CN1314485C - Surface modification of titanium oxide base light catalyzed material - Google Patents
Surface modification of titanium oxide base light catalyzed material Download PDFInfo
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- CN1314485C CN1314485C CNB2004100308409A CN200410030840A CN1314485C CN 1314485 C CN1314485 C CN 1314485C CN B2004100308409 A CNB2004100308409 A CN B2004100308409A CN 200410030840 A CN200410030840 A CN 200410030840A CN 1314485 C CN1314485 C CN 1314485C
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Abstract
The present invention relates to a surface modification method for a titanium oxide base photocatalysis material, which comprises: the titanium oxide base photocatalysis material is cleaned, a hydrolysis inhibition agent, a titanium source and a metal ion organic solution are orderly added in according to the proportion that the molar ratio is equal to 0.1 to 100: 1: 0.0001 to 0.2, an excess alkali solution of which the quantity is corresponding to that of the neutralizing hydrolysis inhibition agent and the hydrolysis titanium source is added after a mixture is dispersed uniformly, the titanium source is hydrolyzed until completely converted into titanium hydroxides, and an obtained crude product is dispersed in an acidic dilute solution, uniformly mixed, centrifugated, washed and dried to obtain the surface modification titanium oxide base photocatalysis material. The photocatalysis material modified by the method obtains the good photocatalysis effect which can not be realized by single method modification, the service life of photoproduction electrons and empty holes of the present invention are prolonged, a surface defect and active hydroxy are increased, the photocatalytic activity is increased, and the present invention can be used for the fields of materials before modification and cal also effectively generate degradation for most of pollution articles in water bodies and in the air.
Description
Technical field
The invention belongs to the conductor photocatalysis material technical field, specifically relate to a kind of surface modifying method of titania based catalysis material.
Background technology
The conductor photocatalysis technology is that the semi-conducting material that utilizes ultraviolet light irradiation to have photocatalytic activity causes light-catalyzed reaction.TiO
2Catalysis material is a kind of conductor photocatalysis material that is subjected to extensive concern in recent years.Studies show that in a large number dyestuff, surfactant, organohalogen compounds, agricultural chemicals, oils, cyanide etc. can both be by TiO
2Finish photocatalytic degradation effectively, decolouring, detoxification, mineralising are the inorganic molecules material, thereby eliminate the pollution to environment.In addition, TiO
2That light-catalyzed reaction also has is nontoxic, catalytic activity is high, oxidability is strong, good stability, reaction condition gentleness, use that equipment needed thereby is simple, secondary pollution is little, easy operating, to low concentration pollutant and vapor phase contaminants also have good effect of removing, catalysis material to be easy to get, operating cost is low, to be expected with sunshine be to react advantage such as light source.Thereby, TiO
2Catalysis material is a kind of very promising material of curbing environmental pollution, and passes through TiO
2The work that the preparation of catalysis material and modification further improve its photocatalytic activity also just becomes the emphasis that people study.
In order to improve TiO
2Photocatalytic activity, it is material modified that the researcher adopts the whole bag of tricks such as metal ion mixing, noble metal loading, surperficial acidifying, semiconductor are compound, surface sensitizing usually, and obtained certain effect.For example, mix in the powder preparation process, or adopt radio-frequency technique to carry out ion and inject, these methods all are to use single method to carry out modification, are not suitable for big industrial production, and still inaccessiable desirable good light catalytic effect.
Summary of the invention
The objective of the invention is to overcome and use single method that titania based catalysis material is carried out modification, be not suitable for big industrial production, and the defective of still inaccessiable desirable good light catalytic effect, thereby provide a kind of surface modifying method that has the good light catalytic effect and be fit to big industrial titania based catalysis material.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of surface modifying method of titania based catalysis material, with modified method synergistic application such as surface coating, doping and acidifyings, when coating, mix, be that titanium source and doping metals successively add in the system hydrolysis simultaneously to or be deposited in titania based material surface, carry out acidification afterwards, it specifically comprises following step:
1) titania based catalysis material is carried out cleaning: earlier with titania based catalysis material 100～500 ℃ of roastings, can adsorbable organic pollution to remove the surface; Should directly be soaked in or use ultrasonic wave to be dispersed in the anhydrous organic solution by titania based catalysis material again;
2) disperse: in the mixed system that step 1) obtains in molar ratio 0.1～100: 1: 0.0001～0.20 ratio adds the ethanol or the acetone soln of hydrolysis inhibitor, titanium source and metal ion successively, stirs or sonic oscillation makes mixture be uniformly dispersed;
3) hydrolysis: under stirring or sonic oscillation, to step 2) add excess base solution in the mixed system that obtains with respect to the amount in neutralizing hydrolysis inhibitor and hydrolysis titanium source, be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, dry, obtained at surface doping the titania based catalysis material crude product of metal ion;
4) surperficial acidifying: the crude product that step 3) is obtained is in vacuum drying, and disperse or be dipped in the acid solution, till pH detection paper mixed liquor is acidity, centrifugal then, washing, oven dry obtains the titania based catalysis material of surface modification.
Titania based catalysis material in the described step 1) comprises the film of particle, the titanium dioxide of titanium dioxide, at other suprabasil titanium deoxid films with wrapped the titanium deoxid film that is attached to other particle surfaces; The thickness of film is 2nm～1 μ m.
Anhydrous organic solution in the described step 1) is for the organic solvent of water content below 1wt%, to be easy to Separation of Solid and Liquid.
Anhydrous organic solution in the described step 1) is ethanol or acetone.
Described step 2) hydrolysis inhibitor is acetic acid or isopropyl alcohol.
Described step 2) metal ion is to be selected from a kind of in Mg, Ca, Sr, Ba, Sc, Y, V, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Sn, Pb, Cu, Zn, the lanthanide series.
The aqueous slkali of described step 3) is the aqueous solution of inorganic base, comprises ammoniacal liquor, sodium hydroxide solution, potassium hydroxide solution.
The acid of described step 4) is inorganic middle strong acid, comprises nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, perchloric acid.
The surface modifying method of titania based catalysis material provided by the invention is that technology such as surface coating, metal ion mixing and surperficial acidifying are coupled, coated the mixed titanyl compound of other metallic elements of one deck on titania based catalysis material surface, carry out acidifying with acid then, metal ion on the outer surface of material after coating is dissolved away, thereby obtain the material that a kind of new photocatalysis performance is strengthened.Catalysis material after this modification has obtained the inaccessible good light catalytic effect of single method modification, its light induced electron and hole life prolong, blemish and activity hydroxy increase, increase before photocatalytic activity is more unmodified, before can being applied to modification, the applied field of material, also can produce degradation to water body and airborne most pollutant effectively.
The specific embodiment
Embodiment 1,
With TiO
2(the earlier wide nanosecond science and technology Co., Ltd in Zibo produces powder, particulate titanium dioxide, wherein Detitanium-ore-type and rutile-type ratio are about 1: 1, the about 80nm of particle diameter) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and ferric nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
Use the forward and backward TiO of modification
2(Zibo earlier wide nanosecond science and technology Co., Ltd) powder carries out photocatalytic degradation to methylene blue, is light source with the uviol lamp of two 20W, is catalyst with the 1g powder, stirring reaction in the 1.5L cylindrical container, the TiO before the modification
2Powder is 30% 60 minutes photocatalytic degradation rate, and the titania based catalysis material of modification is 69% 60 minutes photocatalytic degradation rate, has improved 130% than unmodified.
Embodiment 2,
Surface crystallization there is 1 μ m TiO
2The sheet glass of film can adsorbable organic pollution to remove the surface 100 ℃ of roastings, place the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 0.1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.01ml, butyl titanate 0.04ml and ferric nitrate, sonic oscillation 20min; Drip excessive ammonia, be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
Use the forward and backward surface crystallization of modification that TiO is arranged
2Sheet glass methylene blue is carried out photocatalytic degradation, be light source with the uviol lamp of two 20W, electromagnetic agitation reaction in the 250ml beaker, the surface crystallization before the modification has TiO
2Sheet glass be 10% 120 minutes photocatalytic degradation rate, the titania based catalysis material of modification is 21% 60 minutes photocatalytic degradation rate, has improved 110% than unmodified.
Embodiment 3,
The surface is coated with 2nm thickness T iO
2SiO
2Powder (diameter 60nm) 5g can adsorbable organic pollution to remove the surface 500 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and ferric nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
Use the forward and backward powder of modification that methylene blue is carried out photocatalytic degradation, uviol lamp with two 20W is a light source, with the 1g powder is catalyst, stirring reaction in the 1.5L cylindrical container, powder before the modification is 12% 60 minutes photocatalytic degradation rate, the titania based catalysis material of modification is 24% 60 minutes photocatalytic degradation rate, has improved 100% than unmodified.
Embodiment 4,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml acetone of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds isopropyl alcohol 0.1ml, butyl titanate 0.4ml and ferric nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the acetone volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 60% 60 minutes photocatalytic degradation rate, has improved 100% than unmodified.
Embodiment 5,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol (commercially available absolute ethyl alcohol removes water treatment again) of water content below 0.1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and ferric nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 69% 60 minutes photocatalytic degradation rate, has improved 130% than unmodified.
Embodiment 6,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, acetone soln (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and ferric nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 69% 60 minutes photocatalytic degradation rate, has improved 130% than unmodified.
Embodiment 7,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and ferric nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 69% 60 minutes photocatalytic degradation rate, has improved 130% than unmodified.
Embodiment 8,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and ferric nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive sodium hydrate solution, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 69% 60 minutes photocatalytic degradation rate, has improved 130% than unmodified.
Embodiment 9,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and ferric nitrate, sonic oscillation 20min; Electromagnetic agitation drips the excessive hydrogen potassium oxide solution, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 69% 60 minutes photocatalytic degradation rate, has improved 130% than unmodified.
Embodiment 10,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and magnesium acetate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 40% 60 minutes photocatalytic degradation rate, has improved 33% than unmodified.
Embodiment 11,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and calcium nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 42% 60 minutes photocatalytic degradation rate, has improved 40% than unmodified.
Embodiment 12,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and strontium nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 75% 60 minutes photocatalytic degradation rate, has improved 150% than unmodified.
Embodiment 13,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and barium nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 35% 60 minutes photocatalytic degradation rate, has improved 16% than unmodified.
Embodiment 14,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and scandium nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 50% 60 minutes photocatalytic degradation rate, has improved 67% than unmodified.
Embodiment 15,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and yttrium nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 60% 60 minutes photocatalytic degradation rate, has improved 100% than unmodified.
Embodiment 16,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) lml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and sodium metavanadate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 63% 60 minutes photocatalytic degradation rate, has improved 110% than unmodified.
Embodiment 17,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 0.1: 1: 0.15) that adds acetic acid 0.00625ml, butyl titanate 0.4ml and ammonium chromate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 33% 60 minutes photocatalytic degradation rate, has improved 10% than unmodified.
Embodiment 18,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 40: 1: 0.15) that adds acetic acid 0.25ml, butyl titanate 0.4ml and ammonium molybdate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 81% 60 minutes photocatalytic degradation rate, has improved 170% than unmodified.
Embodiment 19,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, add acetic acid 0.625ml, butyl titanate 0.4ml and ammonium paratungstate. ethanol solution (0.01485mol/L) 1ml (the mol ratio is 100: 1: 0.15), sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 67.5% 60 minutes photocatalytic degradation rate, has improved 125% than unmodified.
Embodiment 20,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and manganese nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 66% 60 minutes photocatalytic degradation rate, has improved 120% than unmodified.
Embodiment 21,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.00001mol/L) 0.1ml (the mol ratio is 16: 1: 0.0001) that adds acetic acid 0.1ml, butyl titanate 0.4ml and nitric acid Cobalt, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 66% 60 minutes photocatalytic degradation rate, has improved 110% than unmodified.
Embodiment 22,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.001485mol/L) 1ml (the mol ratio is 16: 1: 0.015) that adds acetic acid 0.1ml, butyl titanate 0.4ml and nickel nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 61.5% 60 minutes photocatalytic degradation rate, has improved 105% than unmodified.
Embodiment 23,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 0.2ml (the mol ratio is 16: 1: 0.03) that adds acetic acid 0.1ml, butyl titanate 0.4ml and rubidium nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 81% 60 minutes photocatalytic degradation rate, has improved 170% than unmodified.
Embodiment 24,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.0198mol/L) 1ml (the mol ratio is 16: 1: 0.2) that adds acetic acid 0.1ml, butyl titanate 0.4ml and stannic chloride, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 58.5% 60 minutes photocatalytic degradation rate, has improved 95% than unmodified.
Embodiment 25,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.001485mol/L) 0.4ml (the mol ratio is 16: 1: 0.006) that adds acetic acid 0.1ml, butyl titanate 0.4ml and plumbi nitras, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 57% 60 minutes photocatalytic degradation rate, has improved 90% than unmodified.
Embodiment 26,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and copper nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 36% 60 minutes photocatalytic degradation rate, has improved 20% than unmodified.
Embodiment 27,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and zinc nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 39% 60 minutes photocatalytic degradation rate, has improved 30% than unmodified.
Embodiment 28,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and lanthanum nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 90% 60 minutes photocatalytic degradation rate, has improved 200% than unmodified.
Embodiment 29,
With TiO
2Powder 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and cerous nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 81% 60 minutes photocatalytic degradation rate, has improved 170% than unmodified.
Embodiment 30,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and gadolinium nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 91% 60 minutes photocatalytic degradation rate, has improved 270% than unmodified.
Embodiment 31,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and ferric nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive nitric acid concentrated solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 69% 60 minutes photocatalytic degradation rate, has improved 130% than unmodified.
Embodiment 33,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and ferric nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive hydrochloric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 88.5% 60 minutes photocatalytic degradation rate, has improved 195% than unmodified.
Embodiment 34,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and ferric nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive phosphoric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 60% 60 minutes photocatalytic degradation rate, has improved 100% than unmodified.
Embodiment 35,
With TiO
2Powder (with embodiment 1) 5g can adsorbable organic pollution to remove the surface 300 ℃ of roastings, use ultrasonic wave to be scattered in the 150ml absolute ethyl alcohol of water content below 1wt% then, ethanol solution (0.01485mol/L) 1ml (the mol ratio is 16: 1: 0.15) that adds acetic acid 0.1ml, butyl titanate 0.4ml and ferric nitrate, sonic oscillation 20min; Electromagnetic agitation drips excessive ammonia, and be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, natural ageing 24h, vacuum drying is complete to the ethanol volatilization; Add excessive perchloric acid weak solution (be added into pH detection paper solution be acid), stir, centrifugal, washing, 120 ℃ of oven dry make the titania based catalysis material of modification.
The method of use embodiment 1 is the photocatalysis effect of the forward and backward material of modification relatively, and the titania based catalysis material of modification is 54% 60 minutes photocatalytic degradation rate, has improved 80% than unmodified.
Claims (9)
1, a kind of surface modifying method of titania based catalysis material comprises following step:
1) titania based catalysis material is carried out cleaning: earlier with titania based catalysis material 100～500 ℃ of roastings; Should directly be soaked in or use ultrasonic wave to be dispersed in the anhydrous organic solution by titania based catalysis material again;
2) disperse: in the mixed system that step 1) obtains in molar ratio 0.1～100: 1: 0.0001～0.20 ratio adds the ethanol or the acetone soln of hydrolysis inhibitor, titanium source and metal ion successively, and mixture is mixed;
3) hydrolysis: under stirring or sonic oscillation, to step 2) add excess base solution in the mixed system that obtains with respect to the amount in neutralizing hydrolysis inhibitor and hydrolysis titanium source, be hydrolyzed and be converted into the hydroxide of titanium until the titanium source fully, dry, obtained at surface doping the titania based catalysis material crude product of metal ion;
4) surperficial acidifying: the crude product that step 3) is obtained is in vacuum drying, and disperse or be dipped in the acid solution, till pH detection paper mixed liquor is acidity, centrifugal then, washing, oven dry obtains the titania based catalysis material of surface modification.
2, the surface modifying method of titania based catalysis material as claimed in claim 1, it is characterized in that the titania based catalysis material in the described step 1) comprises the film of particle, the titanium dioxide of titanium dioxide, at other suprabasil titanium deoxid films with wrapped the titanium deoxid film that is attached to other particle surfaces.
3, the surface modifying method of titania based catalysis material as claimed in claim 1 or 2 is characterized in that, the thickness of described film is 2nm～1 μ m.
4, the surface modifying method of titania based catalysis material as claimed in claim 1 is characterized in that, the anhydrous organic solution in the described step 1) is the organic solvent of water content below 1wt%.
As the surface modifying method of claim 1 or 4 described titania based catalysis materials, it is characterized in that 5, the anhydrous organic solution in the described step 1) is ethanol or acetone.
6, the surface modifying method of titania based catalysis material as claimed in claim 1 is characterized in that, described step 2) hydrolysis inhibitor be acetic acid or isopropyl alcohol.
7, the surface modifying method of titania based catalysis material as claimed in claim 1, it is characterized in that described step 2) metal ion be to be selected from a kind of in Mg, Ca, Sr, Ba, Sc, Y, V, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Sn, Pb, Cu, Zn, the lanthanide series.
8, the surface modifying method of titania based catalysis material as claimed in claim 1 is characterized in that, the aqueous slkali of described step 3) is the aqueous solution of inorganic base, comprises ammoniacal liquor, sodium hydroxide solution, potassium hydroxide solution.
9, the surface modifying method of titania based catalysis material as claimed in claim 1 is characterized in that, the acid of described step 4) is inorganic middle strong acid, comprises nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, perchloric acid.
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| CNB2004100308409A CN1314485C (en) | 2004-04-08 | 2004-04-08 | Surface modification of titanium oxide base light catalyzed material |
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| CNB2004100308409A CN1314485C (en) | 2004-04-08 | 2004-04-08 | Surface modification of titanium oxide base light catalyzed material |
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| CN102969168A (en) * | 2012-10-31 | 2013-03-13 | 彩虹集团公司 | Process for preparing doped titanium dioxide sol for dye-sensitized solar cell |
| CN112169514A (en) * | 2020-09-30 | 2021-01-05 | 佛山市顺德区金磊环保科技有限公司 | Combined type oil smoke purifier |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999043616A1 (en) * | 1998-02-24 | 1999-09-02 | Rotem Amfert Negev Ltd. | A modified titanium dioxide and a method for its preparation |
| JP2002088276A (en) * | 2000-09-19 | 2002-03-27 | Asahi Kasei Corp | Antifouling coating agent |
| CN1385237A (en) * | 2001-05-16 | 2002-12-18 | 中国科学院化学研究所 | Process for preparing modified titanium dioxide nano photocatalysis material |
| CN1397377A (en) * | 2002-08-14 | 2003-02-19 | 清华大学 | Process for preparing photocatalytic TiO2 film used to clean water and air |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999043616A1 (en) * | 1998-02-24 | 1999-09-02 | Rotem Amfert Negev Ltd. | A modified titanium dioxide and a method for its preparation |
| EP1060128A1 (en) * | 1998-02-24 | 2000-12-20 | Rotem Amfert Negev Ltd. | A modified titanium dioxide and a method for its preparation |
| JP2002088276A (en) * | 2000-09-19 | 2002-03-27 | Asahi Kasei Corp | Antifouling coating agent |
| CN1385237A (en) * | 2001-05-16 | 2002-12-18 | 中国科学院化学研究所 | Process for preparing modified titanium dioxide nano photocatalysis material |
| CN1397377A (en) * | 2002-08-14 | 2003-02-19 | 清华大学 | Process for preparing photocatalytic TiO2 film used to clean water and air |
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