CN103588245A - Preparation method for hollow carbon/titanium dioxide composite nano material - Google Patents
Preparation method for hollow carbon/titanium dioxide composite nano material Download PDFInfo
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- CN103588245A CN103588245A CN201310554834.2A CN201310554834A CN103588245A CN 103588245 A CN103588245 A CN 103588245A CN 201310554834 A CN201310554834 A CN 201310554834A CN 103588245 A CN103588245 A CN 103588245A
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Abstract
The invention relates to a preparation method for a hollow carbon/titanium dioxide composite nano material. TiO2 (titanium dioxide) is generated on the surface of a carbon shell by taking TiF4 (titanium tetrafluoride) as a titanium source, an ethanol/water mixed solution as a solvent and silicon dioxide wrapped by carbon as a hard template through hydrolysis of the titanium source by an in-situ etching method, and the silicon dioxide template can be effectively removed through byproducts HF produced in a reaction process, so that the carbon/titanium dioxide composite nano material which has a hollow characteristic and a uniform appearance can be prepared. The method disclosed by the invention can be used for preparing the hollow carbon/titanium dioxide composite nano material with a good crystallization effect and high performance; furthermore, the byproducts HF can be fully used; therefore, the cost is saved, the efficiency is improved, and the environment pollution is effectively prevented.
Description
Technical field
The present invention relates to a kind of preparation method of hollow carbon/titanium dioxide composite nano material.
Background technology
Nano-TiO
2because of it, there is the outstanding advantages such as wide material sources, with low cost, Stability Analysis of Structures and excellent performance, and standby being popular, be in recent years semiconductor material for one of environmental protection and energy technology field most study, new and high technology material most with prospects.However, TiO
2itself still comes with some shortcomings: the one, and greater band gap, thus low to sunlight utilization ratio, catalyzed reaction efficiency is not high, limited its application, the 2nd, the easy complex light in electron hole, spectral absorption narrow range, in use easy inactivation.In order further to improve its effective rate of utilization, expand its range of application, people have attempted multiple method of modifying, wherein to TiO
2comparatively pay close attention to the compound research of other materials, this is mainly because the abundant combining nano TiO of matrix material
2and the advantage of carrier, thereby form, have complementary advantages, its performance of more effective raising and efficiency.Wherein, take matrix material that carbon nanomaterial prepared as carrier receives much concern because of its unique advantage.Practice shows, carbon/TiO
2composite nano materials has following outstanding advantages: (1) carbon nanomaterial has high specific surface area conventionally, can effectively strengthen the contact area between substrate molecule and catalyzer, thereby improves reaction efficiency; (2) carbon nanomaterial has good electroconductibility, can improve the ability that electronics transmits, and makes up pure phase TiO
2deficiency; (3) supporting role of carbon skeleton, makes the TiO of its load
2have stable structure more, thereby increased stability and the returnability in reaction process.
At present, what the preparation of hollow carbon/titanium dioxide nano material mainly adopted is the method for hard template method and high temperature pyrolysis carbon matrix precursor, but conventional hard template method must be used strong acid or highly basic to remove template, cost but also complex operation have so not only been increased, waste time and energy, be unfavorable for very much environmental protection; And the method for high temperature pyrolysis has increased again a large amount of energy consumptions virtually.
Summary of the invention
The object of the invention is to overcome some problems that exist in prior art, a kind of preparation method of hollow carbon/titanium dioxide composite nano material is provided, present method can obtain pattern homogeneous, hollow carbon/titanic oxide nano compound material of well-crystallized.
For achieving the above object, the following technical scheme of a kind of employing of the present invention:
A preparation method for hollow carbon/titanium dioxide composite nano material, is characterized in that the concrete steps of the method are:
A. the coated silica nano material of carbon is added deionized water in, being mixed with concentration is the uniform dispersion A of 0.008-0.012 g/ mL;
B. by titanium tetrafluoride (TiF
4) put into ethanol, being mixed with concentration is 0.1-0.5 mmol/mL uniform dispersion B;
Under the condition stirring, step b gained dispersion liquid B is dropwise slowly splashed in step a gained dispersion liquid A, under 60～180 ℃ of conditions, react 4-12 h; After having reacted, product is through centrifugal, washing, oven dry; Finally roasting 3 h under tube furnace 400-600 ℃ inert atmosphere, obtain hollow carbon/titanium dioxide composite nano material.
Compared with prior art, the technology of the present invention has following remarkable advantage:
The present invention be take titanium tetrafluoride in the process of ，Tai source, titanium source hydrolysis, and the by product hydrofluoric acid (HF) that utilizes its hydrolysis to produce successfully removes silicon oxide template, adopts the mixed solvent of ethanol and water simultaneously, can effectively suppress TiF
4hydrolysis rate, thereby the titanium dioxide that makes to produce is grown in the surface of carbon shell more equably.And TiF
4the by product HF that hydrolysis produces, just in time can remove the silicon-dioxide in template, thereby forms hollow structure, finally forms hollow carbon/titanium dioxide composite nano material of pattern homogeneous, well-crystallized.The method of this original position etching has not only obtained the hollow carbon/titanium dioxide composite nano material of excellent performance, the more important thing is and by product HF can be made full use of, and has not only saved cost, has improved efficiency, has effectively avoided especially environmental pollution.The inventive method technique is simple, and mild condition had both avoided removing in traditional technology the loaded down with trivial details of hard template, had realized again economical reaction.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of gained hollow carbon/titanium dioxide composite nano material in the embodiment of the present invention 1.
Fig. 2 is the TEM photo of gained hollow carbon/titanium dioxide composite nano material in the embodiment of the present invention 1.
Fig. 3 is the SEM photo of gained hollow carbon/titanium dioxide composite nano material in the embodiment of the present invention 1.
Embodiment
the silica nano material that carbon is coated prepare reference: Antonio B. Fuertes, et al.,
chem. Commun., 2012,48,6124-6126.Concrete steps are:
A. the mixture (volume ratio of second alcohol and water is 2:1) that measures 40 mL ethanol (ethanol) and deionized water, adds 1.3 mL ammoniacal liquor (NH
3h
2o), mix, stir 0.5 h at 30 ℃; Measure 1.4 mL tetraethyl orthosilicates (TEOS) and join in above-mentioned solution, after mixing, then take 0.2 g Resorcinol with electronic balance, after adding and making to dissolve completely, then to add concentration be 37 wt% 0.3 mL formaldehyde solutions, continues reaction 24 h;
B. above-mentioned mixing solutions is packed in the band teflon-lined autoclave of 100 mL, at 110 ℃, react 24 h; After having reacted, product is taken out from reactor, through steps such as centrifugal, the washing of routine, oven dry, obtain the present invention and prepare the coated silica nano material of needed template-carbon;
Embodiment mono-:
A. with electronic balance, accurately take the coated silica nano material of carbon of the upper step preparation of 0.1 g, join in 10 mL deionized waters, ultrasonic make dispersed;
B. with electronic balance, accurately take 2.5 mmol titanium tetrafluoride (TiF
4) put into 10 mL ethanol, ultrasonic, after being uniformly dispersed, under the condition stirring, dropwise slowly splash in step suspension liquid, drip off rear to be mixed even, mixed solution is all packed in the band teflon-lined autoclave of 100 mL, under 180 ℃ of conditions, react 6 h;
C. after having reacted, product is taken out from reactor, through centrifugal, washing, oven dry, nitrogen, protect under environment the steps such as roasting, obtain hollow carbon/composite titania material prepared by the present invention.
Prepared sample is carried out to physical property sign, and its partial results as shown in drawings.Resulting materials is hollow structure, and the particle on surface is piled up in surface with sheet, and pattern homogeneous, and its particle diameter is in 150 nm left and right, and the platy shaped particle on surface is about 25 nm.
Embodiment bis-:
With electronic balance, accurately take 2.5 mmol titanium tetrafluoride (TiF
4) put into 10 mL deionized waters, ultrasonic, after being uniformly dispersed, under the condition stirring, dropwise slowly splash in step suspension liquid, drip off rear to be mixed even, mixed solution is all packed in the band teflon-lined autoclave of 100 mL, under 180 ℃ of conditions, react 6 h.
Acquired results and embodiment 1 have bigger difference, and difference is the TiO obtaining
2for particle is larger, and shape is inhomogeneous, can not be coated on equably on the surface of template.
Embodiment tri-:
With electronic balance, accurately take 2.5 mmol titanium tetrafluoride (TiF
4) put into 10 mL deionized waters, ultrasonic, after being uniformly dispersed, under the condition stirring, dropwise slowly splash in step suspension liquid, drip off rear to be mixed even, mixed solution is all packed in the band teflon-lined autoclave of 100 mL, under 60 ℃ of conditions, react 12 h.
Acquired results and embodiment 1 have bigger difference, and difference is that, under cold condition, silica template can not effectively be removed, and major part also all maintains the original state, surface TiO
2still for platy shaped particle is piled up.
Referring to accompanying drawing, Fig. 1 is the XRD spectra of the embodiment of the present invention 1 gained hollow carbon/titanium dioxide composite nano material.XRD analysis: carry out on Japanese RigaKu D/max-2550 type X-ray diffractometer; Adopt CuK α diffraction.Known from Fig. 1, gained TiO 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 transmission electron microscope (TEM) picture of the embodiment of the present invention 1 gained hollow carbon/titanium dioxide composite nano material.Tem analysis: adopt the JEOL-200CX of Jeol Ltd. type transmission electron microscope observation material pattern.From TEM picture, can find out, hollow carbon/titanic oxide nano compound material pattern homogeneous prepared by the present invention, inner for diameter is about the cavity of 100 nm, the particle on surface exists with the form of sheet accumulation, its particle diameter is about 150 nm, and the maximum particle diameter of surperficial sheet is about 25 nm.
Referring to accompanying drawing, Fig. 3 is scanning electronic microscope (SEM) picture of the embodiment of the present invention 1 gained hollow carbon/titanium dioxide composite nano material.Sem analysis: adopt the JSM-6700F of Jeol Ltd. sem observation material pattern.Therefrom can find out, hollow carbon/titanic oxide nano compound material prepared by the present invention has uniform ball-like structure, from fragmentation particle can see obvious cavity structure, consistent with the result of TEM.
Claims (1)
1. a preparation method for hollow carbon/titanium dioxide composite nano material, is characterized in that the concrete steps of the method are:
A. the coated silica nano material of carbon is added deionized water in, being mixed with concentration is 0.008-0.012 g/ mL uniform dispersion A;
B. by titanium tetrafluoride (TiF
4) put into ethanol, being mixed with concentration is the uniform dispersion B of 0.1-0.5 mmol/mL;
C. under the condition stirring, step b gained dispersion liquid B is dropwise slowly splashed in step a gained dispersion liquid A, under 60～180 ℃ of conditions, react 4-12 h; After having reacted, product is through centrifugal, washing, oven dry; Finally roasting 3 h under retort furnace 400-600 ℃ inert atmosphere, obtain hollow carbon/titanium dioxide composite nano material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105056929A (en) * | 2015-07-20 | 2015-11-18 | 重庆文理学院 | Graphene/titanium dioxide composite adopting hollow microspherical structure and preparation method of composite |
| CN114180620A (en) * | 2021-11-30 | 2022-03-15 | 陕西科技大学 | Preparation method for preparing titanium dioxide/carbon cathode by taking polypyrrole as template |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080107866A (en) * | 2007-06-08 | 2008-12-11 | 인하대학교 산학협력단 | Process for producing of high functional hollow titania nano particle with poly methyl methacrylate |
| CN103130266A (en) * | 2012-12-15 | 2013-06-05 | 王滨 | Preparation method of titanium dioxide hollow ball constructed by nano slices |
-
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080107866A (en) * | 2007-06-08 | 2008-12-11 | 인하대학교 산학협력단 | Process for producing of high functional hollow titania nano particle with poly methyl methacrylate |
| CN103130266A (en) * | 2012-12-15 | 2013-06-05 | 王滨 | Preparation method of titanium dioxide hollow ball constructed by nano slices |
Non-Patent Citations (2)
| Title |
|---|
| GUOHONG WANG ET AL.: "Facile Synthesis and Photocatalytic Property of Titania/Carbon Composite Hollow Microspheres with Bimodal Mesoporous Shells", 《INTERNATIONAL JOURNAL OF PHOTOENERGY》 * |
| LIXIN ZHANG ET AL.: "Fabrication and characterisation of hollow carbon/anatase titania", 《MICRO & NANO LETTERS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105056929A (en) * | 2015-07-20 | 2015-11-18 | 重庆文理学院 | Graphene/titanium dioxide composite adopting hollow microspherical structure and preparation method of composite |
| CN107486110A (en) * | 2015-07-20 | 2017-12-19 | 重庆文理学院 | A kind of method of efficient degradation methylene blue |
| CN107486110B (en) * | 2015-07-20 | 2019-01-22 | 重庆文理学院 | A kind of method of efficient degradation methylene blue |
| CN114180620A (en) * | 2021-11-30 | 2022-03-15 | 陕西科技大学 | Preparation method for preparing titanium dioxide/carbon cathode by taking polypyrrole as template |
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Effective date of registration: 20161031 Address after: 200072 Zhabei District Yanchang Road, Shanghai, No. 149 Patentee after: Shanghai top Asset Management Co., Ltd. Patentee after: Jiao Zheng Address before: 200444 Baoshan District Road, Shanghai, No. 99 Patentee before: Shanghai University |
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Effective date of registration: 20170321 Address after: 200444 Baoshan District Road, Shanghai, No. 99 Patentee after: Shanghai University Address before: 200072 Zhabei District Yanchang Road, Shanghai, No. 149 Patentee before: Shanghai top Asset Management Co., Ltd. Patentee before: Jiao Zheng |
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