CN104628030A - Fluoride-free preparation method of titanium dioxide of similar graphene structure - Google Patents
Fluoride-free preparation method of titanium dioxide of similar graphene structure Download PDFInfo
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- CN104628030A CN104628030A CN201510050502.XA CN201510050502A CN104628030A CN 104628030 A CN104628030 A CN 104628030A CN 201510050502 A CN201510050502 A CN 201510050502A CN 104628030 A CN104628030 A CN 104628030A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
Abstract
The invention provides a fluoride-free preparation method of titanium dioxide of a similar graphene structure and belongs to the technical field of nanomaterial preparation. The material is composed of titanium dioxide nanosheets having the size of greater than 500nm. The preparation method mainly comprises the following steps: by taking ethylene glycol and ethanol as reaction solvents, inhibiting quick decomposition of titanium isopropylate by use of concentrated hydrochloric acid under the action Pluronic P123, performing a solvothermal reaction, growing micro flake titanium dioxide by virtue of self-assembly, and further growing to obtain titanium dioxide having a large area and an ultra-thin similar graphene structure. According to the preparation method, titanium dioxide having the large area and the ultra-thin similar graphene structure is synthesized for the first time and can be widely applied to photo/electro/chemocatalysis, the electrode materials of new energy batteries and the like.
Description
Technical field
What the present invention relates to is the technology in a kind of nano material, new energy materials field, the specifically floride-free preparation method of a kind graphene-structured titanium dioxide.
Background technology
The structure of appropriate design nano material has material impact for its performance and application, especially at energy environment, as significant in fields such as solar cell, photochemical catalysis, ultracapacitors, therefore construct and design nano material by rational method and more and more come into one's own.Two-dimension nano materials-Graphene, owing to having the constitutional features of single or multiple carbon atom thickness, and there is very high charge mobility, good mechanical flexibility and optical transparence, high chemical stability, excellent conduction, heat conductivility, shown wide application prospect in photochemical catalysis, lithium ion battery, ultracapacitor, solar cell, biosensor etc.As the Two-dimensional Inorganic material with class graphene-structured, also cause great concern now.As the MoS of class Graphene laminate structure
2, the sandwich structure of its larger specific surface area and uniqueness makes that its adsorptive power is stronger, electroconductibility is higher, catalytic performance is better, also has very high scientific research and using value.
Titanium dioxide is as the very important semiconductor material with wide forbidden band of one, and because its safety non-toxic, stable chemical nature, efficiency be high, pollution-free etc., advantage is widely used in every field.Prepare a lot of difform TiO at present
2structure, as the nano particle crystal of zero dimension, the nanometer stick array of one dimension, the nanometer sheet of two dimension, and the multilevel hierarchy of three-dimensional, these specific structure designs and manufacture are all for improving its performance.In the structure design of these uniquenesses, there is the nanometer sheet of high reaction activity, effectively can improve light collection efficiency and carrier flow speed, cause scientific research person's more and more research enthusiasm.As everyone knows, fluorion significantly can reduce the surface energy in (001) face, for TiO
2pattern have tremendous influence.
Prior art is as document (Chao Hu, et al, J.Mater.Chem.A, 2014,2:2040 – 2043) be the anatase titania nanometer sheet superstructure that Morphological control agent synthesizes exposure (001) crystal face with hydrofluoric acid, show superior photocatalysis performance; Open (bulletin) the day 2014.10.08 of Chinese patent literature CNCN104085920A, disclose a kind of preparation method of two-dimensional sheet titanium dioxide nanoplate material, this technology chemical liquid phase stripping method, three-layer laminated Ti
3alC
2be immersed in the HF aqueous solution under powder room temperature condition, remove Al atom, will still retain the Ti of two-dirnentional structure
3c
2in-situ oxidation is TiO
2nanometer sheet.But adopt F ? system, the HF that uses in building-up process of major part has strong corrodibility, becomes one of important factor of its application of restriction; And by the flaky material that the method is peeled off, compared to Graphene, its class graphene-structured can not be given prominence to, because its thickness major part is at more than 10nm, its size is also less comparatively speaking.
But, how to obtain ultra-thin, a large-sized two-dimensional sheet TiO
2quite challenging, owing to contacting unstable (001) face, TiO
2nanometer sheet is easy to be assembled into laminate structure.Therefore, the Graphene of large specific surface area and adjustable surface property becomes the carrier of the desirable heterogeneous growth of active guest materials.Ultra-thin TiO prepared by document (Zhiyuan Wang et al, J.Mater.Chem.A, 2014,2:8893 – 8901)
2/ graphene composite material is used for lithium ion battery, and Graphene is not only conducive to the exchange between the Li ion of additional interfaces storage, ensures the electroconductibility that electrode has had and high flexible substrates, the TiO of load simultaneously
2nanometer sheet, due to intrinsic open channel, effectively reduces diffusion length.Although these advantages are very attractive, graphene composite material is utilized also to encounter some restrictions.Such as, the preparation of Graphene needs usually by peeling off the so very long and process for complexity of graphite and the carbonization temperature of needs is very high.Therefore, a kind of simple method is developed for the preparation of the TiO with Graphene characteristic
2, tool is of great significance.
Summary of the invention
The present invention is directed to prior art above shortcomings, the floride-free preparation method of one kind graphene-structured titanium dioxide is proposed, adopt solvent thermal self-assembled growth, by Reasonable Regulation And Control tensio-active agent and solvent, prepare the titanium dioxide with big area, ultra-thin class graphene-structured.
The present invention is achieved by the following technical solutions:
The present invention relates to the floride-free preparation method of a kind graphene-structured titanium dioxide, titanium source fast decoupled is suppressed by concentrated hydrochloric acid, and join in the reaction solvent containing ethylene glycol, ethanol and nonionic surface active agent, fully to suppress the growth in <001> direction, become small plate-like titanium dioxide finally by solvent thermal reaction self-assembled growth, a step-length great achievement of going forward side by side has the titanium dioxide of big area, ultra-thin class graphene-structured.
Described titanium source is the consumption of TTIP (titanium isopropylate) is 5.25g;
Described concentrated hydrochloric acid refers to that massfraction is the hydrogen chloride solution of 37%, and consumption is 3.75g;
Described nonionic surface active agent is preferably Pluronic P123, and its consumption is 0.5 ~ 2g;
The consumption of described ethanol is 15g;
The consumption of described ethylene glycol is 50 ~ 200mL;
Described solvent thermal reaction temperature is 100 ~ 200 DEG C, and the reaction times is 12 ~ 36 hours;
The present invention relates to the class graphene-structured titanium dioxide that aforesaid method prepares, have graphene-structured, its thickness is 2 ~ 5nm, and size is more than 500nm, and sheet interlayer spacing is
Technique effect
Compared with prior art, technique effect of the present invention comprises
1) the present invention's solvent-thermal method, prepares ultra-thin titanium dioxide nanoplate, have class graphene-structured, and dimensioned area is large; And adopt F ? system, the HF that uses in building-up process of major part has strong corrodibility; And by the flaky material that the method is peeled off, compared to Graphene, its class graphene-structured can not be given prominence to, because its thickness major part is at more than 10nm, its size is also less comparatively speaking.
2) compared to the method for chemical vapour deposition and stripping, solvent thermal in situ synthesis of the present invention, reaction conditions controlled (temperature, time, starting material), simple to operate, laboratory apparatus is cheap, the good characteristics such as productive rate is high, favorable repeatability.
3) titanium dioxide has the structure of big area, ultra-thin class graphene-structured, transferring charge is faster, specific surface area is larger, be conducive to the transmission of electronics in electrochemical reaction process and being separated of hole, at catalytic material, solar cell, has application potential widely in ultracapacitor and lithium electricity energy storage material.
Accompanying drawing explanation
Fig. 1 is the overall TEM figure of the titanium dioxide with class graphene-structured of preparation in the embodiment of the present invention 1.
Fig. 2 is that the titanium dioxide high power TEM with class graphene-structured of preparation in the embodiment of the present invention 1 schemes.
Fig. 3 is the titanium dioxide diffraction pattern figure with class graphene-structured of preparation in the embodiment of the present invention 1.
Embodiment
Elaborate to embodiments of the invention below, the present embodiment is implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
The present embodiment comprises the steps:
1) 5.25g TTIP being added to 3.75g massfraction is in the concentrated hydrochloric acid of 37%, stirs 15min;
2) 1g Pluronic P123 is added in 15g ethanol, stir 30min; Then add in step 1 gained mixed solution and stir 30min;
3) get 20mL step 2 gained mixed solution, add in the beaker filling 150mL ethylene glycol, stir 30min;
4) above-mentioned steps 3 gained mixed solution is poured into reactor, 150 DEG C of thermal treatments, are incubated 12 hours, the product centrifugation obtained, and with 60 DEG C of oven dry in deionized water and dehydrated alcohol repetitive scrubbing 3 times, loft drier, obtain the titanium dioxide with class graphene-structured.
As shown in FIG. 1 to 3, the effect of the titanium dioxide that the present embodiment prepares is: the titanium dioxide prepared, and has Graphene ultrathin nanometer chip architecture, and size is more than 500nm, and sheet interlayer spacing is
Embodiment 2
The present embodiment comprises the steps:
1) 5.25g TTIP being added to 3.75g massfraction is in the concentrated hydrochloric acid of 37%, stirs 15min;
2) 0.5g Pluronic P123 is added in 15g ethanol, stir 30min; Then add in step 1 gained mixed solution and stir 30min;
3) get 20mL step 2 gained mixed solution, add in the beaker filling 50mL ethylene glycol, stir 30min;
4) pour above-mentioned solution into reactor, 100 DEG C of thermal treatments, be incubated 12 hours, the product centrifugation obtained, and with 60 DEG C of oven dry in deionized water and dehydrated alcohol repetitive scrubbing 3 times, loft drier, obtain the titanium dioxide with class graphene-structured.
Embodiment 3
The present embodiment comprises the steps:
1) 5.25g TTIP being added to 3.75g massfraction is in the concentrated hydrochloric acid of 37%, stirs 15min;
2) 1.5g Pluronic P123 is added in 15g ethanol, stir 30min; Then add in step 1 gained mixed solution and stir 30min;
3) get 20mL step 2 gained mixed solution, add in the beaker filling 100mL ethylene glycol, stir 30min;
4) pour above-mentioned solution into reactor, 200 DEG C of thermal treatments, be incubated 12 hours, the product centrifugation obtained, and with 60 DEG C of oven dry in deionized water and dehydrated alcohol repetitive scrubbing 3 times, loft drier, obtain the titanium dioxide with class graphene-structured.
Embodiment 4
The present embodiment comprises the steps:
1) 5.25g TTIP being added to 3.75g massfraction is in the concentrated hydrochloric acid of 37%, stirs 15min;
2) 2g Pluronic P123 is added in 15g ethanol, stir 30min; Then add in step 1 gained mixed solution and stir 30min;
3) get 20mL step 2 gained mixed solution, add in the beaker filling 200mL ethylene glycol, stir 30min;
4) pour above-mentioned solution into reactor, 100 DEG C of thermal treatments, be incubated 24 hours, the product centrifugation obtained, and with 60 DEG C of oven dry in deionized water and dehydrated alcohol repetitive scrubbing 3 times, loft drier, obtain the titanium dioxide with class graphene-structured.
Claims (6)
1. the floride-free preparation method of a kind graphene-structured titanium dioxide, it is characterized in that, suppress titanium source fast decoupled by concentrated hydrochloric acid, join in the reaction solvent containing ethylene glycol, ethanol and nonionic surface active agent, through solvent thermal reaction, finally obtain the titanium dioxide of class graphene-structured.
2. the floride-free preparation method of class graphene-structured titanium dioxide according to claim 1, is characterized in that, described titanium source is titanium isopropylate.
3. the floride-free preparation method of class graphene-structured titanium dioxide according to claim 1, is characterized in that, described nonionic surface active agent is Pluronic P123.
4. the floride-free preparation method of the class graphene-structured titanium dioxide according to claim 1 or 2 or 3, is characterized in that, the consumption in described titanium source is 5.25g; Described concentrated hydrochloric acid refers to that massfraction is the hydrogen chloride solution of 37%, and consumption is 3.75g; The consumption of described nonionic surface active agent is 0.5 ~ 2g; The consumption of described ethanol is 15g; The consumption of described ethylene glycol is 50 ~ 200mL.
5. the floride-free preparation method of class graphene-structured titanium dioxide according to claim 1, is characterized in that, described solvent thermal reaction temperature is 100 ~ 200 DEG C, and the reaction times is 12 ~ 36 hours.
6. the class graphene-structured titanium dioxide that method prepares according to above-mentioned arbitrary claim, is characterized in that having graphene-structured, and its thickness is 2 ~ 5nm, and size is more than 500nm, and sheet interlayer spacing is
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105771991A (en) * | 2016-02-22 | 2016-07-20 | 南开大学 | Method for preparing efficient fungicide ferroferric oxide/titanium dioxide nanosheet |
| CN105883752A (en) * | 2016-04-28 | 2016-08-24 | 北京科技大学 | Two-phase interface preparation method of ultrathin two-dimensional carbon nanomaterial |
| CN106495212A (en) * | 2016-11-09 | 2017-03-15 | 中国科学院新疆理化技术研究所 | A kind of preparation method of the humidity sensor material based on ultra-thin titanium dioxide nanosheet |
| CN107285376A (en) * | 2017-07-18 | 2017-10-24 | 浙江大学 | A kind of two-dimentional TiO2Ultrathin nanometer piece and preparation method thereof |
| CN112457741A (en) * | 2020-11-09 | 2021-03-09 | 内蒙古电力（集团）有限责任公司巴彦淖尔电业局 | Epoxy resin corrosion paint and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105771991A (en) * | 2016-02-22 | 2016-07-20 | 南开大学 | Method for preparing efficient fungicide ferroferric oxide/titanium dioxide nanosheet |
| CN105883752A (en) * | 2016-04-28 | 2016-08-24 | 北京科技大学 | Two-phase interface preparation method of ultrathin two-dimensional carbon nanomaterial |
| CN105883752B (en) * | 2016-04-28 | 2017-12-08 | 北京科技大学 | A kind of two-phase interface preparation method of ultra-thin two-dimension carbon nanomaterial |
| CN106495212A (en) * | 2016-11-09 | 2017-03-15 | 中国科学院新疆理化技术研究所 | A kind of preparation method of the humidity sensor material based on ultra-thin titanium dioxide nanosheet |
| CN107285376A (en) * | 2017-07-18 | 2017-10-24 | 浙江大学 | A kind of two-dimentional TiO2Ultrathin nanometer piece and preparation method thereof |
| CN112457741A (en) * | 2020-11-09 | 2021-03-09 | 内蒙古电力（集团）有限责任公司巴彦淖尔电业局 | Epoxy resin corrosion paint and preparation method thereof |
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| CN104628030B (en) | 2016-07-06 |
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