CN100496709C - A multi-channel titania photocatalysis membrane and method for making same - Google Patents
A multi-channel titania photocatalysis membrane and method for making same Download PDFInfo
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- CN100496709C CN100496709C CNB2007101656200A CN200710165620A CN100496709C CN 100496709 C CN100496709 C CN 100496709C CN B2007101656200 A CNB2007101656200 A CN B2007101656200A CN 200710165620 A CN200710165620 A CN 200710165620A CN 100496709 C CN100496709 C CN 100496709C
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Abstract
The invention relates to a titanium dioxide photocatalytic film of a multi-channel structure, and the surface structure has two areas: one area is a flat area formed by nano-sized titanium dioxide particles, and the flat area is of a continuous whole structure; the other area has channels embedded on the flat area, the channels mutually and independently exist, and the dimension is of a micron size. The invention has the whole structure that a titanium dioxide thin film is provided with a plurality of channels. The titanium dioxide photocatalytic film is prepared by a mature sol-gel method, but besides a usual component, a nontoxic organic component is also added into the sol formulation. Through the process of the heat treatment and the agglomeration, a molecule of an organism generates the decomposition and the volatilization to leave the channels on a titanium dioxide film layer. The channels increase the surface area of the obtained photocatalytic film, and thereby the photocatalytic degradation efficiency of products is enhanced.
Description
Technical field:
The present invention relates to a kind of titanium deoxid film, relate in particular to a kind of photocatalytic titania film of many channel structures, and preparation method thereof.
Background technology:
Titanium dioxide (TiO
2) not only have very wide valence-band level and a very high photocatalytic activity, and have outstanding advantages such as nontoxic, stable in properties, resistance to chemical attack and photoetch, so become the research focus of photochemical catalyst, become a kind of photochemical catalyst that development potentiality is arranged most, (the king ancestral that aspect organic matter degradations such as the removing of wastewater treatment, air cleaning, petroleum pollution, antibiotic, the anti-mist of super hydrophilic, all is widely used, Zhang Fengbao, Zhang Qiancheng. chemical industry and engineering, 2004,21 (4): 248-253; Peill N J, Hoffmann M R.Environ.Sci.Technol, 1996,30:2806-2812.).
Although titanium dioxide is a kind of good photochemical catalyst, but because the powder particle catalyst exists the light absorption utilization rate low in actual applications, in suspended phase, be difficult to separate and reclaim and easily cohesion, in the gas-solid phase photocatalytic process then catalyst easily shortcoming such as taken away by air-flow, when actual pollution control, make the practical application of this technology be restricted, thereby restricted industrialization (the product rock of titanium dioxide optical catalyst, Fei Xuening, Jiang Yuanguang. environment and protection, 2004, (3): 53-54; The king ancestral, Zhang Fengbao, Zhang Qiancheng. chemical industry and engineering, 2004,21 (4): 248-253.).The load technology of fixed catalyst is the effective way king ancestral who solves this difficult problem, Zhang Fengbao, Zhang Qiancheng. chemical industry and engineering, 2004,21 (4): 248-253; Peill N J, Hoffmann M R.Environ.Sci.Technol, 1996,30:2806-2812.), also be ideal form (king ancestral, the Zhang Fengbao of the design of modulation active component and catalyst system and catalyzing, Zhang Qiancheng. chemical industry and engineering, 2004,21 (4): 248-253; Rachel A, SubrahmsnyamM, Boule P.Applied Catalysis B:Environmental, 2002,37 (4): 301-308.).Good titanium dioxide optical catalyst carrier should have higher specific surface area, have certain intensity and impact resistance, wherein studying more carrier material mainly is (king ancestral, Zhang Fengbao such as glass, pottery, adsorbent, Zhang Qiancheng. chemical industry and engineering, 2004,21 (4): 248-253.), and the metal species carrier of reporting after late 1990s (Ding Shifeng, Tang Chaoqun, Li Qingxiang. Treatment of Industrial Water, 2003,23 (3): 46-48; Zhu Yongfa, Li Wei, what Yu, still quiet. SCI, 2003,24 (3): 465-468.) research is very few, but has seen combination properties such as its more excellent intensity, shock-resistant, chemical stability and installation.
The carrying method of photochemical catalyst on carrier mainly contains (king ancestrals such as vapor phase method, sol-gel process (Sol-Gel), powder sintering method, coupling mull technique, ion-exchange, liquid phase deposition, hydrolysis sedimentation, doping method, direct dip-coating thermal decomposition method and cross-linking method, Zhang Fengbao, Zhang Qiancheng. chemical industry and engineering, 2004,21 (4): 248-253.), wherein sol-gel process can repeatedly repeat to increase the thickness of titanium dioxide, gained carried titanium dioxide film has higher photocatalytic activity and fastness preferably, and is evenly distributed.This method technology is simple, mild condition, technology is adjustable, and is suitable for the load on the complicated shape carrier, is the most frequently used method at present.
The activity of loaded titanium dioxide photocatalyst depends primarily on the surface state of titanium dioxide catalytic membrane, comprise factors such as surface area and surface roughness, and the suction-operated of surface state and catalyst and extinction efficient have confidential relation (king ancestral, Zhang Fengbao, Zhang Qiancheng. chemical industry and engineering, 2004,21 (4): 248-253.).Document [Shen Hangyan, Zhang Jinxia, Tang Xinshuo. Chinese Journal of Chemical Physics, 2001,14 (4): 497-500.] discover that if the titanium deoxid film surface that makes is more coarse, specific area is bigger, then catalytic activity is just bigger.
Summary of the invention:
The object of the present invention is to provide a kind of high-ratio surface photocatalytic titania film and preparation method thereof with many channel structures.The preparation method adopts conventional sol-gel technology, selects for use the avirulence organic matter as making the raceway groove composition, selects the carrier of porous material as titanium dioxide film for use; Analyze the surface topography of this rete, and investigate its photocatalytic activity, provide a kind of efficient higher photocatalysis system.
It is carrier that photocatalytic titania film of the present invention adopts the porous foam nickel of high-ratio surface, film surface has a large amount of raceway grooves, these raceway grooves have further increased the specific area of photochemical catalyst, it is characterized in that: porous carrier is a three-dimensional net structure, pore-size and porosity are adjustable, and be connective good, helps containing dirty fluid flowing betwixt, the raceway groove yardstick of film surface can not influence rete adhering to and working strength carrier at micron order.
The avirulence organic matter that the present invention uses is methylcellulose, its adding mode is: earlier methylcellulose and deionized water are mixed with pasty liquid by mass ratio 1:10～1:20, then that this pasty liquid and preparation titanium deoxid film is used conventional colloidal sol mixes with volume ratio 1:1 and stirs, replace TiO 2 sol to soak nickel porous with this mixed liquor, apply at last and heat treatment, promptly obtain having the photocatalytic titania film of many channel structures.
The Technology for Heating Processing that the present invention adopts is: the sample that will coat titanium deoxid film is put into Muffle furnace, earlier furnace temperature is risen to 100～120 ℃ of oven dry moisture, lentamente furnace temperature is risen to 400～500 ℃ from 100～120 ℃ then, and under this temperature constant temperature 20～40 minutes, naturally cool to room temperature at last.This heat treatment mode not only can be removed moisture, nitric acid and the organic substance in the gel preferably, also can make the titanium dioxide sintering form high-intensity nano thin-film, and combine securely with the nickel foam carrier.
Not with the raceway groove method of making of the present invention, by the photocatalytic titania film of the identical conventional sol-gel technology gained of other conditionally completes, have the film layer structure of comparison " smooth ", also have surface area still less certainly.Find through experiment, compare with conventional sol-gel technology gained photocatalytic titania film, the photocatalytic titania film that the present invention has channel structure has stronger photo-catalysis capability, this illustrates that channel structure of the present invention has increased the activated centre of photocatalysis membrana, thereby has improved photocatalysis efficiency.
The photocatalytic titania film of the present invention's preparation has following characteristics and advantage:
1) photocatalytic titania film of the present invention is made up of nano particle, is many channel structures, and the raceway groove yardstick is in micron-sized scope, and it is more even to distribute.These raceway grooves do not influence rete to the adhering to and working strength of carrier, and have increased the specific area of photocatalysis system.
2) photocatalytic titania film of the present invention is carried on the nickel foam of multi-hole state, because carrier has bigger specific area, has therefore further enlarged the photocatalysis place of rete.
3) preparation method of the present invention is easy to operate, and equipment is simple, and is practical.
Description of drawings:
The surface topography scanning electron micrograph of Fig. 1 photocatalytic titania film of the present invention has shown the nanostructured of rete, and rete is evenly distributed.
Fig. 2 the present invention has the photocatalytic titania film microstructure of channel structure, has shown that the raceway groove that this rete presents " inlays " form.
Fig. 3 and Fig. 2 have shown the smooth form that this rete presents with the conventional titanium deoxid film microstructure of multiplication factor, mean that it has than Fig. 2 product specific area and surface-active center still less.
The macro morphology scanning electron micrograph of Fig. 4 titanium dioxide photocatalysis body of the present invention system has shown the netted form of class of loose structure, and hole wherein is interconnected.
The degradation rate figure line of Fig. 5 photocatalytic degradation methyl orange solution.The situation of two kinds of carrier systems all shows among the figure, and the photocatalytic degradation efficient that titanium dioxide photocatalysis body of the present invention is is higher than corresponding conventional titanium dioxide photocatalysis body and is.
The specific embodiment:
Embodiment 1:
1) preparation of conventional TiO 2 sol: adopt butyl titanate [Ti (OBu)
4] (chemical pure) be raw material, measures a certain amount of butyl titanate, under stirring condition, add acetylacetone,2,4-pentanedione (AcAc, analyze pure: as inhibitor, to delay the intense hydrolysis of butyl titanate).To be mixed evenly after, under stirring condition, add again absolute ethyl alcohol (analyze pure, used ethanol volume be overall ethanol volume 2/3rds).Nitric acid (analyzing pure), deionized water and the absolute ethyl alcohol of aequum (used ethanol volume be overall ethanol volume 1/3rd) are mixed (annotate: mixing order is " nitric acid+deionized water+absolute ethyl alcohol ") and stir, under strong agitation, slowly be added drop-wise in the above-mentioned solution, obtain stable TiO 2 sol.The ratio of the mole of above-mentioned substance is: Ti (OBu)
4: EtOH:H
2O:HNO
3: AcAc=1:18:2:0.2:0.5.The effect one that adds nitric acid is to suppress hydrolysis, the 2nd, and make the colloid ion lotus that becomes positively charged, thereby stop the micelle cohesion.Colloidal sol with this method preparation is highly stable, can be in airtight stable placement under the lucifuge condition about 1 year under the room temperature.
2) preparation of TiO 2 sol of the present invention: the 25g granular methylcellulose of wadding a quilt with cotton is sneaked in the 300ml deionized water, and glass bar stirs, and becomes uniform starchiness emulsion after a period of time.This emulsion is mixed with volume ratio 1:1 with TiO 2 sol and stir, replace conventional TiO 2 sol to soak nickel porous, apply then and heat treatment with this mixed liquor.
3) load and heat treatment: with size is 25 * 60cm
2Porous foam nickel plate (thickness is 2～3mm) to place the acetone ultrasonic cleaning 10 minutes, again by ethanol ultrasonic cleaning 10 minutes, by deionized water ultrasonic cleaning 5 minutes, dries up standby at last.With cleaned nickel foam carrier horizontal positioned in the sol solutions that configures, soaked 5 minutes, utilize desk-top sol evenning machine to adopt spin coating method plated film then.The sample that coats titanium deoxid film is put into Muffle furnace, be warming up to 100 ℃ with 30 minutes earlier, be warming up to 450 ℃ through 200 minutes again, and under this temperature constant temperature 30 minutes, naturally cool to room temperature then, obtain having the photocatalytic titania film of channel structure, its configuration of surface is seen Fig. 2.
Can repeat the above-mentioned steps several times, to obtain the rete of desired thickness.Number of repetition in this experiment is 3 times.
Comparative Examples: need not replace conventional TiO 2 sol for TiO 2 sol mixed liquor of the present invention in the foregoing description, other conditionally completes are with above-mentioned embodiment, obtain conventional sol-gel technology photocatalytic titania film at last, have the even curface structure, its form is seen Fig. 3.
Embodiment 2: the photocatalytic titania film and the conventional sol-gel technology photocatalytic titania film of Comparative Examples method gained that have channel structure with the present invention of embodiment 1 method gained are experimental subjects, carry out the contrast experiment of photocatalytic degradation methyl orange solution.This experiment selects for use methyl orange as the waste water model, is because methyl orange has the typical structure of dye class compound---and azo and fear the quinoid structure, its photocatalytic degradation speed is compared the row that belong to than difficult degradation with other typical dye.
In the experiment of this photocatalytic degradation, the initial concentration of methyl orange is 10mg/L.The sample size of foamed nickel supported titanium dioxide film is 25 * 60 * 2.6mm
3, the volume of used methyl orange solution is 150mL, contains in the 500mL beaker.Experiment is carried out on the normal temperature photocatalysis apparatus of design voluntarily, and light source is the quartzy bactericidal lamp of the ultraviolet of 15W, and its dominant wavelength is 253.7nm.Sample is apart from the about 10cm in fluorescent tube center, and orientation levels is parallel to fluorescent tube, and the methyl orange solution liquid level did not have the about 1cm of the upper surface of sample.Illumination is every the 20min once sampling, and the solution of the upper surface top of materialsing is analyzed in spectrophotometer.According to the methyl orange calibration curve, calculate reactant concentration, and then calculate degradation rate, draw out degradation rate and time relation at last as shown in Figure 5.Wherein Fig. 5 a and Fig. 5 b are respectively the nickel foam carrier of two kinds of porositys, and two picture group lines show that all the present invention has the photocatalytic degradation rate curve of the photocatalytic titania film of channel structure, always occupy the top of conventional sol-gel technology photocatalytic titania film.This explanation, the photocatalytic degradation ability of gained photocatalytic titania film of the present invention is greater than conventional sol-gel technology gained photocatalytic titania film.
Claims (3)
1. the titanium deoxid film of channel structure more than a kind, it is characterized in that: this titanium deoxid film is " inlaying " nanometer film structure of " raceway groove " in a large number, these " raceway grooves " that exist have micron-sized yardstick mutually isolatedly, raceway groove has increased the surface area of gained photocatalysis membrana, thereby can improve the photocatalytic degradation efficient of product.
2. the preparation method of the described many channel structures titanium deoxid film of claim 1, adopt ripe sol-gel technology, it is characterized in that: its carrier is a nickel foam, colloidal sol is made up of the usual component methylate cellulose of preparation titanium deoxid film, and methylcellulose effect wherein is and causes the raceway groove that increases surface area on titanium deoxid film.
3. the application of the described titanium deoxid film of claim 1 aspect photocatalysis or photoelectrocatalysis.
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| CN106757374A (en) * | 2016-12-27 | 2017-05-31 | 重庆中鼎三正科技有限公司 | A kind of method of use TiO 2 sol deposition of titanium oxide whisker |
| CN107055679A (en) * | 2017-06-16 | 2017-08-18 | 莆田学院 | A kind of photocatalytic degradation device and its application for water process |
| CN107858683B (en) * | 2017-11-30 | 2019-11-08 | 河南机电职业学院 | A kind of multifunctional antibiotic film and preparation method thereof |
| CN112768138B (en) * | 2020-12-18 | 2022-04-22 | 安捷利电子科技（苏州）有限公司 | Preparation method of pattern with narrow channel |
| CN113373026A (en) * | 2021-06-15 | 2021-09-10 | 东北电力大学 | Adjustable static magnetic field and nickel-based additive composite strengthening device for improving biogas yield |
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