CN101596457B - Nanometer titanium dioxide photocatalyst co-doped with boron and other elements and preparation method thereof - Google Patents
Nanometer titanium dioxide photocatalyst co-doped with boron and other elements and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a nanometer titanium dioxide photocatalyst co-doped with boron and other elements and a preparation method thereof. The method uses titanate and boric acid as a titanium source and a boron source; the other doped elements comprise one or more of transition metal, rare-earth metal or nonmetal; and the method adopts acetic acid, nitric acid or citric acid as a hydrolysis catalyst and a mixture of alcohol and water as a reaction system and prepares the nanometer titanium dioxide photocatalyst co-doped with the boron and the other elements by a sol-gel reaction and calcinations. The nanometer titanium dioxide co-doped with the boron and other elements prepared by the method can absorb visible light and has catalytic activity of the visible light.
Description
Technical field
The present invention relates to a kind of visual responsing titania light catalyst and preparation method thereof, relate in particular to nano titanium dioxide photocatalyst of a kind of visible-light response type boron and other element codope and preparation method thereof, belong to environmental chemical engineering, new material technology field.
Background technology
In the Environmental Chemistry field, titanium dioxide is demonstrating wide application prospect because of its superior function aspect the photocatalysis.Yet titanium dioxide belongs to wide bandgap semiconductor (sharp titanium titanium dioxide band-gap energy is 3.2eV), only has ultraviolet light just can make titanium dioxide generation electron transition, thereby produces electron-hole pair.Yet ultraviolet light only accounts for about 5% of sunshine, therefore prepare the study hotspot that the titanium deoxide catalyst with visible light catalysis activity is at present domestic and international light-catalyzed reaction aspect by modifying titanium dioxide, people have carried out the research of multiple method of modifying for this reason, wherein doping metals and nonmetal be common method of modifying, the mechanism that their modifying titanium dioxides improve catalytic activity is also different, and the effect of doping vario-property raising catalytic activity is relevant with kind and the content of foreign atom.The method of doping vario-property generally has sol-gel process, coprecipitation, hydro-thermal method, ion implantation, photocatalytic deposition method etc.Existing modified titanium dioxide doped document or exist manufacturing cost high, high to equipment requirement, be difficult to realize large-scale industrial production; Perhaps prepared titania-doped absorption band edge red shift is not enough far away etc.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of boron and other element coblended nano TiO 2 light catalyst and preparation method thereof are provided.Utilize the synergy of codope to come modifying titanium dioxide, with absorbing the band edge red shift to farther zone, further improve visible light catalysis activity; Prepare this coblended nano TiO 2 by sol gel reaction and calcination processing, reaction condition is gentle, is convenient to control and accomplish scale production.Prepared coblended nano TiO 2 can absorb visible light in the frequency range of non-constant width, and has visible light catalysis activity.
To achieve these goals, the invention provides the nano titanium dioxide photocatalyst of a kind of boron and other element codope, be mixed in titanium dioxide optical catalyst boron and other elements, described other elements can be in transition metal, rare earth metal or the nonmetalloid one or more; The total content of described boron and other elements is 0.5-35%, and preferable range is 0.8-32% (above ratio is the mole percent with respect to titanium atom).Boron and other element atomic ratios are 0.5-1.5: 0.6-38, and preferable range is 0.8-1.2: 0.8-30.In preferred embodiment of the present invention, most preferred condition is: boron is 1%, and other elements are 2-30% (with respect to the mole percent of titanium atom).
Described transition metal is iron, cobalt, nickel; Described rare earth element is ytterbium, lanthanum, cerium, praseodymium and europium; Described nonmetalloid is carbon, nitrogen, silicon or sulphur.
The present invention also provides the preparation method of the nano titanium dioxide photocatalyst of described boron and other element codope, mainly be to use titanate esters to do the titanium source, boric acid and other adulterant (generally using with the form of its salt) are by sol gel reaction and calcination method preparation.
Described titanate esters is butyl titanate, tetraethyl titanate, isopropyl titanate, and the content of described boron and other elements is 0.5-35%, and preferable range is 0.8-32% (above ratio is the mole percent with respect to titanium atom).Boron and other element atomic ratios are 0.5-1.5: 0.6-38, and preferable range is 0.8-1.2: 0.8-30.In preferred embodiment of the present invention, most preferred condition is: boron is 1%, and other elements are 2-30% (with respect to the mole percent of titanium atom).
Specifically, to use acetic acid (or nitric acid, citric acid) as the hydrolysis catalyst, (preferred volume ratio is alcohol: water=5-20: titanate esters generation hydrolysis 1) at the alcohol and water mixture, the further condensation of product, obtain titania gel, with titania gel heat treatment and grinding, the dry gel powder that last calcining and grinding is crossed obtains the codoping modified nano titanium oxide of visible-light response type again.Wherein, described alcohol is ethanol or isopropyl alcohol.
Preferably, the step of described preparation is as follows:
1) in the mixed solvent of the inorganic salts of boric acid and other element that will mix into are water-soluble and acetic acid, adds ethanol again or isopropyl alcohol obtains solution A;
2) titanate esters is dissolved in obtains solution B in the alcohol;
3) solution B slowly is added drop-wise in the solution A under magnetic agitation, dropwises rear continuation and stirs 2 hours with preparation colloidal sol C;
4) at room temperature ageing of colloidal sol C was obtained gel D in 3 days;
5) gel D was obtained xerogel E in 10 hours 80 ℃ of lower vacuum drying;
6) xerogel E is ground in agate mortar obtain powder F;
7) under 400-700 ℃, powder F was calcined in Muffle furnace 2 hours;
8) burnt powder is ground to form nanometer powder again in agate mortar, thereby obtain product.
Adopt boron and other element coblended nano TiO 2 of this law preparation, its particle size range is 6.2-12.5nm, can absorb visible light, absorbs band edge red shift 600nm extremely nearly, and has visible light catalysis activity.
The specific embodiment
Below by embodiment the present invention is specifically described; present embodiment is only for the present invention is further illustrated; can not be interpreted as limiting the scope of the invention, those skilled in the art's content according to the present invention is made some non-intrinsically safe modifications, all belongs to protection domain of the present invention.
Embodiment 1
0.001mol boric acid and 0.002mol ammonium fluoride are dissolved in 20mL distilled water and the 15mL glacial acetic acid mixed liquor, add 80mL ethanol and obtain solution A; The 0.1mol tetrabutyl titanate is dissolved in the 80mL absolute ethyl alcohol obtains solution B; Magnetic agitation was added drop-wise to solution B in the solution A in 60 minutes; Dropwise and continue to stir 1 hour, at room temperature ageing of the colloidal sol of generation 72 hours is then 80 ℃ of lower vacuum drying 10 hours; Grinding xerogel to the particle diameter that generates in agate mortar is about 10nm, the xerogel that will grind is again put into Muffle furnace, 600 ℃ of lower calcinings 2 hours, burnt powder is ground in agate mortar again, thereby obtain flaxen visible-light response type boron and nitrogen co-doped nano titanium oxide, its particle diameter is 10.0nm, titania-doped 1% boron atom and 2% nitrogen-atoms (with respect to the mol ratio of titanium atom) of containing of this kind.
The checking of visible light catalysis activity: take by weighing the boron of 0.05g preparation-nitrogen co-doped nano titanium oxide, join and contain in the self-control quartz reactor that 50mL concentration is 50mg/L phenol.Then the ultrasonic dispersion of this mixture was reached adsorption equilibrium in 1 hour in the stirring of lucifuge condition lower magnetic force after 5 minutes, open the above-mentioned suspension of light source irradiation that filters through filter plate (410nm), the degradation rate of 3 hours phenol of irradiation is 45.9%.
Embodiment 2
0.002mol boric acid, 0.002mol nine water ferric nitrates (III) and 0.002mol six water cerous nitrates (III) are dissolved in 20mL distilled water and the 15mL glacial acetic acid mixed liquor, add 80mL ethanol and obtain solution A; The 0.1mol tetrabutyl titanate is dissolved in the 80mL absolute ethyl alcohol obtains solution B; Magnetic agitation was added drop-wise to solution B in the solution A in 60 minutes; Dropwise and continue to stir 2 hours, at room temperature ageing of the colloidal sol of generation 72 hours is then 80 ℃ of lower vacuum drying 10 hours; Grinding xerogel to the particle diameter that generates in agate mortar is about 10nm, the xerogel that will grind is again put into Muffle furnace, 500 ℃ of lower calcinings 2 hours, burnt powder is ground in agate mortar again, thereby obtain visible-light response type boron, iron and cerium coblended nano TiO 2, its particle diameter is 11.2nm, titania-doped 2% boron atom, 2% iron atom and 2% cerium atom (with respect to the mol ratio of titanium atom) of containing of this kind.
The checking of visible light catalysis activity: take by weighing boron, iron and the cerium coblended nano TiO 2 of 0.05g preparation, join that to contain 50mL concentration be 10mg/L 2, in the self-control quartz reactor of 4-chlorophenesic acid (DCP).Then the ultrasonic dispersion of this mixture was reached adsorption equilibrium in 1 hour in the stirring of lucifuge condition lower magnetic force after 5 minutes, open the above-mentioned suspension of light source irradiation that filters through filter plate (410nm), the degradation rate of 3 hours DCP of irradiation is 60.3%.
Embodiment 3
0.0005mol boric acid and 0.0005mol nine water ferric nitrates (III) are dissolved in 10mL distilled water and the 8mL glacial acetic acid mixed liquor, add 30mL ethanol and obtain solution A; 0.05mol tetrabutyl titanate and 3.12g ethyl orthosilicate be dissolved in the 50mL absolute ethyl alcohol obtain solution B; Magnetic agitation was added drop-wise to solution B in the solution A in 40 minutes; Dropwise and continue to stir 2 hours, at room temperature ageing of the colloidal sol of generation 72 hours is then 80 ℃ of lower vacuum drying 10 hours; Grinding xerogel to the particle diameter that generates in agate mortar is about 10nm, the xerogel that will grind is again put into Muffle furnace, 600 ℃ of lower calcinings 2 hours, burnt powder is ground in agate mortar again, thereby obtain visible-light response type boron and iron coblended nano TiO 2/silica, its particle diameter is 6.2nm, titania-doped 1% boron atom, 1% iron atom and 30% silicon atom (with respect to the mol ratio of titanium atom) of containing of this kind.
The checking of visible light catalysis activity: take by weighing boron and the iron codope titanium dioxide/silica of 0.05g preparation, join and contain in the self-control quartz reactor that 50mL concentration is 50mg/L phenol.Then the ultrasonic dispersion of this mixture was stirred 1 hour at lucifuge condition lower magnetic force after 5 minutes, open the above-mentioned suspension of light source irradiation that filters through filter plate (410nm), the degradation rate of phenol is 50.5% in 3 hours.
Embodiment 4
0.001mol boric acid, 0.001mol six water nickel nitrates (II) are dissolved in 20mL distilled water and the 15mL glacial acetic acid mixed liquor, add 80mL ethanol and obtain solution A; The 0.05mol tetrabutyl titanate is dissolved in the 80mL absolute ethyl alcohol obtains solution B; Magnetic agitation was added drop-wise to solution B in the solution A in 60 minutes; Dropwise and continue to stir 2 hours, at room temperature ageing of the colloidal sol of generation 72 hours is then 80 ℃ of lower vacuum drying 10 hours; Grinding xerogel to the particle diameter that generates in agate mortar is about 10nm, the xerogel that will grind is again put into Muffle furnace, 500 ℃ of lower calcinings 2 hours, burnt powder is ground in agate mortar again, thereby obtain visible-light response type boron, nickel co-doped nano titanium oxide, its particle diameter is 12.5nm, titania-doped 2% boron atom, 2% nickel (with respect to the mol ratio of titanium atom) of containing of this kind.
The checking of visible light catalysis activity: take by weighing the boron of 0.05g preparation-lanthanum co-doped nano titanium oxide, join and contain in the self-control quartz reactor that 50mL concentration is 50mg/L phenol.Then the ultrasonic dispersion of this mixture was reached adsorption equilibrium in 1 hour in the stirring of lucifuge condition lower magnetic force after 5 minutes, open the above-mentioned suspension of light source irradiation that filters through filter plate (410nm), the degradation rate of 3 hours phenol of irradiation is 48.2%.
Embodiment 5
0.001mol boric acid, 0.0005mol lanthanum nitrate hexahydrate (III) are dissolved in 20mL distilled water and the 15mL glacial acetic acid mixed liquor, add 80mL ethanol and obtain solution A; The 0.05mol tetrabutyl titanate is dissolved in the 80mL absolute ethyl alcohol obtains solution B; Magnetic agitation was added drop-wise to solution B in the solution A in 30 minutes; Dropwise and continue to stir 2 hours, at room temperature ageing of the colloidal sol of generation 72 hours is then 80 ℃ of lower vacuum drying 10 hours; Grinding xerogel to the particle diameter that generates in agate mortar is about 10nm, the xerogel that will grind is again put into Muffle furnace, 500 ℃ of lower calcinings 2 hours, burnt powder is ground in agate mortar again, thereby obtain visible-light response type boron, lanthanum co-doped nano titanium oxide, its particle diameter is 9.7nm, titania-doped 2% boron atom, 1% lanthanum (with respect to the mol ratio of titanium atom) of containing of this kind.
The checking of visible light catalysis activity: take by weighing the boron of 0.05g preparation-lanthanum co-doped nano titanium oxide, join that to contain 50mL concentration be 10mg/L 2, in the self-control quartz reactor of 4-chlorophenesic acid (DCP).Then the ultrasonic dispersion of this mixture was reached adsorption equilibrium in 1 hour in the stirring of lucifuge condition lower magnetic force after 5 minutes, open the above-mentioned suspension of light source irradiation that filters through filter plate (410nm), the degradation rate of 3 hours DCP of irradiation is 57.2%.
Comparative example 1
The 0.002mol ammonium fluoride is dissolved in 20mL distilled water and the 15mL glacial acetic acid mixed liquor, adds 80mL ethanol and obtain solution A; The 0.1mol tetrabutyl titanate is dissolved in the 80mL absolute ethyl alcohol obtains solution B; Magnetic agitation was added drop-wise to solution B in the solution A in 60 minutes; Dropwise and continue to stir 1 hour, at room temperature ageing of the colloidal sol of generation 72 hours is then 80 ℃ of lower vacuum drying 10 hours; Grinding xerogel to the particle diameter that generates in agate mortar is about 10nm, the xerogel that will grind is again put into Muffle furnace, 600 ℃ of lower calcinings 2 hours, burnt powder is ground in agate mortar again, obtain nitrogen-doped titanium dioxide, its particle diameter is 11.9nm, titania-doped 2% nitrogen-atoms (with respect to the mol ratio of titanium atom) that contains of this kind.
The checking of visible light catalysis activity: take by weighing the nitrogen-doped nanometer titanium dioxide of 0.05g preparation, join and contain in the self-control quartz reactor that 50mL concentration is 50mg/L phenol.Then the ultrasonic dispersion of this mixture was reached adsorption equilibrium in 1 hour in the stirring of lucifuge condition lower magnetic force after 5 minutes, open the above-mentioned suspension of light source irradiation that filters through filter plate (410nm), the degradation rate of 3 hours phenol of irradiation is 30.6%.
Comparative example 2
0.002mol nine water ferric nitrates (III) are dissolved in 20mL distilled water and the 15mL glacial acetic acid mixed liquor, add 80mL ethanol and obtain solution A; The 0.1mol tetrabutyl titanate is dissolved in the 80mL absolute ethyl alcohol obtains solution B; Magnetic agitation was added drop-wise to solution B in the solution A in 60 minutes; Dropwise and continue to stir 2 hours, at room temperature ageing of the colloidal sol of generation 72 hours is then 80 ℃ of lower vacuum drying 10 hours; Grinding xerogel to the particle diameter that generates in agate mortar is about 10nm, the xerogel that will grind is again put into Muffle furnace, 500 ℃ of lower calcinings 2 hours, burnt powder is ground in agate mortar again, it is titania-doped to obtain iron, its particle diameter is 13.3nm, titania-doped 2% iron atom (with respect to the mol ratio of titanium atom) that contains of this kind.
The checking of visible light catalysis activity: take by weighing the iron doped nano titanium dioxide of 0.05g preparation, join that to contain 50mL concentration be 10mg/L 2, in the self-control quartz reactor of 4-chlorophenesic acid (DCP).Then the ultrasonic dispersion of this mixture was reached adsorption equilibrium in 1 hour in the stirring of lucifuge condition lower magnetic force after 5 minutes, open the above-mentioned suspension of light source irradiation that filters through filter plate (410nm), the degradation rate of 3 hours DCP of irradiation is 10.2%.
Comparative example 3
0.001mol boric acid is dissolved in 20mL distilled water and the 15mL glacial acetic acid mixed liquor, adds 80mL ethanol and obtain solution A; The 0.1mol tetrabutyl titanate is dissolved in the 80mL absolute ethyl alcohol obtains solution B; Magnetic agitation was added drop-wise to solution B in the solution A in 60 minutes; Dropwise and continue to stir 1 hour, at room temperature ageing of the colloidal sol of generation 72 hours is then 80 ℃ of lower vacuum drying 10 hours; Grinding xerogel to the particle diameter that generates in agate mortar is about 10nm, the xerogel that will grind is again put into Muffle furnace, 600 ℃ of lower calcinings 2 hours, burnt powder is ground in agate mortar again, obtain boron doped titanic oxide, its particle diameter is 12.5nm, the titania-doped 1% boron atom (with respect to the mol ratio of titanium atom) that contains of this kind.
The checking of visible light catalysis activity: take by weighing the boron doped nano titanium dioxide of 0.05g preparation, join and contain in the self-control quartz reactor that 50mL concentration is 50mg/L phenol.Then the ultrasonic dispersion of this mixture was reached adsorption equilibrium in 1 hour in the stirring of lucifuge condition lower magnetic force after 5 minutes, open the above-mentioned suspension of light source irradiation that filters through filter plate (410nm), the degradation rate of 3 hours phenol of irradiation is 23.3%.
Claims (8)
1. the nano titanium dioxide photocatalyst of a boron and other element codope, boron and other elements have mixed in this titanium dioxide optical catalyst, described other elements are one or more in transition metal, rare earth metal or the nonmetalloid, it is characterized in that described transition metal is iron, cobalt and nickel; Described nonmetalloid is carbon, nitrogen, silicon or sulphur;
The total amount of described boron and other elements is 0.5-35% with respect to the mole percent of titanium atom; The atomic ratio of described boron and other elements is 0.5-1.5: 0.6-38; By the inorganic salts with boric acid and the element that will mix, use acetic acid, nitric acid or citric acid as the hydrolysis catalyst, titanate esters generation hydrolysis in the alcohol and water mixture, the further condensation of product, obtain titania gel, with titania gel heat treatment and grinding, the dry gel powder of crossing 500-600 ℃ of calcining and grinding at last obtains the codoping modified nano titanium oxide of visible-light response type again; Wherein, described alcohol is ethanol or isopropyl alcohol.
2. the nano titanium dioxide photocatalyst of boron according to claim 1 and other element codope is characterized in that described rare earth element is ytterbium, lanthanum, cerium, praseodymium and europium.
3. the nano titanium dioxide photocatalyst of boron according to claim 1 and other element codope, the total amount that it is characterized in that described boron and other elements is 0.8-32% with respect to the mole percent of titanium atom.
4. the nano titanium dioxide photocatalyst of boron according to claim 1 and other element codope, the atomic ratio that it is characterized in that described boron and other elements is 0.8-1.2: 0.8-30.
5. the nano titanium dioxide photocatalyst of boron according to claim 1 and other element codope, the content that it is characterized in that described boron is 1% with respect to the mole percent of titanium atom, and the content of described other elements is 2-30% with respect to the mole percent of titanium atom.
6. method for preparing the nano titanium dioxide photocatalyst of boron claimed in claim 1 and other element codope, to use titanate esters as the titanium source, boric acid is as the boron source, other doped chemical comprises transition metal, rare earth metal or nonmetalloid, by the inorganic salts with boric acid and the element that will mix, use acetic acid, nitric acid or citric acid are as the hydrolysis catalyst, titanate esters generation hydrolysis in the alcohol and water mixture, the further condensation of product, obtain titania gel, again with titania gel heat treatment and grinding, the dry gel powder of crossing 500-600 ℃ of calcining and grinding at last obtains the codoping modified nano titanium oxide of visible-light response type; Wherein, described alcohol is ethanol or isopropyl alcohol.
7. the preparation method of the nano titanium dioxide photocatalyst of boron according to claim 6 and other element codope is characterized in that described titanate esters is butyl titanate, tetraethyl titanate, isopropyl titanate; Described transition metal is iron, cobalt and nickel; Described rare earth element is ytterbium, lanthanum, cerium, praseodymium and europium; Described nonmetalloid is carbon, nitrogen, silicon or sulphur; Described alcohol is ethanol or isopropyl alcohol.
8. the preparation method of the nano titanium dioxide photocatalyst of boron according to claim 6 and other element codope is characterized in that its main preparation process is as follows:
1) in the mixed solvent of the inorganic salts of boric acid and the element that will mix are water-soluble and acetic acid, adds ethanol again or isopropyl alcohol obtains solution A;
2) titanate esters is dissolved in obtains solution B in the alcohol;
3) solution B slowly is added drop-wise in the solution A under magnetic agitation, dropwises rear continuation and stirs 2 hours with preparation colloidal sol C;
4) at room temperature ageing of colloidal sol C was obtained gel D in 3 days;
5) gel D was obtained xerogel E in 10 hours 80 ℃ of lower vacuum drying;
6) xerogel E is ground in agate mortar obtain powder F;
7) under 500-600 ℃, powder F was calcined in Muffle furnace 2 hours;
8) burnt powder is ground to form nanometer grade powder again in agate mortar, thereby obtain product.
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| CN103806270A (en) * | 2014-02-18 | 2014-05-21 | 南通纺织职业技术学院 | Modified titanium dioxide hydrosol and preparation method thereof |
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