CN103588244B - Without the method for the sandwich hollow titanium dioxide nano material of template synthesis - Google Patents
Without the method for the sandwich hollow titanium dioxide nano material of template synthesis Download PDFInfo
- Publication number
- CN103588244B CN103588244B CN201310554230.8A CN201310554230A CN103588244B CN 103588244 B CN103588244 B CN 103588244B CN 201310554230 A CN201310554230 A CN 201310554230A CN 103588244 B CN103588244 B CN 103588244B
- Authority
- CN
- China
- Prior art keywords
- nano material
- sandwich hollow
- tio
- titanium dioxide
- template
- 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
Abstract
The present invention relates to a kind of method without the sandwich hollow titanium dioxide nano material of template synthesis.The present invention is with titanium sulfate (Ti (SO
4)
2) be titanium source, water is solvent, under the condition of crystallization promoting agent made by glycerine, adopt simple effective economic environmental protection without template, by simple Hydrothermal Synthesis process, the TiO of unique sandwich hollow structure must be had
2nano material.Obtained sandwich hollow TiO can be found out from XRD spectra
2nano material has typically anatase structured.The sandwich hollow TiO that this legal system is standby
2nano material has potential application prospect in fields such as environment, the energy and biomedicines.
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 the very important metal oxide semiconductor of one, titanium dioxide (TiO
2) nano material has the characteristic of many excellences, it not only has very strong oxidation capacity can be oxidized Organic substance in water, but also have the features such as affinity is strong, stable chemical nature, nontoxic, cost is low, therefore every field is widely used in, 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.But, in its application process, it is found that the impact of performance by several factors of material, as size, specific surface area, porousness, crystalline phase, degree of crystallinity and pattern etc.Therefore, scholars all wish can by controlling building-up process or exploring that some new synthetic methods reach morphology controllable, particle diameter is adjustable and the meticulous modulation of other physico-chemical properties, 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 the structure such as spherical, nanometer rod, fibre pipe.Although preparation TiO
2the method of nano material has a lot, but template is still considered to the very important technology of one of nano materials, utilizes its space confinement effect or structure-directing effect can carry out cutting effectively to the size of synthetic materials, pattern, structure etc.But template also comes with some shortcomings, the tensio-active agent being mostly some costlinesses adopted as soft template method and aggregate thereof, although process is flexible, morphology controllable is not strong, and synthesis cost is higher; Although hard template method controllability is strong, because need first to synthesize template, then template removed with strong acid or highly basic etc., 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 existed in prior art, a kind of method without the sandwich hollow titanium dioxide nano material of Template preparation 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 titanium sulfate (Ti (SO again
4)
2), continue to stir, make it mix; Wherein the mol ratio of glycerine and titanium sulfate is 80 ~ 150
:1; Then under 80 ~ 130 DEG C of conditions, 1 ~ 24 h is reacted; After having reacted, after deionized water and washing with alcohol, centrifugation, dry, finally in retort furnace 400 ~ 600 DEG C of air atmospheres, calcine 3 h, namely 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 and water reaction generation TiOSO
4, TiOSO subsequently
4generate the presoma of titanium with glycerine, under hydrothermal conditions, the organic matter precursor hydrolysis of these titaniums generates TiO
2small-particle glomeration, along with carrying out further 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, these nano particles dissolve again, deposit thus 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.By TiO prepared 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 embodiments all operate by the operation steps of technique scheme.
Embodiment 1
A. take 20.0 g deionized waters and 0.13 mol glycerine respectively with electronic balance, put into beaker mixing and stirring;
B. 0.0013 mol titanium sulfate (Ti (SO is taken with electronic balance
4)
2) join above-mentioned solution for continuous and stir 0.5 h, make it mix;
C. above-mentioned mixing solutions is poured in band teflon-lined autoclave, under 110 DEG C of conditions, react 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 DEG C, finally be placed in retort furnace air atmosphere, 550 DEG C of calcining 3 h, obtain sandwich hollow TiO prepared by the present invention
2nano material.
Obtained sample is carried out 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, unlike in a step
Take 15.0 g deionized waters and 0.13 mol glycerine respectively with electronic balance, put into beaker mixing and stirring.
Acquired results and embodiment 1 basic simlarity, difference is the TiO obtained
2appearance of nano material heterogeneity, reunites more serious.
Embodiment 3
The preparation process of the present embodiment is identical with embodiment 1 with step, unlike in step c
Above-mentioned mixing solutions is poured in band teflon-lined autoclave, under 110 DEG C of conditions, react 2.5 h.
Acquired results and embodiment 1 have bigger difference, obtained TiO
2for full particle, surface irregularity hairiness bayonet fittings.
Embodiment 4
The preparation process of the present embodiment is identical with embodiment 1 with step, unlike in step c
Above-mentioned mixing solutions is poured in band teflon-lined autoclave, under 80 DEG C of conditions, react 6 h.
Acquired results and embodiment 1 have bigger difference, the TiO obtained
2for the bead of solid reunion, and smooth surface.
See 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.
See accompanying drawing, Fig. 2 is the sandwich hollow TiO of the embodiment of the present invention 1 gained
2transmission electron microscope (TEM) picture of nano material.Tem analysis: adopt Jeol Ltd. JEOL-200CX type transmission electron microscope observation material morphology.As can be seen from TEM picture, the TiO that the present invention obtains
2nano material, have unique sandwich hollow structure, its particle diameter is between 700 ~ 900 nm.
See accompanying drawing, Fig. 3 is the sandwich hollow TiO of the embodiment of the present invention 1 gained
2scanning electron microscope (SEM) picture of nano material.Sem analysis: adopt NEC company JSM-6700F type emission scan electron microscope observation material morphology.As can be seen from SEM picture, the TiO that the present invention obtains
2nano material, spherical surface is coarse; And from the particle of breakage, obvious sandwich hollow structure can be seen, 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 153.85 ~ 385 g
:after the ratio of 1 mol is uniformly mixed; Add titanium sulfate (Ti (SO again
4)
2), continue to stir, make it mix; Wherein the mol ratio of glycerine and titanium sulfate is 100 ~ 150
:1; Then under 110 ~ 130 DEG C of conditions, 6 ~ 24 h are reacted; After having reacted, after deionized water and washing with alcohol, centrifugation, dry, finally in retort furnace 400 ~ 600 DEG C of air atmospheres, calcine 3 h, namely 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 CN103588244A (en) | 2014-02-19 |
| CN103588244B true 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) |
Families Citing this family (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 |
| CN107746074B (en) * | 2017-11-09 | 2019-04-30 | 沈阳工业大学 | A kind of titanium dioxide of core-shell structure mesoporous material and preparation method thereof with cavity |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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) |
Family Cites Families (2)
| 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 |
-
2013
- 2013-11-11 CN CN201310554230.8A patent/CN103588244B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| "Mesoporous Anatase Titania Hollow Nanostructures though Silica-Protected Calcination";Ji Bong Joo et al.;《Adv Funct Mater》;20120111;第22卷(第1期);第166-174页 * |
| "水热法制备高相变温度的二氧化钛纳米结构空心球";刘姝君等;《精细石油化工》;20100531;第27卷(第3期);第1-4页 * |
| "水热界面反应制备二氧化钛空心微球";展红全等;《中国陶瓷》;20111130;第47卷(第11期);第7-11页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103588244A (en) | 2014-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103193273B (en) | Preparation method of extra-long manganese dioxide nanowires | |
| CN102698728B (en) | Titanium dioxide nanotube/ graphene composite material and preparation method thereof | |
| CN103691433B (en) | A kind of Ag doped Ti O 2material, and its preparation method and application | |
| CN105502286B (en) | A kind of porous nano NiFe2O4Preparation method | |
| CN105600828B (en) | A kind of porous nano CuFe2O4Preparation method | |
| CN105836807B (en) | A kind of two-dimensional slice self assembly multilevel hierarchy tungsten oxide and its preparation method and application | |
| CN105129849A (en) | Flowerlike nano-sized titanium dioxide material and template-free preparation method thereof | |
| CN101817548A (en) | Method for preparing zinc oxide hollow spheres | |
| CN110357158B (en) | Three-dimensional sea urchin-shaped nano-structure TaO2Preparation method of F material | |
| CN101792172A (en) | Method for preparing copper hydroxide and copper oxide nano material and application | |
| CN103359773A (en) | Preparation method of zinc oxide nanorod | |
| CN103641165A (en) | Method for preparing titanium dioxide nanotube by using natural mineral as formwork | |
| CN105621474A (en) | Hyperbranched graded cuprous oxide nanomateiral and preparation method and application thereof | |
| CN103480395A (en) | Preparation and application of core-shell-structure bismuth sulfide@bismuth oxide composite microspheres | |
| 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 | |
| CN103833080B (en) | A kind of preparation method of molybdic acid cadmium porous ball | |
| CN105883910A (en) | Preparation method and product for perovskite SrTiO3 porous nano particles | |
| CN102644111A (en) | Preparation method of titanium dioxide hierarchical nano-tube ordered array consisting of controllable-morphology anatase single-crystal particles | |
| Wang et al. | Free-standing and flexible 0D CeO 2 nanodot/1D La (OH) 3 nanofiber heterojunction net as a novel efficient and easily recyclable photocatalyst | |
| CN107866212A (en) | A kind of rectangular patch photocatalyst of zinc oxide, preparation method and its application in photocatalytic hydrogen production by water decomposition |
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 |