CN103588244A - Method for preparing sandwiched hollow TiO2 nano material with template free method - Google Patents
Method for preparing sandwiched hollow TiO2 nano material with template free method Download PDFInfo
- Publication number
- CN103588244A CN103588244A CN201310554230.8A CN201310554230A CN103588244A CN 103588244 A CN103588244 A CN 103588244A CN 201310554230 A CN201310554230 A CN 201310554230A CN 103588244 A CN103588244 A CN 103588244A
- Authority
- CN
- China
- Prior art keywords
- nano material
- tio2 nano
- tio
- preparing
- sandwiched
- 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
Abstract
The invention relates to a method for preparing a sandwiched hollow TiO2 nano material with a template free method. Under the condition that Ti(SO4)2 is used as a titanium source, water is used as a solvent and glycerin is used as a crystallization auxiliary, the simple, efficient, economic and environment-friendly template free method is adopted to obtain the TiO2 nano material with a unique sandwiched hollow structure through a simple hydrothermal synthesis process. From a XRD spectrum, the prepared sandwiched hollow TiO2 nano material has a typical anatase structure. The sandwiched hollow TiO2 nano material prepared by the method has potential application prospects in the fields of environment, energy sources, biomedicine and the like.
Description
Technical field
The present invention relates to a kind of preparation method of hollow titanium dioxide nano material, particularly a kind of method without the sandwich hollow titanium dioxide nano material of template synthesis.
Background technology
As a kind of very important metal oxide semiconductor, titanium dioxide (TiO
2) nano material has the characteristic of many excellences, it not only have very strong oxidation capacity can oxidizing water in organism, but also have the features such as affinity is strong, stable chemical nature, nontoxic, cost is low, therefore be widely used in every field, as chromatographic separation, catalytic oxidation-reduction reaction, visible light catalytic water of decomposition, dye-sensitized solar cell, lithium ion battery, gas sensor and drug delivery etc.Yet in its application process, the performance that it is found that material is subject to the impact of several factors, as size, specific surface area, porousness, crystalline phase, degree of crystallinity and pattern etc.Therefore, scholars wish to reach that pattern is controlled, particle diameter is adjustable and the meticulous modulation of other physico-chemical properties by controlling building-up process or exploring some new synthetic methods, to obtaining the TiO of excellent performance
2nano material.
At present, increasing research focuses on the TiO with special appearance and character
2in the design of nanometer or micrometer structure, as structures such as spherical, nanometer rod, fibre pipes.Although preparation TiO
2the method of nano material has a lot, but template is still considered to a kind of very important technology of nano materials, utilizes its space confinement effect or structure-directing effect to carry out cutting effectively to the size of synthetic materials, pattern, structure etc.Yet template also comes with some shortcomings, as tensio-active agent and the aggregate thereof that some are expensive that be mostly of soft template method employing, although process is flexible, pattern controllability is not strong, and synthetic cost is higher; Although hard template method controllability is strong, because need to first synthesize template, then with strong acid or highly basic etc., template to be removed, operation is wasted time and energy, not only unfavorable to environment, and production efficiency is not high.
Summary of the invention
The object of the invention is to overcome some problems that exist in prior art, a kind of method of preparing sandwich hollow titanium dioxide nano material without template is provided.
For achieving the above object, the present invention by the following technical solutions:
Without a method for the sandwich hollow titanium dioxide nano material of template synthesis, it is characterized in that the step that has of the method is: by deionized water and glycerine by 76 ~ 385 g
:after the ratio of 1 mol is uniformly mixed; Add again titanium sulfate (Ti (SO
4)
2), continue to stir, it is mixed; Wherein the mol ratio of glycerine and titanium sulfate is 80 ~ 150
:1; Then under 80 ~ 130 ℃ of conditions, react 1 ~ 24 h; After having reacted, use after deionized water and washing with alcohol, centrifugation, dry, finally in 400 ~ 600 ℃ of air atmospheres of retort furnace, calcine 3 h, obtain sandwich hollow TiO
2nano material.
In technological process of the present invention, first water and glycerine are mixed to form the solvent system of a homogeneous phase, Ti (SO
4)
2add rear dissolving and water reaction generation TiOSO
4, TiOSO subsequently
4with the presoma of glycerine generation titanium, under hydrothermal condition, the hydrolysis of the organic matter precursor of these titaniums generates TiO
2small-particle glomeration, along with further carrying out of reaction, the TiO of gathering
2small-particle again dissolves under hydrothermal and assembles and forms larger nano particle, and meanwhile, under the effect of Ostwald ripening effect, thereby these nano particles again dissolve, deposit and form final sandwich hollow structure.
The present invention adopts without template, with water, titanium sulfate (Ti (SO
4)
2) and glycerine be raw material, by simple water-heat process, prepare the TiO with unique sandwich hollow structure
2nano material.The inventive method has simple to operate, and reaction conditions is gentle, and raw material is easy to get, and cost is low, yield advantages of higher.The TiO preparing by this method
2titanium nano material has unique sandwich hollow structure, has wide prospects for commercial application.
Accompanying drawing explanation
Fig. 1 is the sandwich hollow TiO of gained in the embodiment of the present invention 1
2the XRD spectra of nano material.
Fig. 2 is the sandwich hollow TiO of gained in the embodiment of the present invention 1
2the TEM photo of nano material.
Fig. 3 is the sandwich hollow TiO of gained in the embodiment of the present invention 1
2the SEM photo of nano material.
Embodiment
All embodiment all operate by the operation steps of technique scheme.
Embodiment 1
A. with electronic balance, take respectively 20.0 g deionized waters and 0.13 mol glycerine, put into beaker mixing and stirring;
B. with electronic balance, take 0.0013 mol titanium sulfate (Ti (SO
4)
2) join above-mentioned solution for continuous and stir 0.5 h, it is mixed;
C. above-mentioned mixing solutions is poured in band teflon-lined autoclave, under 110 ℃ of conditions, reacted 6 h;
D., after having reacted, product is taken out from reactor, with deionized water and ethanol repetitive scrubbing, centrifugal after, product is dried at 60 ℃, finally be placed in retort furnace air atmosphere, 550 ℃ of calcining 3 h, obtain sandwich hollow TiO prepared by the present invention
2nano material.
Prepared sample is carried out to physical property sign, and its partial results as shown in drawings.Resulting materials is sandwich hollow structure, and its particle diameter is between 700 ~ 900 nm.
Embodiment 2
The preparation process of the present embodiment is identical with embodiment 1 with step, and different is in a step
With electronic balance, take respectively 15.0 g deionized waters and 0.13 mol glycerine, put into beaker mixing and stirring.
Acquired results is substantially similar to embodiment 1, and difference is the TiO obtaining
2appearance of nano material heterogeneity, reunites more serious.
Embodiment 3
The preparation process of the present embodiment is identical with embodiment 1 with step, and different is in c step
Above-mentioned mixing solutions is poured in band teflon-lined autoclave, under 110 ℃ of conditions, reacted 2.5 h.
Acquired results and embodiment 1 have bigger difference, the TiO making
2for full particle, surface irregularity hairiness thorn-like structure.
Embodiment 4
The preparation process of the present embodiment is identical with embodiment 1 with step, and different is in c step
Above-mentioned mixing solutions is poured in band teflon-lined autoclave, under 80 ℃ of conditions, reacted 6 h.
Acquired results and embodiment 1 have bigger difference, the TiO obtaining
2for the bead of solid reunion, and smooth surface.
Referring to accompanying drawing, Fig. 1 is the sandwich hollow TiO of the embodiment of the present invention 1 gained
2the XRD spectra of nano material.XRD analysis: carry out on Japanese RigaKu D/max-2550 type X-ray diffractometer; Adopt CuK α diffraction.Known from Fig. 1, the sandwich hollow TiO of gained of the present invention
2nano material has typically anatase structured, consistent with standard spectrogram (PDF No:21-1272), has no other assorted peak, proves that it is pure crystal phase structure.
Referring to accompanying drawing, Fig. 2 is the sandwich hollow TiO of the embodiment of the present invention 1 gained
2the transmission electron microscope of nano material (TEM) picture.Tem analysis: adopt the JEOL-200CX of Jeol Ltd. type transmission electron microscope observation material pattern.From TEM picture, can find out the TiO that the present invention makes
2nano material, has unique sandwich hollow structure, and its particle diameter is between 700 ~ 900 nm.
Referring to accompanying drawing, Fig. 3 is the sandwich hollow TiO of the embodiment of the present invention 1 gained
2the scanning electron microscope of nano material (SEM) picture.Sem analysis: adopt the JSM-6700F of NEC company type emission scan electron microscope observation material pattern.From SEM picture, can find out the TiO that the present invention makes
2nano material, spherical surface is coarse; And from damaged particle, can see obvious sandwich hollow structure, consistent with TEM result.
Claims (1)
1. without a method for the sandwich hollow titanium dioxide nano material of template synthesis, it is characterized in that the step that has of the method is: by deionized water and glycerine by 76 ~ 385 g
:after the ratio of 1 mol is uniformly mixed; Add again titanium sulfate (Ti (SO
4)
2), continue to stir, it is mixed; Wherein the mol ratio of glycerine and titanium sulfate is 80 ~ 150
:1; Then under 80 ~ 130 ℃ of conditions, react 1 ~ 24 h; After having reacted, use after deionized water and washing with alcohol, centrifugation, dry, finally in 400 ~ 600 ℃ of air atmospheres of retort furnace, calcine 3 h, obtain sandwich hollow TiO
2nano material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310554230.8A CN103588244B (en) | 2013-11-11 | 2013-11-11 | Without the method for the sandwich hollow titanium dioxide nano material of template synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310554230.8A CN103588244B (en) | 2013-11-11 | 2013-11-11 | Without the method for the sandwich hollow titanium dioxide nano material of template synthesis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103588244A true CN103588244A (en) | 2014-02-19 |
| CN103588244B CN103588244B (en) | 2015-10-07 |
Family
ID=50078611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310554230.8A Expired - Fee Related CN103588244B (en) | 2013-11-11 | 2013-11-11 | Without the method for the sandwich hollow titanium dioxide nano material of template synthesis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103588244B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105133013A (en) * | 2015-07-28 | 2015-12-09 | 中国人民解放军军械工程学院 | Three-dimensional hollow titanium dioxide assembled from (001) surfaces, and preparation method and application thereof |
| CN107746074A (en) * | 2017-11-09 | 2018-03-02 | 沈阳工业大学 | A kind of titanium dioxide of core-shell structure mesoporous material with cavity and preparation method thereof |
| CN116212843A (en) * | 2023-02-14 | 2023-06-06 | 甘肃自然能源研究所 | Preparation method and application of self-template capable of realizing structural regulation and control of flower-like, hollow and solid titanium dioxide microspheres |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002074431A1 (en) * | 2001-03-21 | 2002-09-26 | Max-Planck-Gesellschaft Zur Förderung Der Wissenschaften | Hollow spheres from layered precursor deposition on sacrificial colloidal core particles |
| KR100616362B1 (en) * | 2005-06-16 | 2006-08-28 | 권용구 | Process for high functional hollow titania nano particle |
| CN101121112A (en) * | 2007-05-17 | 2008-02-13 | 浙江大学 | Method for preparing hollow microsphere with hydrogel microsphere as stencil |
| CN102838162A (en) * | 2011-06-21 | 2012-12-26 | 中国科学院过程工程研究所 | Porous titanium dioxide hollow sphere, its preparation and method for adsorbing Cr(VI) |
-
2013
- 2013-11-11 CN CN201310554230.8A patent/CN103588244B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002074431A1 (en) * | 2001-03-21 | 2002-09-26 | Max-Planck-Gesellschaft Zur Förderung Der Wissenschaften | Hollow spheres from layered precursor deposition on sacrificial colloidal core particles |
| KR100616362B1 (en) * | 2005-06-16 | 2006-08-28 | 권용구 | Process for high functional hollow titania nano particle |
| CN101121112A (en) * | 2007-05-17 | 2008-02-13 | 浙江大学 | Method for preparing hollow microsphere with hydrogel microsphere as stencil |
| CN102838162A (en) * | 2011-06-21 | 2012-12-26 | 中国科学院过程工程研究所 | Porous titanium dioxide hollow sphere, its preparation and method for adsorbing Cr(VI) |
Non-Patent Citations (3)
| Title |
|---|
| JI BONG JOO ET AL.: ""Mesoporous Anatase Titania Hollow Nanostructures though Silica-Protected Calcination"", 《ADV FUNCT MATER》, vol. 22, no. 1, 11 January 2012 (2012-01-11), pages 166 - 174, XP 001571751, DOI: doi:10.1002/adfm.201101927 * |
| 刘姝君等: ""水热法制备高相变温度的二氧化钛纳米结构空心球"", 《精细石油化工》, vol. 27, no. 3, 31 May 2010 (2010-05-31), pages 1 - 4 * |
| 展红全等: ""水热界面反应制备二氧化钛空心微球"", 《中国陶瓷》, vol. 47, no. 11, 30 November 2011 (2011-11-30), pages 7 - 11 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105133013A (en) * | 2015-07-28 | 2015-12-09 | 中国人民解放军军械工程学院 | Three-dimensional hollow titanium dioxide assembled from (001) surfaces, and preparation method and application thereof |
| CN107746074A (en) * | 2017-11-09 | 2018-03-02 | 沈阳工业大学 | A kind of titanium dioxide of core-shell structure mesoporous material with cavity and preparation method thereof |
| CN116212843A (en) * | 2023-02-14 | 2023-06-06 | 甘肃自然能源研究所 | Preparation method and application of self-template capable of realizing structural regulation and control of flower-like, hollow and solid titanium dioxide microspheres |
| CN116212843B (en) * | 2023-02-14 | 2024-01-19 | 甘肃自然能源研究所 | Preparation method and application of self-template capable of realizing structural regulation and control of flower-like, hollow and solid titanium dioxide microspheres |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103588244B (en) | 2015-10-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103193273B (en) | Preparation method of extra-long manganese dioxide nanowires | |
| CN103771485B (en) | A kind of controllable method for preparing of cupric oxide three-dimensional manometer self-assembly | |
| CN1258479C (en) | Titanium oxide nano tube and preparing method thereof | |
| CN103908972A (en) | Recyclable BiOX/TiO2 composite photocatalyst and preparation method thereof | |
| CN101817548A (en) | Method for preparing zinc oxide hollow spheres | |
| CN105645459B (en) | A kind of surface modification sea urchin shape ZnO/TiO2Composite and preparation method thereof | |
| CN105129849A (en) | Flowerlike nano-sized titanium dioxide material and template-free preparation method thereof | |
| CN101311376A (en) | Method for preparing strontium titanate nanometer powder of one-dimensional structure | |
| CN103691433A (en) | Ag-doped TiO2 material, and preparation method and application thereof | |
| CN101792172A (en) | Method for preparing copper hydroxide and copper oxide nano material and application | |
| CN103877966A (en) | Preparation method of heterostructure photocatalyst | |
| CN103641165A (en) | Method for preparing titanium dioxide nanotube by using natural mineral as formwork | |
| CN108675339B (en) | Preparation method of rodlike self-assembled spherical zinc-cadmium-sulfur solid solution material | |
| CN105621474A (en) | Hyperbranched graded cuprous oxide nanomateiral and preparation method and application thereof | |
| CN101941734A (en) | Tin oxide nanomaterial and preparation method thereof | |
| CN103588244B (en) | Without the method for the sandwich hollow titanium dioxide nano material of template synthesis | |
| CN104310466A (en) | Hollow titanium dioxide microsphere based on gel sphere precursor and preparation method of hollow titanium dioxide microsphere | |
| CN102070178A (en) | Method for preparing yttrium oxide micro-nano-materials based on hydrothermal technology regulation and control | |
| CN100591620C (en) | Preparation of high photocatalysis activity titanium dioxide nano-stick by non-hydrosol-gel method and surface functionalization | |
| CN107930611A (en) | A kind of carbon dots titanium dioxide hollow microballoon composite nano-catalyst and preparation method and application | |
| CN104787800A (en) | Flower-ball-shaped titanium dioxide and preparation method thereof | |
| CN108996548B (en) | Preparation method of orthorhombic phase nano-rod-shaped molybdenum trioxide | |
| CN103833080B (en) | A kind of preparation method of molybdic acid cadmium porous ball | |
| CN102644111A (en) | Preparation method of titanium dioxide hierarchical nano-tube ordered array consisting of controllable-morphology anatase single-crystal particles | |
| CN108031481B (en) | Ultrathin bismuth oxyhalide nanosheet photocatalyst stripped by silver intercalation and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151007 Termination date: 20191111 |