CN101444725A - Method for preparing load type titanium dioxide photocatalytic film - Google Patents

Abstract

The invention discloses a method for preparing a load type titanium dioxide photocatalytic film. The method comprises titanium dioxide sol preparation, titanium dioxide film coating by ultrasonic, dipping and pulling, and drying and calcining. As the method organically combines technology of sol-gel, ultrasonic coated film and dipping and pulling, the load type titanium dioxide photocatalytic film prepared by the method has an even and compact surface, basically does not have shedding phenomenon after three times of acid dipping and ultrasonic oscillating cleaning during a process of 200 hours use, and the photocatalytic efficiency of the film after cleaning is basically not changed. The load type titanium dioxide photocatalytic film has the advantages of stable photocatalytic property, basically invariable degradation velocity, firm attachment, difficult fall-off, high photocatalytic activity and stability and long service life.

Description

A kind of preparation method of load type titanium dioxide photocatalytic film

Technical field

The present invention relates to a kind of preparation method of load type titanium dioxide photocatalytic film, belong to the catalysis material preparing technical field.

Background technology

Because of titanium dioxide (TiO ₂) photocatalytic oxidation can effectively remove poisonous and harmful substance in the empty G﹠W, and non-secondary pollution, be 21 century environmental friendliness catalytic purification new technology, so the research of the preparation of highly efficient titania photocatalyst and photocatalytic activity thereof has been one of domestic and international most active research field in recent years.Because in use there is easy inactivation in the powder titanium dioxide photochemical catalyst, easily condense, be difficult to shortcoming such as recoverys, is unfavorable for the industrialization promotion use; And the load type titania film has ease-to-operate and controllability advantage, and good theoretical research and actual application value are arranged.

The method for preparing at present the load type titania film has: vapour deposition process (vapor deposition), liquid phase deposition (Liquid Phase Deposition), sol-gel process (Sol-gel Method), alkoxide hydrolysis (alkoxide hydrolyzing method) etc.There is following problem in said method: on microstructure, and supported titanium ₂There is uniform TiO in film surface more ₂Crystalline particle, size is from tens to nanometers up to a hundred, and is whole in conjunction with not tight between particle, there are hole, space or form agglomerated particle at carrier surface, thereby have fastness difference, and especially on the big carrier of specific area, more be easy to generate the uneven phenomenon of plated film, influence supported titanium ₂The photocatalysis service life of film.Chinese patent literature CN1634653 discloses a kind of preparation method of loaded nano titanium dioxide photocatalysis film, this method is with pure butyl titanate and absolute ethyl alcohol, diethanol amine, water, Macrogol 600 is a raw material, by the chemical reaction under the normal temperature, obtain the faint yellow TiO 2 sol of transparent and stable, adopt dipping one czochralski method at woven wire area load titanium deoxid film then, in Muffle furnace, calcine down at last in 450～550 ℃, get final product a kind of nano titanium dioxide photocatalysis film that is carried on the stainless steel wire net surface, though the method has higher heat endurance and quantum efficiency, and have advantages such as with low cost and technology is simple, but prepared load type titanium dioxide photocatalytic film is at UV-irradiation, still be easy to generate under the situations such as sluicing and come off, degradation problem under the catalytic activity.

Summary of the invention

The preparation method who the purpose of this invention is to provide the load type titanium dioxide photocatalytic film of a kind of adhesion-tight, difficult drop-off, photocatalytic activity and stability height and long service life is to solve above-mentioned existing in prior technology defective and problem.

For achieving the above object, technical scheme of the present invention is as follows:

The preparation method of load type titanium dioxide photocatalytic film of the present invention comprises that TiO 2 sol preparation, dipping lift and the drying and calcining step, is characterized in that also comprise ultrasonic titanium dioxide coating film step, the concrete operations step is as follows:

A) TiO 2 sol preparation

Absolute ethyl alcohol and the pure butyl titanate volume ratio with 3:1～5:1 is mixed; Transfer pH to 2～4 with rare nitric acid; Stirred 0.5～1.5 hour down at 15～40 ℃; Got final product in 18～36 hours 15～40 ℃ of following lucifuge ageings;

B) ultrasonic titanium dioxide coating film

The sheet glass of cleaning surfaces is immersed in the TiO 2 sol, adopt ultrasonic wave that the carrier sheet glass was carried out the titanium dioxide coating film 1～2 minute down at 15～40 ℃;

C) dipping lifts

The carrier sheet glass that will carry out ultrasonic titanium dioxide coating film with the speed of 1mm/s at the uniform velocity lifts out from colloidal sol;

D) drying and calcining

At first at room temperature dry naturally, place baking oven then,, promptly get a kind of optically catalytic TiO 2 film that is carried on glass sheet surface after cooling off naturally at last 450 ℃～550 ℃ calcinings 1～2 hour in 105 ℃ of dryings 0.5 hour.

Compared with prior art, the present invention has following beneficial effect:

Because the present invention organically combines sol-gel, ultrasonic coated film and the dipping technology of lifting, therefore the surperficial even compact of the prepared load type titanium dioxide photocatalytic film of preparation method of the present invention, in 200 hours process of use, experienced and do not had obscission substantially after 3 acid soak add cleaned by ultrasonic vibration, photocatalysis efficiency after cleaning does not have to change substantially, photocatalysis performance is stable, degradation rate is constant substantially, has the advantage of adhesion-tight, difficult drop-off, photocatalytic activity and stability height and long service life.

Description of drawings

Fig. 1 is AFM (AMF) photo of the prepared load type titanium dioxide photocatalytic film of the present invention, and wherein: a is the plane image pattern, and b is the height image pattern;

Fig. 2 is AFM (AMF) photo of the prepared load type titanium dioxide photocatalytic film of reference examples, and wherein: a is the plane image pattern, and b is the height image pattern;

Fig. 3 adds cleaned by ultrasonic vibration and AFM (AMF) photo of use after 200 hours for the prepared load type titanium dioxide photocatalytic film of the present invention through 3 acid soak;

Fig. 4 adds cleaned by ultrasonic vibration and AFM (AMF) photo of use after 200 hours for the prepared load type titanium dioxide photocatalytic film of reference examples through 3 acid soak;

When Fig. 5 carries out photochemical catalytic oxidation to SMZ at the use initial stage and after using 200 hours and going through 3 acid soak to add cleaned by ultrasonic vibration respectively for the prepared load type titanium dioxide photocatalytic film of the present invention and reference examples, the degradation rate phenogram of SMZ, wherein: what represented is that film of the present invention carries out photochemical catalytic oxidation at the use initial stage to SMZ, * expression to be film of the present invention carry out photochemical catalytic oxidation to SMZ after adding cleaned by ultrasonic vibration using 200 hours and went through 3 acid soak; ◆ expression be that the reference examples film carries out photochemical catalytic oxidation at the use initial stage to SMZ, ▲ expression to be the reference examples film carry out photochemical catalytic oxidation to SMZ after adding cleaned by ultrasonic vibration using 200 hours and went through 3 acid soak;

Fig. 6 for the prepared load type titanium dioxide photocatalytic film of the present invention and reference examples respectively at the use initial stage with when using 200 hours and going through 3 acid soak and methylene blue being carried out photochemical catalytic oxidation after adding cleaned by ultrasonic vibration, the degradation rate curve map of methylene blue, wherein :-◆-expression is that film of the present invention carries out photochemical catalytic oxidation at the use initial stage to methylene blue, being film of the present invention use 200 hours and going through 3 acid soak and methylene blue is carried out photochemical catalytic oxidation after adding cleaned by ultrasonic vibration of-△-expression;--expression be that the reference examples film carries out photochemical catalytic oxidation at the use initial stage to methylene blue ,-*-expression to be the reference examples film carry out photochemical catalytic oxidation to methylene blue after adding cleaned by ultrasonic vibration using 200 hours and went through 3 acid soak.

The specific embodiment

The invention will be further described below by embodiment, and its purpose only is better to understand content of the present invention and unrestricted protection scope of the present invention:

Embodiment

A) TiO 2 sol preparation

Absolute ethyl alcohol and the pure butyl titanate volume ratio with 4:1 is mixed; Transfer pH to 3 with rare nitric acid; The lucifuge ageing got final product in 24 hours after stirring 1 hour under 25 ℃;

B) ultrasonic titanium dioxide coating film

The sheet glass of cleaning surfaces is immersed in the TiO 2 sol, adopt ultrasonic wave that the carrier sheet glass was carried out the titanium dioxide coating film 1～5 minute down at 25 ℃;

C) dipping lifts

The carrier sheet glass that will carry out ultrasonic titanium dioxide coating film with the speed of 1mm/s at the uniform velocity lifts out from colloidal sol;

D) drying and calcining

At first at room temperature dry naturally, place baking oven then,, promptly get a kind of optically catalytic TiO 2 film that is carried on glass sheet surface after cooling off naturally at last 480 ℃ of calcinings 1～2 hour in 105 ℃ of dryings 0.5 hour.

Reference examples

A) TiO 2 sol preparation

Absolute ethyl alcohol and the pure butyl titanate volume ratio with 4:1 is mixed; Transfer pH to 3 with rare nitric acid; The lucifuge ageing got final product in 24 hours after stirring 1 hour under 25 ℃;

B) dipping lifts

The sheet glass of cleaning surfaces is immersed in the TiO 2 sol, sheet glass is at the uniform velocity lifted out from colloidal sol with the speed of 1mm/s;

C) drying and calcining

At first at room temperature dry naturally, place baking oven then,, promptly get a kind of optically catalytic TiO 2 film that is carried on glass sheet surface after cooling off naturally at last 480 ℃ of calcinings 1～2 hour in 105 ℃ of dryings 0.5 hour.

By Fig. 1 and Fig. 2 as can be seen: adopt preparation method's prepared film of the present invention surface even compact, and adopt reference examples method prepared film rough surface.

By Fig. 3 and Fig. 4 as can be seen: do not have obscission substantially after adopting preparation method's prepared film of the present invention to add cleaned by ultrasonic vibration through 200 hours use and 3 acid soak; Adopt reference examples method prepared film through same use and clean after the phenomenon that obviously comes off is then arranged.

By Fig. 5 and Fig. 6 as can be seen: adopt preparation method's prepared film of the present invention not have variation substantially using 200 hours and went through the photocatalysis efficiency of 3 acid soak after adding cleaned by ultrasonic vibration, photocatalysis performance is stablized, degradation rate is constant substantially; And adopt reference examples method prepared film obviously decline and photocatalysis performance poor stability to occur using 200 hours and went through the photocatalysis performance of 3 acid soak after adding cleaned by ultrasonic vibration.

Claims (1)

1. the preparation method of a load type titanium dioxide photocatalytic film comprises that TiO 2 sol prepares, dipping lifts and the drying and calcining step, it is characterized in that also comprise ultrasonic titanium dioxide coating film step, the concrete operations step is as follows:

A) TiO 2 sol preparation

Absolute ethyl alcohol and the pure butyl titanate volume ratio with 3:1～5:1 is mixed; Transfer pH to 2～4 with rare nitric acid; Stirred 0.5～1.5 hour down at 15～40 ℃; Got final product in 18～36 hours 15～40 ℃ of following lucifuge ageings;

B) ultrasonic titanium dioxide coating film

The sheet glass of cleaning surfaces is immersed in the TiO 2 sol, adopt ultrasonic wave that the carrier sheet glass was carried out the titanium dioxide coating film 1～5 minute down at 15～40 ℃;

C) dipping lifts

The carrier sheet glass that will carry out ultrasonic titanium dioxide coating film with the speed of 1mm/s at the uniform velocity lifts out from colloidal sol;

D) drying and calcining

At first at room temperature dry naturally, place baking oven then,, promptly get a kind of optically catalytic TiO 2 film that is carried on glass sheet surface after cooling off naturally at last 450 ℃～550 ℃ calcinings 1～2 hour in 105 ℃ of dryings 0.5 hour.

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