CN102600905A - Semiconductor hetero-junction/conductive polymer fiber membrane composite photocatalyst and preparation method thereof - Google Patents
Semiconductor hetero-junction/conductive polymer fiber membrane composite photocatalyst and preparation method thereof Download PDFInfo
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- CN102600905A CN102600905A CN201210037508XA CN201210037508A CN102600905A CN 102600905 A CN102600905 A CN 102600905A CN 201210037508X A CN201210037508X A CN 201210037508XA CN 201210037508 A CN201210037508 A CN 201210037508A CN 102600905 A CN102600905 A CN 102600905A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a semiconductor hetero-junction/conductive polymer fiber membrane composite photocatalyst and a preparation method of the composite photocatalyst, wherein the composite photocatalyst is obtained by loading and scattering a semiconductor hetero-junction on the surface of a conductive polymer fiber membrane by means of chemical bonds complexing; the semiconductor hetero-junction is selected from ZnS-CdS/TiO2, SnS-TiO2, PbS-TiO2, Bi2S3/TiO2, SnS2/TiO2, CdS/TiO2 or SnS-CdS/TiO2; and the conductive polymer fiber membrane with a fiber diameter range of 400nm to 2mum is obtained by mixing a polymer with a conductive material and performing electrostatical spinning. According to the semiconductor hetero-junction/conductive polymer fiber membrane composite photocatalyst provided by the invention, as the conductivity of conductive polymer fibers and the structure of the hetero-junction are utilized, electrons and holes are easy to separate in a sewage treating and hydrogen producing process, and the catalytic efficiency of the catalyst is improved.
Description
One, technical field
The present invention relates to composite photo-catalyst of a kind of degradable organic pollutant simultaneously and hydrogen production by water decomposition gas and preparation method thereof, specifically a kind of heterojunction semiconductor/conducting polymer tunica fibrosa composite photo-catalyst that utilizes solar energy while photocatalysis degradation organic contaminant and hydrogen production by water decomposition gas and preparation method thereof.
Two, background technology
Along with the fast development of economy, energy shortage and environmental pollution have become the major issue that current urgent need solves, and the clean new and renewable sources of energy of exploitation is one of approach of head it off.Hydrogen Energy has cleaning, renewable, advantages such as fuel value is high, environmentally safe, has received the very big concern of industrial quarters with society.
Since (Nature, 1972,238 (5358): 37-38) report TiO such as Fujishima in 1972
2Since the light decomposition water hydrogen producing phenomenon on the monocrystalline electrode, the preparation method of the photochemical catalyst that uses when light hydrogen production by water decomposition gas and light decomposing organic pollutant emerges in an endless stream.But, directly use powder shaped light to urge agent to have shortcomings such as difficult Separation and Recovery, operating difficulties.(Journal of Materials Chemistry, 2009,19 (18): such as Zhang 2771-2777) with Ag-TiO
2Hetero-junctions loads on mesoporous SiO
2(KIT-6) on, the bigger serface of catalyst system and catalyzing has significantly improved the adsorption capacity of catalyst, has increased contacting of catalyst and pollutant.(Applied Catalysis A:2005,295 (1): 71-78) utilize the molecular sieve carried CdS nano particle of ETS-4 and ETS-10, find that molecular sieve helps the separation of photogenerated charge, and improve the activity and stability of CdS such as Guan.(Solar Energy Materials and Solar Cells, 2003,80 (4): such as Shangguan 433-441) with TiO
2Film is carried on glass, has high catalysis light hydrogen production by water decomposition gas activity.(Applied Catalysis B:Environmental, 2007,74 (1-2): 53-62) utilize perlite loaded with nano TiO such as Hosseini
2, catalyst swims in the surface of water, through the TiO of load
2Have high photocatalytic activity, and be easy to and be processed separating of water body.(Advanced Materials, 2010,22 (9): be biological template 951), such as Zhou with Pt/N-TiO with the leaf
2Make the leaf shape structure, catalyst system and catalyzing has high activity.(Powder Technology, (In press, Doi:10.1016/j.powtec.2010.12.032)) is with foamed ceramics loaded metal ion doped Ti O for Qiu etc.
2, photocatalysis performance improves.From bibliographical information, the advantage of catalyst after load is fixing has: prevent the loss of catalyst fines particle and be easy to continuous utilization; The utilization rate that helps dispersion, increase surface area and the light source of catalyst; Some carriers can interact with semiconductor particle, hinder the compound of light induced electron and hole and increase the absorption to reactant; Carrier is fixed catalyst, is convenient to catalyst is carried out finishing and processes the reactor of different shape.But the carrier of usefulness mainly is precious metal, SiO such as Pt at present
2, inorganic carriers such as molecular sieve, pottery and glass, shortcoming such as these carrier costs are high, specific area is little and pliability is low and limited the large-scale application of catalyst.
Three, summary of the invention
The present invention aims to provide a kind of heterojunction semiconductor/conducting polymer tunica fibrosa composite photo-catalyst and preparation method thereof; Composite photo-catalyst of the present invention can degradable organic pollutant and coordinate system hydrogen, has the catalytic efficiency height, reclaims easily, cost is low, be easy to realize industrialized characteristics.
Technical solution problem of the present invention adopts following technical scheme:
Heterojunction semiconductor of the present invention/conducting polymer tunica fibrosa composite photo-catalyst is characterized in that: said composite photo-catalyst is that the form load of heterojunction semiconductor through the chemical bond complexing is scattered in the composite photo-catalyst that obtains behind the surface of conducting polymer tunica fibrosa;
Said heterojunction semiconductor is selected from ZnS-CdS/TiO
2, SnS/TiO
2, PbS/TiO
2, Bi
2S
3/ TiO
2, SnS
2/ TiO
2, CdS/TiO
2Or SnS-CdS/TiO
2, said heterojunction semiconductor is of a size of 20-5000nm.
Wherein heterogeneous semiconductor is become ZnS-CdS/TiO
2Or SnS-CdS/TiO
2The time ratio between ZnS and CdS and SnS and the CdS any.
Said conducting polymer tunica fibrosa is the conducting polymer tunica fibrosa that polymer and conductive material is mixed the fibre diameter 400nm-2 μ m that the back high-voltage electrostatic spinning obtains; Wherein polymer is selected from Kynoar, double A type polysulfones, PPSU, polyether sulfone, styrene-maleic anhydride copolymer, acrylic acid hexafluoro butyl ester-methacrylic acid copolymer, methacrylic acid ten difluoro heptyl ester-methacrylic acid copolymers, polyaniline, polystyrene, PEO, polyacrylonitrile, polyethylene glycol oxide, gathers in the styrene one or more, and ratio is any when multiple; Said conductive material is selected from nano-graphite, carbon black, CNT or polyaniline; The addition of conductive material is the 1-10% of polymer quality.
The preparation method of heterojunction semiconductor of the present invention/conducting polymer tunica fibrosa composite photo-catalyst comprises the preparation of conducting polymer tunica fibrosa and each unit process of load of heterojunction semiconductor, it is characterized in that:
The preparation of said conducting polymer tunica fibrosa is that polymer and conductive material are added in the solvent, obtains the mixed solution of viscosity 600cP-1400cP after stirring, and the addition of conductive material is the 1-10% of polymer quality; Mixed solution is obtained the conducting polymer tunica fibrosa that contains a large amount of carboxyls of fibre diameter 400nm-2 μ m through high-voltage electrostatic spinning; Spinning voltage 16000V-30000V, receiving range 16cm-30cm advances speed 0.5-2.OmL/h.
The load of said heterojunction semiconductor comprises load sulfide and load TiO
2Wherein load sulfide is to place mixed solution to soak 0.5-10 days the conducting polymer tunica fibrosa; Said mixed solution is one or more the aqueous solution in bismuth nitrate, zinc compound, lead compound, tin compound, the cadmium compound, and total amount of substance concentration is 0.1-1mol/L; Descended dry 2-8 hour in 40-80 ℃ again; Add thiocarbamide or thioacetyl amine aqueous solution then; The mole of thiocarbamide or thioacetamide be solute substance in the mixed solution the amount sum 0.5-2 doubly; In closed container,, obtain the conducting polymer tunica fibrosa of load sulfide after washing and the drying in 50-200 ℃ of reaction 0.5-10 days; Load TiO
2Be that conducting polymer tunica fibrosa with load sulfide places the aqueous solution of the titanyl sulfate of 0.1-1.0mol/L to soak 0.5-10 days; Add aqueous solution of urea then; The mole of urea be titanyl sulfate mole 0.1-10 doubly; In closed container,, obtain heterojunction semiconductor/conducting polymer tunica fibrosa composite photo-catalyst after washing and the drying in 50-200 ℃ of reaction 0.5-10 days;
Said zinc compound is selected from zinc nitrate, zinc acetate or zinc sulfate;
Said lead compound is selected from plumbi nitras, lead acetate or lead sulfate;
Said tin compound is selected from butter of tin or stannous chloride;
Said cadmium compound is selected from caddy or cadmium sulfate.
The photochemical catalyst of the present invention's preparation can be used for organic pollution and the ability coordinate system hydrogen in the degradation of sewage.Wherein organic pollution comprises formic acid, methyl alcohol, methylene blue, methyl orange, phenol etc.
The present invention adopts the xenon lamp simulated solar irradiation, mainly utilizes the visible light of wavelength greater than 420nm.
The present invention is a carrier with the conducting polymer tunica fibrosa, and polymer can overcome a lot of organic matters and be difficult to the shortcoming as the semiconductor light-catalyst carrier because the architectural feature of itself has good chemical stability.The big electronegativity of the electric conductivity of tunica fibrosa and carboxyl helps right separation and the diffusion in light induced electron-hole in the hetero-junctions, helps improving the catalytic performance of photochemical catalyst; Polymer fiber can promote the degradation in the hole of sulfurized layer enrichment in the hetero-junctions to organic absorption in the aqueous systems, and TiO
2The effect of the photic electron reduction water hydrogen of layer.The surface tension of polymer is low, can suppress the deposition of impurity such as silt on catalyst system and catalyzing that surface tension is high in the water, reduces the possibility that catalyst system and catalyzing is poisoned.Catalyst combines with easy-operating flexible polymeric fiber with chemical bond; Not only improved dispersiveness; And handle loss and the reunion of avoiding catalyst in the coordinate system hydrogen at organic pollution; Improve separable and repeat performance, help the sizable application of composite catalyst in water pollution control.And, be electron donor with pollutant in the waste water, the realization degraded is carried out with hydrogen manufacturing simultaneously.
Compare with known technology, the present invention has the following advantages:
1, be carrier with the conducting polymer tunica fibrosa, the net felt structural load powder photocatalyst that textile fiber material is unique is avoided the loss and the reunion of catalyst in sewage disposal coordinate system hydrogen, improve separable and repeat performance, is easy to realize industrialization.
2, the electric conductivity of polymer fiber membrane carrier and heterogeneous semiconductor junction type catalyst improve the efficient of catalyst degradation pollutant coordinate system hydrogen.
Four, description of drawings
Fig. 1 is composite photo-catalyst photocatalytic process principle signal of the present invention.
Fig. 2 is the sem photograph of conducting polymer tunica fibrosa among the embodiment 2.
Fig. 3 is the sem photograph of composite photo-catalyst among the embodiment 1.Wherein (a) be on the conducting polymer fibres load SnS
2The Electronic Speculum figure of-CdS as can be seen from the figure is dispersed with SnS on the surface of tunica fibrosa
2-CdS particle; (b) be at SnS
2The surface of-CdS particle again load one deck nanoscale TiO
2Electronic Speculum figure.
Fig. 4 be among the embodiment 1 load SnS
2The energy-dispersive spectroscopy figure of the composite photo-catalyst of-CdS particle, as can be seen from the figure, the Sn atomicity is 0.83: 5.22 with the ratio of Cd atomicity.
Fig. 5 is the sem photograph of composite photo-catalyst among the embodiment 2.Wherein (a) be on the conducting polymer tunica fibrosa load Electronic Speculum figure of ZnS-CdS, as can be seen from the figure be dispersed with the ZnS-CdS particle on the surface of tunica fibrosa; (b) be on the surface of ZnS-CdS particle again load one deck nanoscale TiO
2Electronic Speculum figure.
Fig. 6 is the sem photograph of composite photo-catalyst among the embodiment 3.Wherein (a) be on the conducting polymer tunica fibrosa load Electronic Speculum figure of CdS, as can be seen from the figure be dispersed with the CdS particle on the surface of tunica fibrosa; (b) be on the surface of CdS particle again load one deck nanoscale TiO
2Electronic Speculum figure.
Five, the specific embodiment
For further specifying the present invention, enumerate following examples, but be not to be used for limiting the defined invention scope of claim.Used medicine source among the embodiment:
Kynoar: U.S. Su Wei, the trade mark: 6008;
Double A type polysulfones: U.S. Su Wei, the trade mark: P-1700;
PPSU: U.S. Su Wei, the trade mark: R-500;
Styrene-maleic anhydride copolymer: go up maritime affairs and must reach petrochemical industry High-tech company, the trade mark: 214;
Nano-graphite: Nanjing Xian Feng Nono-material Science & Technology Ltd., the trade mark: XF009;
Acrylic acid hexafluoro butyl ester: avenge good fluorine chemistry of silicones Co., Ltd, the trade mark: Actyflon-G01, CAS numbering: 54052-90-3;
Butter of tin: Rugao City's chemical reagent Co., Ltd, CAS numbering: 10026-06-9;
Titanyl sulfate: Dandong City's chemical reagent factory;
Methacrylic acid: Chemical Reagent Co., Ltd., Sinopharm Group, CAS numbering: 79-41-4;
Acetone: Chemical Reagent Co., Ltd., Sinopharm Group, CAS numbering: 67-64-1;
N, N-dimethylacetylamide: Chemical Reagent Co., Ltd., Sinopharm Group, CAS numbering: 127-19-5;
Caddy: Chemical Reagent Co., Ltd., Sinopharm Group, CAS numbering: 7790-78-5;
Zinc acetate: Chemical Reagent Co., Ltd., Sinopharm Group, CAS numbering: 5970-45-6;
Butanone: Chemical Reagent Co., Ltd., Sinopharm Group, CAS numbering: 141-97-9;
Thioacetamide: Chemical Reagent Co., Ltd., Sinopharm Group, CAS numbering: 62-55-5;
Thiocarbamide: Chemical Reagent Co., Ltd., Sinopharm Group, CAS numbering: 62-56-6;
Azodiisobutyronitrile: Chemical Reagent Co., Ltd., Sinopharm Group, CAS numbering: 78-67-1;
Formic acid: Chemical Reagent Co., Ltd., Sinopharm Group, CAS numbering: 64-18-6;
Methyl alcohol: Chemical Reagent Co., Ltd., Sinopharm Group, CAS numbering: 67-56-1;
Methylene blue: Chemical Reagent Co., Ltd., Sinopharm Group, CAS numbering: 7220-79-3,122965-43-9.
Embodiment 1:
3.6g double A type polysulfones, 0.41g styrene-maleic anhydride copolymer and 0.4g nano-graphite add 14mL acetone and 20mLN, in the mixed solvent of N-dimethylacetylamide, stir 24 hours.Electrostatic spinning on the high-voltage electrostatic spinning device then, the conducting polymer tunica fibrosa of the fibre diameter 400nm-2 μ m that obtains.
The conducting polymer tunica fibrosa of above-mentioned preparation is immersed in 25mL 0.25molL
-1Caddy and 25mL 0.25molL
-1In the mixed aqueous solution of butter of tin, soak at room temperature 12h makes Cd
2+, Sn
4+With the abundant complexing of the carboxyl of conducting polymer fiber surface, 50 ℃ of dry 6h under nitrogen protection then; In the hydrothermal reaction kettle that is placed on 50mL, add 40mL0.25molL
-1The thioacetyl amine aqueous solution, 120 ℃ of hydro-thermals reaction 12h naturally cools to room temperature, takes out product and is put in 50mL deionized water for ultrasonic ripple and cleans 3 times, obtains CdS-SnS behind 80 ℃ of vacuum drying 12h
2/ conducting polymer tunica fibrosa is subsequent use.
With CdS-SnS
2/ conducting polymer tunica fibrosa be placed into 50mL hydrothermal reaction kettle in; The titanyl sulfate that adds 20mL 0.25mol/L soaked 12 hours; The urea that adds 20mL 0.1mol/L then, 120 ℃ were reacted 12 hours, and naturally cooled to room temperature; Take out product and be put in 50mL deionized water for ultrasonic ripple cleaning 3 times, 80 ℃ of vacuum drying 12h obtain CdS-SnS
2/ TiO
2/ conducting polymer tunica fibrosa composite photo-catalyst.
Be that example describes with reproducibility water pollutant methyl alcohol in this instance, methyl alcohol is a kind of common water pollutant.Therefore, the elimination of methyl alcohol has important Significance for Environment.
Degraded coordinate system hydrogen reaction is put into a slice CdS/TiO in the methanol aqueous solution of 20vol%
2/ conducting polymer tunica fibrosa composite photo-catalyst (1.0g).Adopting the 500W xenon lamp is built-in light source, with SP-6801 gas chromatograph (5A molecular sieve, N
2As carrier gas) gained gas is carried out quantitative analysis.After the illumination 10 hours, produce the hydrogen of 0.4L, 80% methyl alcohol is degraded.
Embodiment 2:
20g methacrylic acid, 60g acrylic acid hexafluoro butyl ester and 0.4g azodiisobutyronitrile add in the there-necked flask of band nitrogen protection and stirring, and butanone is a solvent, and 70 ℃ were reacted 4 hours.Reaction finishes the back precipitating in the deionized water of 10 times of volumes, and 60 ℃ of vacuum drying obtain acrylic acid hexafluoro butyl ester-methacrylic acid copolymer to constant weight.
5.1g Kynoar, 0.78g acrylic acid hexafluoro butyl ester-methacrylic acid copolymer and 0.1g CNT add 40.0gN, in the dinethylformamide, stir 24h.Electrostatic spinning on the high-voltage electrostatic spinning device then obtains the conducting polymer tunica fibrosa of fibre diameter 400nm-2 μ m.
The conducting polymer tunica fibrosa of above-mentioned preparation is immersed in 25ml 0.25molL
-1Zinc acetate and 25ml 0.25molL
-1In the mixed solution of caddy, soak at room temperature 20 hours makes Zn
2+, Cd
2+With the abundant complexing of the carboxyl of conducting polymer fiber surface, 60 ℃ of dry 6h under nitrogen protection then; In the hydrothermal reaction kettle that is placed on 50mL, add 40.0mL 0.5molL
-1Thiourea solution, 120 ℃ of hydro-thermals reaction 12h naturally cools to room temperature.Take out product and be put in 50mL deionized water for ultrasonic ripple cleaning 3 times, it is subsequent use to obtain ZnS-CdS/ conducting polymer tunica fibrosa behind 60 ℃ of vacuum drying 12h.
ZnS-CdS/ conducting polymer tunica fibrosa is placed into 50mL hydrothermal reaction kettle in, add the titanyl sulfate soak at room temperature 12 hours of 20mL 0.4mol/L, add the urea of 20ml 0.25mol/L subsequently, 120 ℃ of reactions 36 hours naturally cool to room temperature.Take out product and be put in 50mL deionized water for ultrasonic ripple cleaning 3 times, obtain ZnS-CdS/TiO behind 60 ℃ of vacuum drying 12h
2/ conducting polymer tunica fibrosa composite photo-catalyst.
Be that example describes with reproducibility water pollutant formic acid in this instance.
Degraded coordinate system hydrogen reaction is put into a slice ZnS-CdS/TiO in the aqueous formic acid of 40vol%
2/ conducting polymer tunica fibrosa composite photo-catalyst (0.2g).Adopting the 500W xenon lamp is built-in light source, with SP-6801 gas chromatograph (5A molecular sieve, N
2As carrier gas) gained gas is carried out quantitative analysis.After the illumination 20 hours, produce the hydrogen of 0.5L, 85% formic acid is degraded.
Embodiment 3:
2.5g PPSU, 1.0g styrene-maleic anhydride copolymer, 0.8g Kynoar and 0.3g nano carbon black add 8.0g acetone and 22.0gN, in the mixed solvent of N-dimethylacetylamide, stir 24 hours.Electrostatic spinning on the high-voltage electrostatic spinning device then obtains the conducting polymer tunica fibrosa of fibre diameter 400nm-2 μ m.
The conducting polymer tunica fibrosa of above-mentioned preparation is impregnated into 50mL, 0.25molL
-1The caddy aqueous solution in, soak at room temperature 24h makes Cd
2+With the abundant complexing of the carboxyl of conducting polymer fiber surface, 60 ℃ of dry 6h under nitrogen protection then; In the hydrothermal reaction kettle that is placed on 50mL, add 40.0mL 0.4molL
-1The thioacetyl amine aqueous solution, 120 ℃ of hydro-thermals reaction 12h naturally cools to room temperature.Take out product and be put in 50mL deionized water for ultrasonic ripple cleaning 3 times, it is subsequent use to obtain CdS/ conducting polymer tunica fibrosa behind 60 ℃ of vacuum drying 12h.
CdS/ conducting polymer tunica fibrosa is placed into 50mL hydrothermal reaction kettle in; The titanyl sulfate soak at room temperature of interpolation 20mL 0.5mol/L 20 hours; The urea that adds 20mL 0.5mol/L then, 120 ℃ of reaction 24h naturally cool to room temperature; Take out product and be put in 50mL deionized water for ultrasonic ripple cleaning 3 times, obtain CdS/TiO behind 60 ℃ of vacuum drying 12h
2/ conducting polymer fiber composite photochemical catalyst.
Be that example describes with reproducibility water pollutant methylene blue in this instance.
Degraded coordinate system hydrogen reaction is put into a slice CdS/TiO in the aqueous solution of methylene blue of 20mg/L
2/ conducting polymer fiber composite photochemical catalyst.(λ=254nm) is a built-in light source, with SP-6801 gas chromatograph (5A molecular sieve, N to adopt the 500W xenon lamp
2As carrier gas) gained gas is carried out quantitative analysis.After the illumination 3 hours, produce the hydrogen of 7mL, methylene blue 100% is degraded.
Claims (2)
1. heterojunction semiconductor/conducting polymer tunica fibrosa composite photo-catalyst is characterized in that: said composite photo-catalyst is that the form load of heterojunction semiconductor through the chemical bond complexing is scattered in the composite photo-catalyst that obtains behind the surface of conducting polymer tunica fibrosa;
Said heterojunction semiconductor is selected from ZnS-CdS/TiO
2, SnS/TiO
2, PbS/TiO
2, Bi
2S
3/ TiO
2, SnS
2/ TiO
2, CdS/TiO
2Or SnS-CdS/TiO
2, said heterojunction semiconductor is of a size of 20-5000nm;
Said conducting polymer tunica fibrosa is the conducting polymer tunica fibrosa that polymer and conductive material is mixed the fibre diameter 400nm-2 μ m that the back high-voltage electrostatic spinning obtains; Wherein polymer is selected from Kynoar, double A type polysulfones, PPSU, polyether sulfone, styrene-maleic anhydride copolymer, acrylic acid hexafluoro butyl ester-methacrylic acid copolymer, methacrylic acid ten difluoro heptyl ester-methacrylic acid copolymers, polyaniline, polystyrene, PEO, polyacrylonitrile, polyethylene glycol oxide, gathers in the styrene one or more; Said conductive material is selected from nano-graphite, carbon black, CNT or polyaniline; The addition of conductive material is the 1-10% of polymer quality.
2. the preparation method of the described composite photo-catalyst of claim 1 comprises the preparation of conducting polymer tunica fibrosa and each unit process of load of heterojunction semiconductor, it is characterized in that:
The preparation of said conducting polymer tunica fibrosa is that polymer and conductive material are added in the solvent, obtains the mixed solution of viscosity 600cP-1400cP after stirring, and the addition of conductive material is the 1-10% of polymer quality; Mixed solution is obtained the conducting polymer tunica fibrosa of fibre diameter 400nm-2 μ m through high-voltage electrostatic spinning;
The load of said heterojunction semiconductor comprises load sulfide and load TiO
2Wherein load sulfide is to place mixed solution to soak 0.5-10 days the conducting polymer tunica fibrosa; Said mixed solution is one or more the aqueous solution in bismuth nitrate, zinc compound, lead compound, tin compound, the cadmium compound, and total amount of substance concentration is 0.1-1mol/L; Descended dry 2-8 hour in 40-80 ℃ again; Add thiocarbamide or thioacetyl amine aqueous solution then; The mole of thiocarbamide or thioacetamide be solute substance in the mixed solution the amount sum 0.5-2 doubly; In closed container,, obtain the conducting polymer tunica fibrosa of load sulfide after washing and the drying in 50-200 ℃ of reaction 0.5-10 days; Load TiO
2Be that conducting polymer tunica fibrosa with load sulfide places the aqueous solution of the titanyl sulfate of 0.1-1.0mol/L to soak 0.5-10 days; Add aqueous solution of urea then; The mole of urea be titanyl sulfate mole 0.1-10 doubly; In closed container,, obtain heterojunction semiconductor/conducting polymer tunica fibrosa composite photo-catalyst after washing and the drying in 50-200 ℃ of reaction 0.5-10 days;
Said zinc compound is selected from zinc nitrate, zinc acetate or zinc sulfate;
Said lead compound is selected from plumbi nitras, lead acetate or lead sulfate;
Said tin compound is selected from butter of tin or stannous chloride;
Said cadmium compound is selected from caddy or cadmium sulfate.
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