CN104383966A - Preparation method of 3D ordered macroporous polyaniline (OM PANI)/TiO2 composite photocatalytic material and application thereof - Google Patents

Preparation method of 3D ordered macroporous polyaniline (OM PANI)/TiO2 composite photocatalytic material and application thereof Download PDF

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CN104383966A
CN104383966A CN201410728392.3A CN201410728392A CN104383966A CN 104383966 A CN104383966 A CN 104383966A CN 201410728392 A CN201410728392 A CN 201410728392A CN 104383966 A CN104383966 A CN 104383966A
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polyaniline
titanium dioxide
ordered macroporous
dimensional ordered
pani
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李石
杜聪聪
赵东风
郑经堂
王永强
刘广东
刘贺峰
李萌
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China University of Petroleum East China
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Abstract

The invention belongs to a preparation method of a 3D ordered macroporous polyaniline (OM PANI)/TiO2 composite photocatalytic material and application thereof. The preparation method comprises the following steps: A, dipping 3-10g of prepared 3D OM PANI/TiO2 material in 50ml of a hydrochloric acid containing 0.05-0.5ml of an aniline monomer, and carrying out ultrasonic oscillation for 5-20 minutes; B, putting a reaction system in the step A into ice bath, dropwise adding a monomer initiator with the concentration of 0.25-1%, and reacting for 2-5 hours; C, washing a sample by adopting ethyl alcohol and/or diethyl ether, and washing the sample with distilled water; D, drying at the low temperature of 60-80 DEG C so as to obtain the sample. The 3D OM PANI/TiO2 composite material is used for combining the favorable conducting performance of PANI as well as characteristics of the relatively low energy gap with the TiO2 catalytic performance, meanwhile improves the defects that the photoproduction electron-hole recombination rate of a single TiO2 material is high and the visible light response is poor, and achieves the effects of improving the TiO2 photocatalytic quantum efficiency and reinforcing the visible light absorption; meanwhile, the material is at hundreds of nanoscales, is difficult to reunite, is easy to settle, and is good in regeneration performance.

Description

The preparation method of three-dimensional ordered macroporous polyaniline/titanium dioxide composite photocatalyst material and application thereof
Technical field
The invention belongs to a kind of field of photocatalytic material, specifically a kind of preparation method of three-dimensional ordered macroporous polyaniline/titanium dioxide composite photocatalyst material and application thereof.
Background technology
Photocatalysis oxidation technique processes organic wastewater a kind of common method, wherein titanium dioxide (TiO at present 2) be considered to a kind of efficient, environmental protection, have the photocatalyst material of development and application prospect most.But then, due to TiO 2some bottleneck factor of self, as high in photo-generate electron-hole recombination rate, quantum efficiency is lower; Greater band gap (Eg=3.2eV), only can be less than the ultraviolet light of 387nm by response wave length; Particle size is in nanoscale, easily reunites and causes catalytic activity to reduce and be difficult to recycle, thus limit TiO during application 2the practicalization of photochemical catalyst and application.Therefore, how TiO is improved 2the quantum yield of photochemical catalyst, reduces its energy gap, and effectively overcomes nano-TiO 2in practical application, the reunion particularly in aqueous systems solves current TiO 2the emphasis of photocatalysis technology application and focus place.
In order to improve and overcome TiO 2the problems referred to above that photocatalysis technology exists in application, utilize the multiple Method means research such as the modification of doping vario-property, photoactivate, porous material loading to have a large amount of bibliographical informations.(1) doping vario-property research mainly comprises metal-doped, nonmetal doping and metal-doped noble metal (as Pt, Pd, Au, Ag etc.), the transition metal of comprising such as to mix altogether (as Fe 3+, V 5+, W 6+, Cu 2+, Co 2+deng), rare earth element is (as La 3+, Eu 3+, Y) etc.; Nonmetal doping comprises nitrogen, carbon, fluorine, boron, sulphur etc.; And the codope etc. between different element; (2) photoactivate research mainly concentrates on organic dyestuff modification etc.: the research of (3) porous material loading mainly overcomes the shortcoming of the too small easy reunion of nano particle, such as porous carbon materials load, various molecular sieve carried etc.; Although above-mentioned research all makes some progress, also there is the easy compound of electronics and hole, visible light-responded undesirable, titanium dioxide size mainly concentrates on tens nanometers even less rank, titanium dioxide and support materials and the weak point such as easily to peel off.
Nearest research finds, utilizes conductive polymer polyanaline (PANI) material decorated nanometer TiO 2, not only can reduce TiO 2energy gap, expand TiO 2light absorbing wavelength, improves nano-TiO 2visible light catalysis activity, the electric conductivity that meanwhile PANI is excellent can also reduce the recombination rate of photo-generate electron-hole, improves photocatalysis quantum efficiency, and then improves photocatalytic activity.Single PANI material is modified just can improve nano-TiO simultaneously 2the performance of material two aspects, this is at TiO 2the modification field of material is very rare.But from current report, the PANI/TiO of synthesis 2composite mainly contains particulate, film etc., and microscopic dimensions also mainly concentrates on tens Nano grades, and existing easily reunites makes shortcomings such as not easily reclaiming when applying in photocatalysis efficiency reduction, water.
Summary of the invention
According to above-mentioned weak point, the object of the invention is to: a kind of photocatalysis efficiency is high, be easy to the three-dimensional ordered macroporous polyaniline/titanium dioxide composite photocatalyst material reclaimed preparation method and application thereof are provided, can PANI/TiO be expanded 2the research field of composite.
For achieving the above object, technical program of the present invention lies in: a kind of preparation method of three-dimensional ordered macroporous polyaniline/titanium dioxide composite, comprise the steps: that (1) prepares three-dimensional ordered macroporous titanic oxide material, (2) three-dimensional ordered macroporous polyaniline/titanium dioxide composite is prepared, wherein, prepare three-dimensional ordered macroporous polyaniline/titanium dioxide composite to comprise the following steps: A, by the three-dimensional ordered macroporous titanic oxide material 3-10g impregnating dispersion for preparing in the hydrochloric acid solution 50ml containing 0.05-0.5ml aniline monomer, ultrasonic vibration 5-20min, B, the reaction system of step (A) is placed in ice bath, and slowly to drip concentration be 0.25-1% monomer initiator ammonium persulfate solution, drip and terminate rear reaction system and continue reaction 2-5 hour, C, reaction terminate rear employing ethanol and/or washed with diethylether sample several, then use distilled water washing sample for several times, D, by washing after sample in 60-80 DEG C of low temperature drying, obtain three-dimensional ordered macroporous polyaniline/titanium dioxide composite.
Preferably: the macropore diameter of the three-dimensional ordered macroporous titanium dioxide prepared is of a size of 200-800nm, BET specific surface area 50-120m 2/ g.
Preferably: the polyaniline film thickness of described three-dimensional ordered macroporous polyaniline/titanium dioxide composite is at 1-30nm.
Preferably: the described polyaniline of three-dimensional ordered macroporous polyaniline/titanium dioxide composite and the molar ratio range of titanium dioxide are 1:20-1:120.
The present invention also provides a kind of application process of three-dimensional ordered macroporous polyaniline/titanium dioxide composite, and it comprises the steps:
(1) simulated wastewater solution is prepared;
(2) three-dimensional ordered macroporous polyaniline/titanium dioxide composite is mixed mutually with simulated wastewater solution;
(3) mixed solution in light source direct projection step (2), maintenance temperature is 10-40 DEG C, measures the concentration of simulated wastewater solution in solution, until solution decolours completely every 10-30min;
(4) reacted solution is filtered, collect three-dimensional ordered macroporous polyaniline/titanium dioxide composite distilled water and clean oven dry, for subsequent use.
Preferably: described simulated wastewater solution concentration is 40-120mg/L.
Preferably: in described course of reaction, in solution, be blown into air bubbling.
Preferably: described light source is visible light source or ultraviolet source.
Compared to the prior art the present invention has outstanding feature and progress:
(1) three-dimensional ordered macroporous polyaniline/titanium dioxide composite (3DOM PANI/TiO 2) research field of TiO 2-base optical catalyst is expanded to hundreds of nanometers level, avoid reuniting due to particle little Yi thus affecting the shortcoming of its catalytic efficiency.
(2) 3DOM PANI/TiO 2the preparation process of optic catalytic composite material is simple, and weak ultrasonic with under initator effect, aniline aggregates into polyaniline film at macroporous titanium dioxide surface uniform, and the thickness of film is controlled.
(3) 3DOM PANI/TiO 2the macroporous structure of optic catalytic composite material is interconnected by wicket, namely the contact of target molecule in catalyst surface and waste water is conducive to, be conducive to again light through, therefore catalytic activity is high, under ultraviolet light and visible light conditions, all present good photo-catalysis capability, effectively can reduce the concentration of organic pollution.
(4) 3DOM PANI/TiO 2the feature of PANI excellent conductive performance and lower energy gap combines with optically catalytic TiO 2 performance by optic catalytic composite material, the defect of the deficiency of single titanic oxide material photo-generate electron-hole recombination rate height and visible light-responded difference can be improved simultaneously, namely by PANI modification, realize the effect that optically catalytic TiO 2 quantum efficiency improves and strengthens visible absorption simultaneously.
(5) 3DOM PANI/TiO 2optic catalytic composite material is in hundreds of nanometers level, not easily reunites, is easy to sedimentation, and regenerability is good, and after repeatedly recycling, photocatalysis efficiency almost remains unchanged.
Accompanying drawing explanation
Fig. 1 is 3DOM TiO 2sample SEM (a) and TEM (b) photo;
Fig. 2 is 3DOM PANI/TiO 2composite (PANI and TiO 2mol ratio 1:20) SEM (a) and TEM (b) photo;
Fig. 3 is 3DOM PANI/TiO 2composite (PANI and TiO 2mol ratio 1:70) SEM (a) and TEM (b) photo;
Fig. 4 is 3DOM PANI/TiO 2composite (PANI and TiO 2mol ratio 1:120) SEM (a) and TEM (b) photo;
Fig. 5 is 3DOM PANI/TiO 2composite (PANI and TiO 2mol ratio 1:20) visible light conditions decline solution Methyl Orange in Wastewater curve map;
Fig. 6 is 3DOM PANI/TiO 2composite (PANI and TiO 2mol ratio 1:20) rhodamine B curve map of degrading under visible light conditions;
Fig. 7 is 3DOM PANI/TiO 2composite (PANI and TiO 2mol ratio 1:70) ultraviolet light conditions decline solution Methyl Orange in Wastewater curve map;
Fig. 8 is 3DOM PANI/TiO2 composite (PANI and TiO 2mol ratio 1:70) visible light conditions decline solution Methyl Orange in Wastewater curve map;
Fig. 9 is 3DOM PANI/TiO 2composite (PANI and TiO 2mol ratio 1:70) regeneration degraded Methyl Orange in Wastewater curve map under visible light conditions;
Figure 10 is 3DOM PANI/TiO 2composite (PANI and TiO 2mol ratio 1:70) rhodamine B curve map of degrading under ultraviolet light conditions;
Figure 11 is 3DOM PANI/TiO 2composite (PANI and TiO 2mol ratio 1:70) rhodamine B curve map of degrading under visible light conditions;
Figure 12 is 3DOM PANI/TiO 2composite (PANI and TiO 2mol ratio 1:70) regeneration rhodamine B degradation waste water curve map under visible light conditions;
Figure 13 is 3DOM PANI/TiO 2composite (PANI and TiO 2mol ratio 1:120) visible light conditions decline solution Methyl Orange in Wastewater curve map;
Figure 14 is 3DOM PANI/TiO 2composite (PANI and TiO 2mol ratio 1:120) rhodamine B curve map of degrading under visible light conditions.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described.
Preparation embodiment 1
A preparation method for three-dimensional ordered macroporous polyaniline/titanium dioxide composite, comprises the steps:
(1) three-dimensional ordered macroporous titanic oxide material is prepared
First be monomer with styrene, by Emulsifier-free Emulsion Polymerization Technology synthetic polystyrene (PS) microballoon, and it is stand-by to be assembled into PS glue crystal template by natural sediment.
Then take butyl titanate as titanium source, mix with ethanol, hydrochloric acid, glacial acetic acid and distilled water and be made into transparent TiO 2sol solution presoma.PS glue crystal template is soaked in TiO 230min in colloidal sol, then suction filtration removes unnecessary colloidal sol, and dry 2h at 75 DEG C, repeats above-mentioned filling process repeatedly.Finally in tubular heater, the PS template of populated precursor is slowly warming up to 300 DEG C of constant temperature 2-4h, utilizes oxidation decomposition course to remove PS template, then be warming up to 500 DEG C of constant temperature 2h respectively, naturally after cooling, namely obtain the 3DOM TiO of anatase crystal structure 2sample, macropore size can adjust according to glue crystal template size, 3DOM TiO 2the macropore diameter of sample is controlled at 200-800nm.
(2) three-dimensional ordered macroporous polyaniline/titanium dioxide composite is prepared, comprise the following steps: A, by the three-dimensional ordered macroporous titanic oxide material 3g impregnating dispersion for preparing in the hydrochloric acid solution 50ml containing 0.05ml aniline monomer, ultrasonic vibration 5min; B, the reaction system of step (A) is placed in ice bath, and slowly to drip concentration be 0.25% monomer initiator ammonium persulfate solution, drip and terminate rear reaction system and continue reaction 2 hours; C, reaction terminate rear employing ethanol and washed with diethylether sample several, then use distilled water washing sample for several times; D, by washing after sample in 60 DEG C of low temperature dryings, obtain three-dimensional ordered macroporous polyaniline/titanium dioxide composite.
Preparation embodiment 2
A kind of preparation method of three-dimensional ordered macroporous polyaniline/titanium dioxide composite, it prepares three-dimensional ordered macroporous titanic oxide material with embodiment 1, prepare three-dimensional ordered macroporous polyaniline/titanium dioxide composite as different from Example 1 to comprise the following steps: A, by the three-dimensional ordered macroporous titanic oxide material 7g impregnating dispersion for preparing in the hydrochloric acid solution 20ml containing 0.25ml aniline monomer, ultrasonic vibration 15min; B, the reaction system of step (A) is placed in ice bath, and slowly to drip concentration be 0.7% monomer initiator ammonium persulfate solution, drip and terminate rear reaction system and continue reaction 2.5 hours; C, reaction terminate rear employing washed with diethylether sample for several times, then use distilled water washing sample for several times; D, by washing after sample in 70 DEG C of low temperature dryings, obtain three-dimensional ordered macroporous polyaniline/titanium dioxide composite.
Preparation embodiment 3
A kind of preparation method of three-dimensional ordered macroporous polyaniline/titanium dioxide composite, it prepares three-dimensional ordered macroporous titanic oxide material with embodiment 1, prepare three-dimensional ordered macroporous polyaniline/titanium dioxide composite as different from Example 1 to comprise the following steps: A, by the three-dimensional ordered macroporous titanic oxide material 10g impregnating dispersion for preparing in the hydrochloric acid solution 20ml containing 0.5ml aniline monomer, ultrasonic vibration 20min; B, the reaction system of step (A) is placed in ice bath, and slowly to drip concentration be 1% monomer initiator ammonium persulfate solution, drip and terminate rear reaction system and continue reaction 5 hours; C, reaction terminate rear employing ethanol washing sample for several times, then use distilled water washing sample for several times; D, by washing after sample in 80 DEG C of low temperature dryings, obtain three-dimensional ordered macroporous polyaniline/titanium dioxide composite.
By the 3DOM PANI/TiO shown in Fig. 2,3,4 2composite SEM (a) and TEM (b) photo show known, and PANI film is uniformly distributed 3DOM TiO 2macropore hole wall on, form 3DOM PANI/TiO 2nEW TYPE OF COMPOSITE photocatalyst material.By Fig. 2,3,4 compared to Figure 1, although 3DOM is PANI/TiO 2the purer 3DOM TiO of composite macropore hole wall 2become coarse, but do not affect PANI/TiO 2the three-dimensional ordered macroporous structure of composite, also can not affect its photocatalysis performance simultaneously in actual application.
Preparation embodiment 4
A kind of preparation method of three-dimensional ordered macroporous polyaniline/titanium dioxide composite, it prepares three-dimensional ordered macroporous titanic oxide material with embodiment 1, prepare three-dimensional ordered macroporous polyaniline/titanium dioxide composite as different from Example 1 to comprise the following steps: A, by the three-dimensional ordered macroporous titanic oxide material 5g impregnating dispersion for preparing in the hydrochloric acid solution 20ml containing 0.4ml aniline monomer, ultrasonic vibration 10min; B, the reaction system of step (A) is placed in ice bath, and slowly to drip concentration be 0.5% monomer initiator ammonium persulfate solution, drip and terminate rear reaction system and continue reaction 3.5 hours; C, reaction terminate rear employing washed with diethylether sample for several times, then use distilled water washing sample for several times; D, by washing after sample in 65 DEG C of low temperature dryings, obtain three-dimensional ordered macroporous polyaniline/titanium dioxide composite.
Application Example 1
Get 3gPANI and TiO 2the 3DOM PANI/TiO of mol ratio 1:20 2optic catalytic composite material and the organic simulated wastewater of 200ml methyl orange, add in 250mL reactor, and with the xenon lamp of 500W for visible light source, the temperature constant of solution system, at 30 DEG C, continues to pass into air bubbling and makes solid-liquid contact abundant.Take methyl orange as simulating pollution thing, initial concentration is 80mg/L.Illumination reaction is after 60 minutes, and methyl orange solution obviously fades, and close to colourless, degradation curve as shown in Figure 5.In addition, in order to compare with business-like titanium dioxide product, use business-like titanium dioxide P25 photochemical catalyst to repeat above-mentioned experimentation, degradation curve as shown in Figure 5.
Application example 2
Get 3gPANI and TiO 2the 3DOM PANI/TiO of mol ratio 1:20 2optic catalytic composite material and the organic simulated wastewater of 200ml rhodamine B, add in 250mL reactor, and with the xenon lamp of 500W for visible light source, the temperature constant of solution system, at 30 DEG C, continues to pass into air bubbling and makes solid-liquid contact abundant.Take rhodamine B as simulating pollution thing, initial concentration is 80mg/L.Illumination reaction is after 90 minutes, and rhodamine B solution decolours completely, and degradation curve as shown in Figure 6; In addition, in order to compare with business-like titanium dioxide product, use business-like titanium dioxide P25 photochemical catalyst to repeat above-mentioned experimentation, degradation curve as shown in Figure 6.
Application example 3
Get 3gPANI and TiO 2the 3DOM PANI/TiO of mol ratio 1:70 2optic catalytic composite material and the organic simulated wastewater of 200ml methyl orange, add in 250mL reactor, and with the high-pressure sodium lamp of 500W for ultraviolet source, the temperature constant of solution system, at 25 DEG C, continues to pass into air bubbling and makes solid-liquid contact abundant.Take methyl orange as simulating pollution thing, initial concentration is 120mg/L.Illumination reaction is after 30 minutes, and methyl orange solution decolours completely, and degradation curve as shown in Figure 7; Solution in reactor to be removed and by 3DOM PANI/TiO 2material is cleaned with distilled water and is dried, and again put into reactor, with fresh original solution reaction repeated after 30 minutes, methyl orange solution decolours completely; After so repeatedly carrying out degraded regenerative response 5 times, 3DOM PANI/TiO 2after material and fresh original solution react 30 minutes, methyl orange solution still can decolour completely, and regeneration degradation curve is similar to Fig. 7.In addition, in order to compare with business-like titanium dioxide product, use business-like titanium dioxide P25 photochemical catalyst to repeat above-mentioned experimentation, degradation curve as shown in Figure 7.
Application example 4
Get 3gPANI and TiO 2the 3DOM PANI/TiO of mol ratio 1:70 2optic catalytic composite material and the organic simulated wastewater of 200ml methyl orange, add in 250mL reactor, and with the xenon lamp of 500W for visible light source, the temperature constant of solution system, at 30 DEG C, continues to pass into air bubbling and makes solid-liquid contact abundant.Take methyl orange as simulating pollution thing, initial concentration is 40mg/L.Illumination reaction is after 60 minutes, and methyl orange solution decolours completely, and degradation curve as shown in Figure 8; Solution in reactor to be removed and by 3DOM PANI/TiO 2material is cleaned with distilled water and is dried, and again put into reactor, with fresh original solution reaction repeated after 60 minutes, methyl orange solution decolours completely; After so repeatedly carrying out degraded regenerative response 5 times, 3DOM PANI/TiO 2after material and fresh original solution react 60 minutes, methyl orange solution still can decolour completely, and regeneration degradation curve as shown in Figure 9.In addition, in order to compare with business-like titanium dioxide product, use business-like titanium dioxide P25 photochemical catalyst to repeat above-mentioned experimentation, degradation curve as shown in Figure 8.
Application example 5
Get 3gPANI and TiO 2the 3DOM PANI/TiO of mol ratio 1:70 2optic catalytic composite material and the organic simulated wastewater of 200ml rhodamine B, add in 250mL reactor, and with the high-pressure sodium lamp of 500W for ultraviolet source, the temperature constant of solution system, at 10 DEG C, continues to pass into air bubbling and makes solid-liquid contact abundant.Take rhodamine B as simulating pollution thing, initial concentration is 120mg/L.Illumination reaction is after 45 minutes, and rhodamine B solution decolours completely, and degradation curve as shown in Figure 10; Solution in reactor to be removed and by 3DOM PANI/TiO 2material is cleaned with distilled water and is dried, and again put into reactor, with fresh original solution reaction repeated after 45 minutes, rhodamine B solution decolours completely; After so repeatedly carrying out degraded regenerative response 5 times, 3DOM PANI/TiO 2after material and fresh original solution react 30 minutes, rhodamine B solution still can decolour completely, and regeneration degradation curve is similar to Fig. 5.In addition, in order to compare with business-like titanium dioxide product, use business-like titanium dioxide P25 photochemical catalyst to repeat above-mentioned experimentation, degradation curve as shown in Figure 10.
Application example 6
Get 3gPANI and TiO 2the 3DOM PANI/TiO of mol ratio 1:70 2optic catalytic composite material and the organic simulated wastewater of 200ml rhodamine B, add in 250mL reactor, and with the xenon lamp of 500W for visible light source, the temperature constant of solution system, at 40 DEG C, continues to pass into air bubbling and makes solid-liquid contact abundant.Take rhodamine B as simulating pollution thing, initial concentration is 40mg/L.Illumination reaction is after 90 minutes, and rhodamine B solution decolours completely, and degradation curve as shown in figure 11; Solution in reactor to be removed and by 3DOM PANI/TiO 2material is cleaned with distilled water and is dried, and again put into reactor, with fresh original solution reaction repeated after 80 minutes, rhodamine B solution decolours completely; After so repeatedly carrying out degraded regenerative response 5 times, 3DOM PANI/TiO 2after material and fresh original solution react 90 minutes, rhodamine B solution still can decolour completely, and regeneration degradation curve as shown in figure 12.In addition, in order to compare with business-like titanium dioxide product, use business-like titanium dioxide P25 photochemical catalyst to repeat above-mentioned experimentation, degradation curve as shown in figure 11.
Application example 7
Get 3gPANI and TiO 2the 3DOM PANI/TiO of mol ratio 1:120 2optic catalytic composite material and the organic simulated wastewater of 200ml methyl orange, add in 250mL reactor, and with the xenon lamp of 500W for visible light source, the temperature constant of solution system, at 30 DEG C, continues to pass into air bubbling and makes solid-liquid contact abundant.Take methyl orange as simulating pollution thing, initial concentration is 80mg/L.Illumination reaction is after 60 minutes, and methyl orange solution obviously fades, and close to colourless, degradation curve is as shown in Figure of description 13.In addition, in order to compare with business-like titanium dioxide product, use business-like titanium dioxide P25 photochemical catalyst to repeat above-mentioned experimentation, degradation curve is as shown in Figure of description 13.
Application example 8
Get 3gPANI and TiO 2the 3DOM PANI/TiO of mol ratio 1:120 2optic catalytic composite material and the organic simulated wastewater of 200ml rhodamine B, add in 250mL reactor, and with the xenon lamp of 500W for visible light source, the temperature constant of solution system, at 30 DEG C, continues to pass into air bubbling and makes solid-liquid contact abundant.Take rhodamine B as simulating pollution thing, initial concentration is 80mg/L.Illumination reaction is after 90 minutes, and rhodamine B solution decolours completely, and degradation curve is as shown in Figure of description 14; In addition, in order to compare with business-like titanium dioxide product, use business-like titanium dioxide P25 photochemical catalyst to repeat above-mentioned experimentation, degradation curve is as shown in Figure of description 14.

Claims (8)

1. the preparation method of a three-dimensional ordered macroporous polyaniline/titanium dioxide composite, comprise the steps: that (1) prepares three-dimensional ordered macroporous titanic oxide material, (2) three-dimensional ordered macroporous polyaniline/titanium dioxide composite is prepared, it is characterized in that, described preparation three-dimensional ordered macroporous polyaniline/titanium dioxide composite comprises the following steps: A, by the three-dimensional ordered macroporous titanic oxide material 3-10g impregnating dispersion for preparing in the hydrochloric acid solution 50ml containing 0.05-0.5ml aniline monomer, ultrasonic vibration 5-20min; B, the reaction system of step (A) is placed in ice bath, and slowly to drip concentration be 0.25-1% monomer initiator ammonium persulfate solution, drip and terminate rear reaction system and continue reaction 2-5 hour; C, reaction terminate rear employing ethanol and/or washed with diethylether sample several, then use distilled water washing sample for several times; D, by washing after sample in 60-80 DEG C of low temperature drying, obtain three-dimensional ordered macroporous polyaniline/titanium dioxide composite.
2. the preparation method of three-dimensional ordered macroporous polyaniline/titanium dioxide composite according to claim 1, is characterized in that, the macropore diameter of described three-dimensional ordered macroporous titanium dioxide is of a size of 200-800nm, BET specific surface area 50-120m 2/ g.
3. the preparation method of three-dimensional ordered macroporous polyaniline/titanium dioxide composite according to claim 1, is characterized in that, the polyaniline film thickness of described three-dimensional ordered macroporous polyaniline/titanium dioxide composite is at 1-30nm.
4. the preparation method of three-dimensional ordered macroporous polyaniline/titanium dioxide composite according to claim 1, it is characterized in that, the described polyaniline of three-dimensional ordered macroporous polyaniline/titanium dioxide composite and the molar ratio range of titanium dioxide are 1:20-1:120.
5. the application of three-dimensional ordered macroporous polyaniline/titanium dioxide composite according to claim 1, it is characterized in that, it comprises the steps:
(1) simulated wastewater solution is prepared;
(2) three-dimensional ordered macroporous polyaniline/titanium dioxide composite is mixed mutually with simulated wastewater solution;
(3) mixed solution in light source direct projection step (2), maintenance temperature is 10-40 DEG C, measures the concentration of simulated wastewater solution in solution, until solution decolours completely every 10-30min;
(4) reacted solution is filtered, collect three-dimensional ordered macroporous polyaniline/titanium dioxide composite distilled water and clean oven dry, for subsequent use.
6. the application of three-dimensional ordered macroporous polyaniline/titanium dioxide composite according to claim 5, is characterized in that, described simulated wastewater solution concentration is 40-120mg/L.
7. the application of three-dimensional ordered macroporous polyaniline/titanium dioxide composite according to claim 5, is characterized in that, be blown into air bubbling in described course of reaction in solution.
8. the application of three-dimensional ordered macroporous polyaniline/titanium dioxide composite according to claim 5, is characterized in that, described light source is visible light source or ultraviolet source.
CN201410728392.3A 2014-12-03 2014-12-03 Preparation method of 3D ordered macroporous polyaniline (OM PANI)/TiO2 composite photocatalytic material and application thereof Pending CN104383966A (en)

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