CN103878001A - Preparation method and application of fluorine-boron codoped TiO2 nanosheets - Google Patents
Preparation method and application of fluorine-boron codoped TiO2 nanosheets Download PDFInfo
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Abstract
The invention relates to the fields of nanometer structures and nanotechnology and in particular relates to a fluorine-boron codoped TiO2 nanosheet and a preparation method and application of the fluorine boron codoped TiO2 nanosheet. The fluorine-boron codoped TiO2 nanosheet is in an anatase structure, fluorine and boron are doped into crystal lattices, the exposed crystal face is a crystal face (001) and is in the shape of a sheet, the thickness of the nanosheet is 1-100nm, and edges for forming the nanosheet unit are in smooth transition. Compared with pure anatase TiO2 nanoparticles, the fluorine-boron codoped TiO2 nanosheet exposed on the crystal face (001) has the advantages that the absorption rate of visible light is obviously improved, an obvious red shift phenomenon exists, the photogenerated electron-hole migration efficiency is improved, and high-activity crystal face (001) is greatly exposed, so that the photocatalytic performance of the nanosheet is obviously enhanced. The fluorine-boron codoped TiO2 nanosheet can have high application prospects in the aspect of treatment of a photocatalytic environment, for example, the nanosheet can serve as a photocatalyst to be used for water purification.
Description
Technical field
The present invention relates to nano material and field of nanometer technology, specifically relate to a kind of fluorine boron codope TiO
2nanometer sheet, Preparation method and use.
Background technology
Since last century, the seventies photocatalytic phenomenon was found, the lifting of design, preparation and the photocatalytic activity thereof of catalysis material is the forward position hot fields of scientists study always, anatase TiO
2as one of most important metal oxide, in photocatalysis field by extensive and deep research, it have nontoxic, catalytic efficiency is high, good stability, the advantage such as with low cost, is a kind of desirable catalysis material.
Generally, the photocatalytic process of based semiconductor is mainly concerned with three committed steps: 1) exciting light radiation-induced electronics migrates to conduction band by valence band, forms electron-hole pair; 2) electronics that photoinduction produces and hole are to semiconductor surface migration or again compound in semiconductor inside; 3) migrating to surperficial electronics and hole participates in redox reaction.The factor of these three aspects can apply certain impact to the photocatalysis performance of semi-conducting material.First band gap width has determined absorbable light wavelength scope, determines the overall utilization ratio to sunshine; Secondly electric charge is two processes of vying each other to again compound in surperficial migration and body, and more to the electric charge of surface migration, its photocatalysis efficiency is higher, on the contrary photocatalysis efficiency decline; Last specific area is larger, expose the minute surface of crystal face more great Qi photocatalytic activity be stronger.Therefore, current research emphasis mainly concentrates on three fields: band engineering (increase to absorbable light wavelength scope), electron-hole pair regulation and control (in restriction body again compound, increase the charge number to surface migration) and microscopic appearance regulation and control (increasing specific area the more high activity crystal faces of exposure).
1), band engineering
TiO
2(3～3.2eV) can only utilize the ultraviolet light part of sunlight 4%, in order more to effectively utilize solar energy, must carry out certain correction to being with of semi-conducting material, makes its band gap narrow to develop and has visible light-responded high-efficiency photocatalysis material.In order to realize this goal, mainly by reduce valence band edge, rising conduction band edge or conduction band and valence band carried out to the approach such as adjusting continuously simultaneously.And at present conventional a few class specific experiment methods have: metal ion is used to TiO as V, Ni, Cr, Fe, Mn, Ag, Sn, Bi, In, Cu, Ce, Pt, Co, La etc.
2doping, the metallic atom of doping often becomes light induced electron-hole-recombination center, restriction photo-generated carrier separation, to improve its absorption and photocatalytic activity thereof to visible ray; Nonmetalloid is all used to TiO as C, N, Si, S, P, B etc.
2doping or codope, make its absorbing wavelength generation red shift, and then show the visible light photocatalysis active of enhancing.
2), electron-hole pair regulation and control
Because photogenerated charge is two processes of vying each other to surperficial migration and in vivo compound, and the latter is one of major influence factors reducing photochemical catalyst catalytic activity.Noble metal is widely used in TiO as co-catalyst as Au, Ag, Pt, Pd, Ru, Rh, Cu etc.
2photocatalysis research, mainly because its fermi level is significantly lower than semi-conductive, therefore very easily enrichment on these metallics of light induced electron, hole is retained in semiconductor, and metal nanoparticle can provide activated centre for surface light catalytic reaction as co-catalyst simultaneously.
3), microscopic appearance regulation and control
Surface/interface chemical property is the excellent key factor that affects conductor photocatalysis performance.In general, high surface energy band is carried out high catalytic activity, and specific surface area of catalyst is larger, and on surface, reactant more easily adsorbs and the easier desorption of product, and photocatalytic process carries out the next high catalytic activity of easier more soon, high surface energy band, for anatase TiO
2, the crystal face that is exposed to outside under general case is mainly surface energy minimum (101) faces (>94%), rather than surface can the highest, better (001) face of catalytic activity.Therefore synthetic high activity crystal face (001) TiO that exposes
2be an important research direction, the nano particles of a large amount of novelty uniquenesses of preparation and the superstructure with complex hierarchy structure are to strengthen its photocatalytic activity.
Comprehensive above-mentioned discussion, can find out, has the TiO of high photocatalysis efficiency in preparation
2in process, yet there are no bibliographical information and can realize visible light absorbing, high photo-generated carrier transport efficiency, (001) crystal face exposure TiO simultaneously
2controlled technology of preparing.
Summary of the invention
For the technical problem existing in prior art, one of object of the present invention is to provide a kind of fluorine boron codope TiO
2nanometer sheet, this fluorine boron codope TiO
2nanometer sheet obviously improves the absorptivity of visible ray, and has obvious Red Shift Phenomena, has improved the transport efficiency in light induced electron-hole, and a large amount of exposures of (001) high activity crystal face, makes as seen this fluorine boron codope TiO
2the photocatalysis performance of nanometer sheet has obtained remarkable enhancing.
To achieve these goals, the technical solution adopted in the present invention is: a kind of fluorine boron codope TiO
2nanometer sheet, is Anatase structure, and fluorine and boron mix in lattice, and expose crystal face be (001) crystal face, it is pattern in the form of sheets, the thickness of nanometer sheet is 1～100nm, the edge of construction unit nanometer sheet is rounding off.
The TiO that fluorine boron codope of the present invention, (001) crystal face expose
2nanometer sheet, with pure Anatase TiO
2nano particle is compared, the TiO that fluorine boron codope, (001) crystal face expose
2nanometer sheet obviously improves the absorptivity of visible ray, and has obvious Red Shift Phenomena, has improved the transport efficiency in light induced electron-hole, and a large amount of exposures of (001) high activity crystal face, makes as seen this fluorine boron codope TiO
2the photocatalysis performance of nanometer sheet has obtained remarkable enhancing.
Fluorine boron codope TiO
2nanometer sheet can have good application prospect aspect photocatalysis environmental improvement, for example, be used for water purification etc. as photochemical catalyst.
Another object of the present invention is to provide a kind of fluorine boron codope TiO
2the preparation method of nanometer sheet, comprises with titanium source and prepares Anatase TiO
2the method of suspension, and by this Anatase TiO
2suspension and fluorine, boron source there is hydro-thermal reaction to prepare fluorine boron codope TiO
2nanometer sheet, TiCl in reaction system
3with HBF
4between volume ratio be 1:0～1, the temperature of hydro-thermal reaction is 160～250 ℃, the reaction time is 6～15 hours.
Preferably, described titanium source is TiCl
3, this Anatase TiO
2the preparation method of suspension is: measuring 20～35ml ethanolic solution is precursor liquid, slowly adds the 15wt%TiCl of 1～2ml
3solution, formation suspension stirs.
Further preferred, fluorine, boron source that hydro-thermal reaction adopts are HBF
4, the step of this hydro-thermal reaction is: suspension is placed in to consersion unit, drips the 40wt%HBF of 0～1ml
4solution, in consersion unit, is then put consersion unit in air dry oven and is started to react.
Further, after hydro-thermal reaction finishes, be cooled to room temperature, to obtained solidliquid mixture carry out centrifugal, wash and be dried.
Preferably, solid product after solidliquid mixture is centrifugal adopts ethanol washing 3～5 times, then 80 ℃ of freeze-day with constant temperature 6～15 hours in baking oven.
Further, the product obtaining after being dried is through 200～500 ℃ of heat treatments after 3～5 hours, and grind into powder, obtains fluorine boron codope TiO
2nanometer sheet.
Fluorine boron codope TiO of the present invention
2the preparation method of nanometer sheet, respectively with TiCl
3and HBF
4as titanium source and doping and modification reagent, by regulating both influence factors such as ratio, the temperature and time of reaction, a large amount of TiO that expose of (001) high activity crystal face are prepared
2nanometer sheet.Due to the formation in oxygen room on codope effect induction (001) crystal face of F-B, and then expand its absorption region to visible-infrared light district, finally significantly promoted its photocatalysis performance.
Fluorine boron codope TiO of the present invention
2the preparation method of nanometer sheet, technique is simple, be easy to control, obvious as its catalytic effect of photochemical catalyst, and the practical application of photochemical catalyst has been played to great impetus.
Accompanying drawing explanation
Fig. 1 is the TiO that the fluorine boron codope prepared of embodiment 1, (001) crystal face expose
2(a) (Fig. 1 b) with projection Electronic Speculum figure (TEM) for Fig. 1 for the scanning electron microscope (SEM) photograph (SEM) of nanometer sheet.
Fig. 2 is Anatase TiO prepared by comparative example
2fluorine boron codope prepared by nano particle (a), embodiment 2, the TiO that (001) crystal face exposes
2nanometer sheet (b, c, X ray (XRD) diffraction comparison diagram d).
Fig. 3 is Anatase TiO prepared by comparative example
2fluorine boron codope prepared by nano particle, embodiment 3, the TiO that (001) crystal face exposes
2ultraviolet-visible (UV-Vis) the absorption spectrum comparison diagram of nanometer sheet.
Fig. 4 is the TiO that the fluorine boron codope prepared of embodiment 4, (001) crystal face expose
2x-ray photoelectron power spectrum (XPS) figure of nanometer sheet.
Fig. 5 is Anatase TiO prepared by comparative example
2fluorine boron codope prepared by nano particle, embodiment 1, the TiO that (001) crystal face exposes
2nanometer sheet is the degradation effect comparison diagram to methyl orange under visible ray.
The specific embodiment
For further describing the present invention, below in conjunction with drawings and Examples, the present invention is described in further detail, but within therefore not limiting the present invention to described scope of embodiments.
Embodiment 1
The ethanolic solution that measures volume and be 30ml is precursor liquid, slowly adds the 15wt%TiCl of 1ml
3solution, generates uniform suspension for 5 minutes by magnetic stirrer; The solution preparing in above-mentioned steps is poured in the polytetrafluoroethylene (PTFE) autoclave inner bag that volume is 50ml, then dripped the 40wt%HBF of 0.75ml
4solution in reactor inner bag, 210 ℃ of constant temperature 12 hours; The solidliquid mixture obtaining carries out solid-liquid centrifugation, with ethanol washing 4 times 80 ℃ of freeze-day with constant temperature 10 hours; The product obtaining is through 450 ℃ of subsequent heat treatment after 3 hours, and grind into powder, obtains having fluorine boron codope, (001) crystal face that crystallization degree is higher simultaneously and expose TiO
2nanometer sheet.
Embodiment 2
The ethanolic solution that measures volume and be 30ml is precursor liquid, slowly adds the 15wt%TiCl of 1ml
3solution, generates uniform suspension for 5 minutes by magnetic stirrer; The solution preparing in above-mentioned steps is poured in the polytetrafluoroethylene (PTFE) autoclave inner bag that volume is 50ml, then dripped the 40wt%HBF of 0～1ml
4solution in reactor inner bag, 210 ℃ of constant temperature 12 hours; The solidliquid mixture obtaining carries out solid-liquid centrifugation, with ethanol washing 3 times 80 ℃ of freeze-day with constant temperature 10 hours; The product obtaining is through 400 ℃ of subsequent heat treatment after 4 hours, and grind into powder, obtains having fluorine boron codope, (001) crystal face that crystallization degree is higher simultaneously and expose TiO
2nanometer sheet.
Embodiment 3
The ethanolic solution that measures volume and be 30ml is precursor liquid, slowly adds the 15wt%TiCl of 1ml
3solution, generates uniform suspension for 5 minutes by magnetic stirrer; The solution preparing in above-mentioned steps is poured in the polytetrafluoroethylene (PTFE) autoclave inner bag that volume is 50ml, then dripped the 40wt%HBF of 0.5ml
4solution in reactor inner bag, 210 ℃ of constant temperature 12 hours; The solidliquid mixture obtaining carries out solid-liquid centrifugation, with ethanol washing 3 times 70 ℃ of freeze-day with constant temperature 10 hours; The product obtaining is through 400 ℃ of subsequent heat treatment after 3 hours, and grind into powder, obtains having fluorine boron codope, (001) crystal face that crystallization degree is higher simultaneously and expose TiO
2nanometer sheet.
Embodiment 4
The ethanolic solution that measures volume and be 30ml is precursor liquid, slowly adds the 15wt%TiCl of 1ml
3solution, generates uniform suspension for 5 minutes by magnetic stirrer; The solution preparing in above-mentioned steps is poured in the polytetrafluoroethylene (PTFE) autoclave inner bag that volume is 50ml, then dripped the 40wt%HBF of 1ml
4solution in reactor inner bag, 210 ℃ of constant temperature 12 hours; The solidliquid mixture obtaining carries out solid-liquid centrifugation, with ethanol washing 5 times 80 ℃ of freeze-day with constant temperature 12 hours; The product obtaining is through 450 ℃ of subsequent heat treatment after 3 hours, and grind into powder, obtains having fluorine boron codope, (001) crystal face that crystallization degree is higher simultaneously and expose TiO
2nanometer sheet.
Embodiment 5
The ethanolic solution that measures volume and be 30ml is precursor liquid, slowly adds the 15wt%TiCl of 1ml
3solution, generates uniform suspension for 5 minutes by magnetic stirrer; The solution preparing in above-mentioned steps is poured in the polytetrafluoroethylene (PTFE) autoclave inner bag that volume is 50ml, then dripped the 40wt%HBF of 0.5ml
4solution in reactor inner bag, 210 ℃ of constant temperature 12 hours; The solidliquid mixture obtaining carries out solid-liquid centrifugation, with ethanol washing 5 times 80 ℃ of freeze-day with constant temperature 12 hours; The product obtaining is through 450 ℃ of subsequent heat treatment after 3 hours, and grind into powder, obtains having fluorine boron codope, (001) crystal face that crystallization degree is higher simultaneously and expose TiO
2nanometer sheet.
Comparative example:
By the 15wt%TiCl of 1ml
3it is the ethanolic solution of 30ml that solution adds volume, 180 ℃ of constant temperature 12 hours; Take out hydrothermal product, with ethanol washing, dry, 450 ℃ of heat treatments are after 3 hours, and grind into powder, obtains anatase TiO
2nano particle.
Fig. 1 is the TiO that the fluorine boron codope prepared of embodiment 1, (001) crystal face expose
2the scanning electron microscope (SEM) photograph (SEM) of nanometer sheet (Fig. 1 a) and projection Electronic Speculum figure (TEM) (Fig. 1 b), as can be seen from the figure: TiO prepared by embodiment 1
2particle is sheet-like morphology, although diameter is also inhomogeneous, but comparatively homogeneous of its thickness, be generally 1～100nm left and right, the edge of its construction unit nanometer sheet is rounder and more smooth, and there will not be the apparent handing-over of (101) and (001) crystal face edge, and the crystal face major part exposing is (001) crystal face, there is a lot of depressions and pore space structure in nanometer sheet, TEM(Fig. 1 of amplification b) displaing micro picture also can know and see this point.
Fig. 2 is Anatase TiO prepared by comparative example
2fluorine boron codope prepared by nano particle (a), embodiment 2, the TiO that (001) crystal face exposes
2nanometer sheet (b, c, X ray (XRD) diffraction comparison diagram d), as can be seen from the figure: TiO prepared by embodiment 2
2particle is pure Anatase structure, and crystallinity is enhanced.
Fig. 3 is Anatase TiO prepared by comparative example
2fluorine boron codope prepared by nano particle, embodiment 3, the TiO that (001) crystal face exposes
2ultraviolet-visible (UV-Vis) the absorption spectrum comparison diagram of nanometer sheet, as can be seen from the figure: TiO prepared by embodiment 3
2nanometer sheet improves the absorption intensity of visible light wave range, and Red Shift Phenomena has occurred.
Fig. 4 is the TiO that the fluorine boron codope prepared of embodiment 4, (001) crystal face expose
2x-ray photoelectron power spectrum (XPS) figure of nanometer sheet, as can be seen from the figure: fluorine boron codope prepared by embodiment 4, the TiO that (001) crystal face exposes
2in nanometer sheet, fluorine and boron are successfully mixed in lattice.
Essence for a better understanding of the present invention, the TiO exposing below by fluorine boron codope, (001) crystal face
2nanometer sheet is carried out degradation experiment to aqueous dye solutions (methyl orange), illustrate its as photochemical catalyst water purify in purposes.
1, experiment material and method
The TiO exposing by contrast fluorine boron codope, (001) crystal face
2nanometer sheet (prepared by embodiment 1) and Anatase TiO
2nano particle (comparative example preparation) to the degradation rate of Methyl Orange in Wastewater study codope, (001) crystal face exposes TiO
2the impact of photocatalysis performance.
Reaction is used 350W high-pressure sodium lamp as light source, apart from liquid level 10cm, 0.04g photocatalysis sample is put into the methyl orange solution that 50ml concentration is 15mg/L, mixed liquor constantly stirs, get 3ml solution every 20min, remove the catalyst in solution with 5000 revs/min of centrifuges, clear liquid judges its residual concentration by ultraviolet-visual spectrometer test absorption maximum light rate.
2, experimental result
Experimental result as shown in Figure 5, can be found out, than Anatase TiO
2nano particle, fluorine and boron codope, (001) crystal face expose TiO
2nanometer sheet significantly promotes for the degradation capability of methyl orange, confirms that it has good Photocatalytic Degradation Property, is applicable to water removing pollutant field as photochemical catalyst.
Above content is only to design example of the present invention and explanation; affiliated those skilled in the art make various modifications to described specific embodiment or supplement or adopt similar mode to substitute; only otherwise depart from the design of invention or surmount this scope as defined in the claims, all should belong to protection scope of the present invention.
Claims (8)
1. a fluorine boron codope TiO
2nanometer sheet, is Anatase structure, and fluorine and boron mix in lattice, and expose crystal face be (001) crystal face, it is pattern in the form of sheets, the thickness of nanometer sheet is 1～100nm, the edge of construction unit nanometer sheet is rounding off.
2. a fluorine boron codope TiO as claimed in claim 1
2the preparation method of nanometer sheet, comprises with titanium source and prepares Anatase TiO
2the method of suspension, is characterized in that: fluorine boron codope TiO
2the preparation method of nanometer sheet also comprises by this Anatase TiO
2there is hydro-thermal reaction to prepare fluorine boron codope TiO in suspension and fluorine, boron source
2nanometer sheet, TiCl in reaction system
3with HBF
4between volume ratio be 1:0～1, the temperature of hydro-thermal reaction is 160～250 ℃, the reaction time is 6～15 hours.
3. fluorine boron codope TiO according to claim 2
2the preparation method of nanometer sheet, is characterized in that: described titanium source is TiCl
3, this Anatase TiO
2the preparation method of suspension is: measuring 20～35ml ethanolic solution is precursor liquid, slowly adds the 15wt%TiCl of 1～2ml
3solution, formation suspension stirs.
4. fluorine boron codope TiO according to claim 3
2the preparation method of nanometer sheet, is characterized in that: fluorine, boron source that hydro-thermal reaction adopts are HBF
4, the step of this hydro-thermal reaction is: suspension is placed in to consersion unit, drips 0～1ml HBF
440wt%HBF
4solution, in consersion unit, is then put consersion unit in air dry oven and is started to react.
5. fluorine boron codope TiO according to claim 4
2the preparation method of nanometer sheet, is characterized in that: after hydro-thermal reaction finishes, be cooled to room temperature, to obtained solidliquid mixture carry out centrifugal, wash and be dried.
6. fluorine boron codope TiO according to claim 5
2the preparation method of nanometer sheet, is characterized in that: solid product after solidliquid mixture is centrifugal adopts ethanol washing 3～5 times, then 80 ℃ of freeze-day with constant temperature 6～15 hours in baking oven.
7. according to the fluorine boron codope TiO described in claim 5 or 6
2the preparation method of nanometer sheet, is characterized in that: the product obtaining after dry is through 200～500 ℃ of heat treatments after 3～5 hours, and grind into powder, obtains fluorine boron codope TiO
2nanometer sheet.
8. a fluorine boron codope TiO as claimed in claim 1
2the purposes of nanometer sheet, is characterized in that: be for water purification as photochemical catalyst.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492417A (en) * | 2014-12-24 | 2015-04-08 | 陕西科技大学 | Preparation process of fluorine and rare earth element doped nano-titanium dioxide ternary photocatalyst |
| CN104588059A (en) * | 2014-12-24 | 2015-05-06 | 陕西科技大学 | Preparation technology of carbon and rare earth element doped nanometer titanium dioxide ternary photocatalyst |
| CN105126796A (en) * | 2015-07-13 | 2015-12-09 | 华北电力大学 | Preparation method of fluorine-doped lamellar black titanium dioxide nano material |
| CN105772039A (en) * | 2016-05-10 | 2016-07-20 | 宿州学院 | Fluorine and boron co-doped TiO2 nano-plate with crystal planes (001) and oxygen vacancy, method for preparing fluorine and boron co-doped TiO2 nano-plate and application thereof |
| CN108355648A (en) * | 2018-03-05 | 2018-08-03 | 河北工业大学 | A kind of preparation method and applications of titanium-based nano piece composite catalyst |
| CN113789109A (en) * | 2021-08-24 | 2021-12-14 | 福州大学 | Fluorine and boron double-doped graphene/alkyd resin composite coating and preparation method thereof |
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| CN103130266A (en) * | 2012-12-15 | 2013-06-05 | 王滨 | Preparation method of titanium dioxide hollow ball constructed by nano slices |
| JP2013154286A (en) * | 2012-01-30 | 2013-08-15 | Ohara Inc | Photocatalytic porous body |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013154286A (en) * | 2012-01-30 | 2013-08-15 | Ohara Inc | Photocatalytic porous body |
| CN103130266A (en) * | 2012-12-15 | 2013-06-05 | 王滨 | Preparation method of titanium dioxide hollow ball constructed by nano slices |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104492417A (en) * | 2014-12-24 | 2015-04-08 | 陕西科技大学 | Preparation process of fluorine and rare earth element doped nano-titanium dioxide ternary photocatalyst |
| CN104588059A (en) * | 2014-12-24 | 2015-05-06 | 陕西科技大学 | Preparation technology of carbon and rare earth element doped nanometer titanium dioxide ternary photocatalyst |
| CN105126796A (en) * | 2015-07-13 | 2015-12-09 | 华北电力大学 | Preparation method of fluorine-doped lamellar black titanium dioxide nano material |
| CN105126796B (en) * | 2015-07-13 | 2017-12-22 | 华北电力大学 | A kind of preparation method of Fluorin doped sheet black titanium dioxide nano material |
| CN105772039A (en) * | 2016-05-10 | 2016-07-20 | 宿州学院 | Fluorine and boron co-doped TiO2 nano-plate with crystal planes (001) and oxygen vacancy, method for preparing fluorine and boron co-doped TiO2 nano-plate and application thereof |
| CN105772039B (en) * | 2016-05-10 | 2018-08-21 | 宿州学院 | A kind of (001) crystal face fluorine boron codope TiO with Lacking oxygen2The Preparation method and use of nanometer sheet |
| CN108355648A (en) * | 2018-03-05 | 2018-08-03 | 河北工业大学 | A kind of preparation method and applications of titanium-based nano piece composite catalyst |
| CN113789109A (en) * | 2021-08-24 | 2021-12-14 | 福州大学 | Fluorine and boron double-doped graphene/alkyd resin composite coating and preparation method thereof |
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