CN103657625B - A kind of exposure high energy crystal face { preparation method of 001} rutile-type boron doped titanic oxide microballoon - Google Patents
A kind of exposure high energy crystal face { preparation method of 001} rutile-type boron doped titanic oxide microballoon Download PDFInfo
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Abstract
The invention provides a kind of exposure high energy crystal face { 001} rutile-type boron doped titanic oxide (B-TiO
2) preparation method of microballoon, belong to technical field of preparation for inorganic material; Concrete steps titanium boride (TiB) are joined hydrazine contain in the hydrochloric acid solution of sodium fluoride (NaF), strong stirring, then transfer to 200 DEG C of constant temperature in liner four polyvinyl fluoride reactor and keep 12-24 h, naturally cool to room temperature, products therefrom after filtration, precipitates each three times, then at 60 ~ 80 DEG C with distilled water, absolute ethanol washing, dry 12 ~ 24 h, obtained exposure high energy crystal face { 001} rutile-type B-TiO
2microballoon, { 001} exposure almost reaches 100% to high energy crystal face; Preparation technology of the present invention is simple, reproducible; The B-TiO prepared
2microsphere Size is controlled, size is even, and diameter is about 3-5 μm; Boron element is bulk phase-doped, is evenly distributed, and doping size is controlled; And the B-TiO prepared
2microballoon has excellent visible light catalysis activity, is expected to obtain in the field such as photolysis water hydrogen, degradable organic pollutant apply widely.
Description
Technical field
The present invention relates to a kind of preparation method of titanium dioxide microballoon sphere, { preparation method of 001} rutile-type boron doped titanic oxide microballoon, belongs to technical field of preparation for inorganic material to be specifically related to a kind of exposure high energy crystal face.
Background technology
Environmental pollution and energy crisis are two hang-ups of puzzlement current world economy development; a large amount of uses of fossil fuel not only cause huge pollution to global environment and ecology; and these energy are non-renewable resources, the storage content in the whole world estimates that the middle of this century is about to exhaustion.Therefore, problem of environmental pollution how is solved extremely urgent.Since Honda and Fujishima in 1972 etc. find TiO
2since Single Crystalline Electrodes has certain redox property under the effect of light, scientists is solve environmental pollution this difficult problem to propose an energy-efficient solution: utilize sunshine to carry out decomposing organic pollutant.
Traditional semiconductor light-catalyst mainly inorganic compound, comprise metal oxide, sulfide, nitride, phosphide and compound thereof etc., most is representational is TiO
2.TiO
2water insoluble, resistance to corrosion strong, cheap and conveniently process, the advantage such as biological function, photochemical properties are stable, environmentally safe, become a kind of desirable photochemical catalyst.But TiO
2band gap be 3.2 eV, only have wavelength just can excite the transition of valence-band electrons lower than the ultraviolet light of 380 below nm, and solar spectrum medium ultraviolet light is less than 5%, and the visible ray that wavelength is 400-750 nm accounts for about 45%, this fundamentally constrains TiO
2the practical application of photochemical catalyst.At present, researcher widens TiO by methods such as doping, semiconductors coupling, dye sensitization, noble-metal-supported and conjugated polymers compounds
2light absorption band edge, improve photocatalytic activity.Doping is to TiO
2a kind of effective method of modification, not only can promote TiO
2the red shift of light absorption band edge, and its photocatalytic activity can be improved.And exposure has exposure high energy crystal face, and { 001} rutile-type boron doped titanic oxide microballoon is not reported so far.
In the preparation of boron doped titanic oxide, current preparation method mainly sol-gel process, the method is used as material mainly boric acid and the triethyl borate in boron source, and titanium source comprises Ti-inorganic salt as TiCl
4and Titanium alkoxides, as isopropyl titanate, butyl titanate.But the doping of the method B is limited in titanium dioxide lattice, because B ion doping is too much, will separate out from titanium dioxide crystal inside and form B
2o
3.Mechano-chemical method also has report, although the preparation process of mechano-chemical method is simple, due to unbalance stress, the domain size distribution of product and the degree of scatter of doped chemical bad.The product purity that hydrothermal synthesis method is formed is high, and good dispersion, is divided into a step and two one-step hydrothermals.After titanium salt solution, sulfuric acid and boric acid are directly carried out hydrothermal treatment consists by Wei Fengyu etc., precipitate and dry at 90 DEG C and obtain the codoping modified catalyst of boron sulphur after repeatedly washing.Zhao Yan rather etc. has prepared B-TiO with two one-step hydrothermals
2, by TiO
2solution mixes with boric acid to stir evenly and is placed in polytetrafluoroethylene (PTFE) reactor, at 85 DEG C of hydro-thermal reaction 5 h, then in 110 DEG C of reaction 20 h, calcines after the colloid drying obtained.
The present invention selects titanium boride as raw material, joins the mixed solution of NaF and hydrochloric acid, reacts under thermal and hydric environment, and a step can obtain to have and expose high energy crystal face { 001} rutile-type boron doped titanic oxide, preparation technology is simple, reproducible.The B-TiO prepared
2microsphere Size is controlled, size is even, and average diameter is about 3-5 μm; Boron element is bulk phase-doped, is evenly distributed, and doping size is controlled; { 001} exposure almost reaches 100% to high energy crystal face.The B-TiO prepared
2microballoon has excellent visible light catalysis activity, is expected to obtain in the field such as photolysis water hydrogen, degradable organic pollutant apply widely.
Summary of the invention
The invention provides a kind of exposure high energy crystal face { 001} rutile-type boron doped titanic oxide (B-TiO
2) preparation method of microballoon, preparation technology is simple, reproducible; The B-TiO prepared
2microsphere Size is controlled, size is even, and average diameter is about 3-5 μm, high energy crystal face 001} exposure almost reaches 100%, and B-TiO
2microballoon has excellent visible light catalysis activity.
For realizing the object of foregoing invention, the technical scheme that the present invention takes is as follows:
A kind of exposure high energy crystal face { 001} rutile-type B-TiO
2the preparation method of microballoon, comprises the steps:
(1) join in the mixed solution of NaF and hydrochloric acid by 500 mg ~ 1000 mg titanium borides, wherein the concentration of NaF is 0.015mol/L, and the concentration of hydrochloric acid is 1-3 mol/L, strong stirring 15 ~ 60 min, obtains mixed liquor;
(2) mixed liquor that step (1) obtains is transferred in the hydrothermal reaction kettle of liner four polyvinyl fluoride;
(3) hydrothermal reaction kettle of liner four polyvinyl fluoride is placed in drying box, keeps constant temperature 200 DEG C, reaction 12 ~ 24 h, then naturally cool to room temperature;
(4) step (3) products therefrom is filtered, precipitate each three times with distilled water, absolute ethanol washing, then at 60 ~ 80 DEG C, dry 12 ~ 24 h, obtained B-TiO
2microballoon.
Titanium boride described in step (1) and sodium fluoride are that analysis is pure, and purity is 99%, and hydrochloric acid is the solution after concentrated hydrochloric acid dilution, and concentrated hydrochloric acid concentration is 36.5%.
Keep constant temperature 200 DEG C described in step (3), reaction 12 ~ 24 h refer to: under hydrothermal conditions, drying box constant temperature is at 200 DEG C, and constant temperature time is 12 ~ 24 h.
Thermostat temperature described in step (3) keeps stable, and temperature fluctuation range is ± 0.1 DEG C.
The one adopting the present invention to prepare exposes high energy crystal face { 001} rutile-type boron doped titanic oxide (B-TiO
2) microballoon be applied to visible ray catalyzes degraded organic contamination reaction, such as at normal temperatures, the reaction time is 2.5h, and result shows B-TiO prepared by the present invention
2microballoon has excellent catalytic activity.
To the B-TiO adopting the inventive method obtained
2d8 ADVANCE type X-ray powder diffractometer (XRD) that microballoon adopts German Bruker company to produce (
λ cu =0.15418 nm) carry out Crystalline form analysis (as Fig. 1), result shows: products therefrom is rutile titanium dioxide; Adopt LEO1530VP type field emission scanning electron microscope (SEM) to carry out morphology analysis (as Fig. 2), result shows: gained titanium dioxide is spherical in shape, and by the active crystal face of much exposure high energy, { 001} nanometer sheet forms, and diameter is about 3-5 μm; Adopt the photoelectricity power spectrum of Britain VG ESM-LAB to carry out XPS analysis (as Fig. 3) to obtained material, result shows to there are B, Ti and O tri-kinds of elements in product, illustrates that there is boron element has successfully been doped in titanium dioxide.
To the B-TiO adopting the inventive method obtained
2microballoon and nitrogen-doped titanium dioxide (N-P25) have carried out the effectiveness comparison (as Fig. 4) of photo-catalytic degradation of methyl-orange under visible ray effect, and result shows, although particle is than about N-P25(50nm) large, the B-TiO of preparation
2microballoon shows more high visible catalytic effect.This photochemical catalyst can in the extensive use such as photolysis water hydrogen, degradable organic pollutant.
the present invention's beneficial effect is compared with prior art:
(1) its technology preparation condition of preparation method of the present invention is gentleer, and equipment is simple.Boron element is bulk phase-doped, is evenly distributed, and doping size is controlled.Without the need to high temperature crystallization, avoid high-temperature process to the pattern of product and stability influence;
(2) be that raw material directly obtains rutile-type B-TiO under hydrothermal conditions with titanium boride
2microballoon, prepared B-TiO
2microballoon has the advantage that size is controlled, size is even, visible light photocatalysis active is high, particularly expose high energy active crystal face 001}, exposure almost reaches 100%;
(3) B-TiO for preparing of the present invention
2compared with the effect that microballoon and nitrogen-doped titanium dioxide (N-P25) have carried out photo-catalytic degradation of methyl-orange under visible ray effect, there is more high catalytic activity.
Accompanying drawing explanation
Fig. 1 is the B-TiO that the present invention obtains
2microballoon X-ray powder diffraction (XRD) figure;
Fig. 2 is the B-TiO that the present invention obtains
2microballoon SEM (SEM) figure;
Fig. 3 is the B-TiO that the present invention obtains
2microballoon photoelectron spectroscopy (XPS) collection of illustrative plates;
Fig. 4 is the B-TiO that the present invention obtains
2microballoon (a) and nitrogen-doped titanium dioxide (N-P25) (b) have carried out the effectiveness comparison figure of photo-catalytic degradation of methyl-orange under visible ray effect.
Detailed description of the invention
Be described in further details the present invention below by embodiment, these embodiments are only used for the present invention is described, do not limit the scope of the invention.
embodiment 1
500 mg titanium boride (TiB are added in the beaker of 250 ml, 99%) contain to 70 ml in the hydrochloric acid solution of 0.015 mol/L sodium fluoride, wherein the concentration of hydrochloric acid is 1.0 mol/L, strong stirring 30 min, then transfer in 100 ml liner four polyvinyl fluoride hydrothermal reaction kettles, put in 200 DEG C of thermostatic drying chambers, under solvent heat condition, keep reaction 24 h.After reaction terminates, naturally cool to room temperature, respectively wash three times with distilled water and absolute ethyl alcohol, obtained after product being placed in 70 DEG C of drying box vacuum drying 12 h.Adopt B-TiO prepared by this step
2microsphere diameter about 3 μm.
embodiment 2
1000 mg titanium boride (TiB are added in the beaker of 250 ml, 99%) contain to 70 ml in the hydrochloric acid solution of 0.015 mol/L sodium fluoride, wherein the concentration of hydrochloric acid is 1.5 mol/L, strong stirring 15 min, then transfer in 100 ml liner four polyvinyl fluoride hydrothermal reaction kettles, put in 200 DEG C of thermostatic drying chambers, under solvent heat condition, keep reaction 18 h.After reaction terminates, naturally cool to room temperature, respectively wash three times with distilled water and absolute ethyl alcohol, obtained after product being placed in 80 DEG C of drying box vacuum drying 12 h.Adopt B-TiO prepared by this step
2microsphere diameter about 3.8 μm.
embodiment 3
800 mg titanium boride (TiB are added in the beaker of 250 ml, 99%) contain to 70 ml in the hydrochloric acid solution of 0.015 mol/L sodium fluoride, wherein the concentration of hydrochloric acid is 2.0 mol/L, strong stirring 40 min, then transfer in 100 ml liner four polyvinyl fluoride hydrothermal reaction kettles, put in 200 DEG C of thermostatic drying chambers, under solvent heat condition, keep reaction 20 h.After reaction terminates, naturally cool to room temperature, respectively wash three times with distilled water and absolute ethyl alcohol, obtained after product being placed in 75 DEG C of drying box vacuum drying 18 h.Adopt B-TiO prepared by this step
2microsphere diameter about 4.2 μm.
embodiment 4
600 mg titanium boride (TiB are added in the beaker of 250 ml, 99%) contain to 70 ml in the hydrochloric acid solution of 0.015 mol/L sodium fluoride, wherein the concentration of hydrochloric acid is 2.5 mol/L, strong stirring 50 min, then transfer in 100 ml liner four polyvinyl fluoride hydrothermal reaction kettles, put in 200 DEG C of thermostatic drying chambers, under solvent heat condition, keep reaction 12h.After reaction terminates, naturally cool to room temperature, respectively wash three times with distilled water and absolute ethyl alcohol, obtained after product being placed in 70 DEG C of drying box vacuum drying 22 h.Adopt B-TiO prepared by this step
2microsphere diameter about 4.8 μm.
embodiment 5
700 mg titanium boride (TiB are added in the beaker of 250 ml, 99%) contain to 70 ml in the hydrochloric acid solution of 0.015 mol/L sodium fluoride, wherein the concentration of hydrochloric acid is 3.0 mol/L, strong stirring 60 min, then transfer in 100 ml liner four polyvinyl fluoride hydrothermal reaction kettles, put in 200 DEG C of thermostatic drying chambers, under solvent heat condition, keep reaction 15 h.After reaction terminates, naturally cool to room temperature, respectively wash three times with distilled water and absolute ethyl alcohol, obtained after product being placed in 80 DEG C of drying box vacuum drying 24 h.Adopt B-TiO prepared by this step
2microsphere diameter about 5 μ.
Claims (4)
1. { preparation method for 001} rutile-type boron doped titanic oxide microballoon, is characterized in that: comprise the steps: to expose high energy crystal face
(1) join in the mixed solution of NaF and hydrochloric acid by 500 mg ~ 1000 mg titanium borides, wherein the concentration of NaF is 0.015mol/L, and the concentration of hydrochloric acid is 1.0-3.0 mol/L, strong stirring 15 ~ 60 min, obtains mixed liquor;
(2) mixed liquor that step (1) obtains is transferred in the hydrothermal reaction kettle of inner liner polytetrafluoroethylene;
(3) hydrothermal reaction kettle of inner liner polytetrafluoroethylene is placed in drying box, keeps constant temperature 200 DEG C, reaction 12 ~ 24 h, then naturally cool to room temperature;
(4) step (3) products therefrom is filtered, precipitate each three times with distilled water, absolute ethanol washing, then at 60 ~ 80 DEG C, dry 12 ~ 24 h, obtained boron doped titanic oxide microballoon.
2. { preparation method of 001} rutile-type boron doped titanic oxide microballoon, is characterized in that one exposure high energy crystal face according to claim 1: titanium boride described in step (1) and sodium fluoride are that analysis is pure, and purity is 99%; Hydrochloric acid is the solution of concentrated hydrochloric acid dilution, and concentrated hydrochloric acid concentration is 36.5%.
3. one according to claim 1 exposes the high energy crystal face { preparation method of 001} rutile-type boron doped titanic oxide microballoon, it is characterized in that: described in step (3), keep constant temperature 200 DEG C, reaction 12 ~ 24 h refer to: under hydrothermal conditions, drying box constant temperature is at 200 DEG C, and constant temperature time is 12 ~ 24 h.
4. the one according to claim 1 or 3 exposes high energy crystal face, and { preparation method of 001} rutile-type boron doped titanic oxide microballoon, is characterized in that: thermostat temperature described in step (3) keeps stable, and temperature fluctuation range is ± 0.1 DEG C.
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| CN104310468B (en) * | 2014-10-14 | 2016-01-27 | 吉林大学 | One prepares the method for monodisperse titanium dioxide (B) nanoparticle |
| CN104607165B (en) * | 2015-02-10 | 2017-04-26 | 哈尔滨工业大学 | Preparation method of photocatalyst containing boron cross-shaped titanium dioxide |
| CN107999050A (en) * | 2017-11-28 | 2018-05-08 | 阜阳师范学院 | A kind of B-TiO2The preparation and its application of photochemical catalyst |
| CN108543528A (en) * | 2018-04-10 | 2018-09-18 | 陕西科技大学 | It is a kind of to prepare different-shape rutile TiO2The method of photochemical catalyst |
| CN108598455B (en) * | 2018-04-26 | 2020-08-11 | 福州大学 | Hierarchical structure TiO2Preparation method of (E) -B and application thereof in lithium ion battery |
| CN113087011A (en) * | 2021-03-31 | 2021-07-09 | 福州大学 | Titanium dioxide B-phase material and preparation method and application thereof |
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