |
| Wang et al. | Efficient hydrogen production from glycerol photoreforming over Ag2OTiO2 synthesized by a sol–gel method | |
| CN110152641A (en) | A kind of amorphous photonic crystal schemochrome material and preparation method thereof with photocatalytic effect | |
| CN110304654A (en) | A kind of amorphous photonic crystal schemochrome material compound based on black titanium dioxide and silica and preparation method thereof | |
| Zou et al. | Enhanced photocatalytic activity of bismuth oxychloride by in-situ introducing oxygen vacancy | |
| CN110201655B (en) | One-step method for preparing hollow TiO2Method and application of nano-microspheres | |
| CN103521248A (en) | Method for preparing graphene-based composite visible light catalysis material | |
| Zhao et al. | Synthesis, performance and action mechanism of carbon black/Ag3PO4 photocatalysts | |
| Wang et al. | Effect of chiral-arrangement on the solar adsorption of black TiO2-SiO2 mesoporous materials for photodegradation and photolysis | |
| Ji et al. | Preparation and photocatalytic properties of carbon/carbon-doped TiO 2 double-layer hollow microspheres | |
| Zhang et al. | Synthesis of Mesoporous TiO2‐Al2O3 Binary Oxides Photocatalyst by Sol‐Gel Method Using PEG1000 as Template | |
| Escamilla-Mejía et al. | Biochars from olive stones as carbonaceous support in Pt/TiO2-carbon photocatalysts and application in hydrogen production from aqueous glycerol photoreforming | |
| CN102381727A (en) | Process for preparing titanium dioxide mesoporous nano-belt material by solvothermal method | |
| CN101342486B (en) | Metallic oxide nano-material | |
| CN107008337B (en) | Non-stoichiometric copper bismuthate nano material and preparation method and application thereof | |
| CN101696109B (en) | Method for preparing mesoporous titanium dioxide microspheres | |
| CN103588244B (en) | Without the method for the sandwich hollow titanium dioxide nano material of template synthesis |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100224 Termination date: 20130423 |