CN104857994B - A kind of photocatalytic oxide nano-crystal thin-film of new structure and preparation method and application - Google Patents
A kind of photocatalytic oxide nano-crystal thin-film of new structure and preparation method and application Download PDFInfo
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Abstract
The invention discloses photocatalytic oxide nano-crystal thin-film of a kind of new structure and preparation method and application.The nano-crystal thin-film structure is P3HT/TiO2Laminated film.The P3HT：TiO2Ratio of weight and number be 12:10.The present invention uses chemical catalysis synthetic method, with FeCl on titanium dioxide nanocrystalline film33-hexyl thiophene of catalytic polymerization formation P3HT/TiO2Laminated film.Show that modification polythiophene can promote the light induced electron on titanium dioxide nanocrystalline film and the quick separating in hole, its photocatalysis performance is significantly better than unmodified P3HT titanium dioxide nanocrystalline film.
Description
Technical field
The invention belongs to photocatalysis technology field, and in particular to a kind of photocatalytic oxide nano-crystal thin-film drop of new structure
Solve organic dyestuff performance and the preparation method of this film.
Background technology
In China or even the whole world, long-term serious water pollution problems affects water resource and utilizes complete with aquatic ecosystem
Whole property, affects body health of people, and this also has become the significant bottleneck of restriction China sustainable development of socio-economy.
Water pollution accident takes place frequently, and the contamination accident of the initiation such as production accident, water pollution long term accumulation is to social economic development of region
Serious threat is constituted, regional society is also had a strong impact on stable.Water pollution in Songhuajiang River event, Taihu Lake Crises of blue-green alge bloom cause it is domestic,
The extensive concern of international community.
China's Taihu Lake basin is detected by GC-MS technologies, 273 kinds of organic chemical pollutants are detected altogether, than 1985
Year many detections 200, wherein there is 21 kinds to belong to priority pollutants（Many cyclophanes such as naphthalene, acenaphthylene, benzofluoranthrene, dibenzanthracene
Hydrocarbon and Nitro Polycyclic Aromatic Hydrocarbons）, 43 kinds belong to incretion interferent（Polychlorinated biphenyls, alkyl phenol, phthalate, maneb
Deng）.For these persistence organic pollutants（POPs）Even if, concentration very little, to the biodegradation under natural environment, light degradation
Deng still with very strong resistance.
The improvement of water pollution mainly experienced three developing stage, early in the twentieth century, due to the toxicity to chemical substance
The effect understanding such as timeliness and biological concentration is not deep enough, and people are prevented and remedied pollution by dilute waste products；Seventies 21 century, preventing and treating
Countermeasure enters " management and control epoch "；In China, originally water pollution control emphasis from controlling aerobic organic pollution（Control
Based on BOD and COD discharge capacitys）The poisonous and harmful priority pollutants of difficult for biological degradation are transferred to nitrogen phosphorus（Volatility halo
Hydro carbons, benzene homologues, phenols, polychlorinated biphenyl, multiring aromatic hydrocarbon, agricultural chemicals, heavy metal and oxide）.However, conventional waste water is handled
Technique does not often reach satisfied treatment effect to such poisonous and hazardous preferential contamination control thing, and is produced in processing procedure
Secondary pollution.Therefore, it is highly desirable to Development of Novel water technology.As physical chemistry, biology and material science etc. are ground
Study carefully application of the achievement in terms of water pollution control, the theory of water pollution processing is just undergoing deep change.Wherein, rising in recent years
Photocatalytic oxidation illustrate good development prospect.
Photocatalysis technology is a kind of emerging efficient, energy-conservation advanced oxidation water technology, it has also become current domestic and international
The focus of wastewater processing technology research.Photocatalytic method is that have band structure TiO using illumination is some2、ZnO、CdS、WO3Etc. luring
Strong oxidative free radical OH is sent out, many difficult chemical reactions realized is carried out under normal conditions, organic contamination of effectively degrading
Thing, reaches except poison, decolourizes, mineralising is the purpose of inorganic molecules.Photocatalytic Oxidation With Semiconductors method is a kind of deep oxidation process,
Can effectively in oxidation dye waste water many difficult degradations organic pollution, reach except poison, decolourize, deodorize, until mineralising is nothing
The purpose of machine small molecule.Semi-conducting material titanium dioxide and zinc oxide etc. are stable because of chemical property, and nontoxic, photocatalytic activity is high,
The advantages of oxidability is strong is as excellent catalysis material.Optically catalytic TiO 2 oxidation technology is organic in oxidative degradation water
There is obvious advantage during pollutant, particularly persistent organic pollutants.Ti chloro things, freon, oily waste water etc. can
By TiO2Catalytic degradation.Wherein waste water from dyestuff mainly includes：Methyl orange, methyl blue, rhodamine 6G, rhodamine B, salicylic acid, hydroxyl
Base azobenzene, disperse scarlet, containing sulfonic polarity azo dyes etc..But due to the limitation of titanium dioxide：(1) light induced electron is empty
Cave is easily combined, and causes photocatalytic activity to reduce；(2) energy gap is wider（3.2 eV）, can only be by institute's accounting in sunshine
Ultraviolet of the example less than 5% is excited.And photo-generate electron-hole recombination velocity is fast, quantum efficiency is relatively low, therefore directly utilizes solar energy
Photocatalysis is carried out to be very limited.
The content of the invention
For the above-mentioned state of the art, the technical problems to be solved by the invention there is provided a kind of photocatalysis of new structure
Oxide nano-crystal thin-film, by promoting the separation of photo-generate electron-hole, can significantly improve the photocatalysis efficiency of nano-crystal thin-film, together
When propose prepare this new structure film method.
Technical scheme disclosed in this invention is as follows：
A kind of TiO for being modified poly- 3- hexyl thiophenes compound2Porous nano-crystal thin-film, it is characterised in that it be by
P3HT/TiO2Film is attached on glass and constituted；3-hexyl thiophene structural formula：
The P3HT：TiO2Ratio of weight and number be 1-2:10, specially 1:10； 1.5:10； 2:10.
The present invention further discloses use chemical catalysis synthetic method with FeCl33-hexyl thiophene of catalytic polymerization, scene
Modification is on nano-crystal titanium dioxide film, it is characterised in that carried out by the steps：（1）Substrate of glass processing：Glass is cut out
Piece is cleaned with cleaning solution, is then cleaned by ultrasonic with distilled water, each in acetone, ethanol solution after drying to be cleaned by ultrasonic 15 minutes,
It is more than hour standby that the glass cleaned up is placed on immersion 24 in aqueous isopropanol；
（2）The preparation of titanium dioxide nanocrystalline film：The P25 titania nanoparticles powder of 1.00 g commercializations is taken to be placed in
In mortar, add 5 and drip triton x-100 and 8 mL n-butanols, grind 3 hours；Ground colloidal tio 2 is utilized into blade coating
Method is scratched in the substrate of glass of wash clean, is then calcined 30 minutes at 450 DEG C in atmosphere；
（3）The preparation of poly- 3- hexyl thiophenes compound：
A liquid：Weigh 5.1904 g FeCl3Solid, is dissolved in 10 mL ether, adds the mol/L HCl of 4 mL 1 molten
Liquid, ultrasonic agitation 15 minutes stands, takes supernatant liquor；
B liquid：Weigh 0.10 g-0.20g 3- hexyl thiophene monomers to be dissolved in 6 mL diethyl ether solutions, shake, mix it
Uniformly；1 titanium deoxid film is first put into A liquid 2 minutes, taken out, B liquid is put into after being cleaned in diethyl ether solution, takes within 10 minutes
Go out, dried up with hair-dryer；
（4）Photocatalysis performance is evaluated：It is placed in 20 μM of methyl orange solutions, under dark condition substrate is reached
To adsorption saturation, the nm low pressure ultraviolet lamps of 28 W 254 are then opened again and carry out photocatalytic degradation, sampling at regular intervals is purple
Outer visible spectrophotometer is determined in methyl orange maximum absorption wavelength（ 517 nm ）The absorbance at place, calculates substrate to be degraded
Residual concentration.
Preparation method of the present invention, wherein step（3）Middle P3HT/TiO2The preparation of film, scene is in nano-crystal dioxy
Change titanium film chemical polymerization thiophene monomer directly on a surface.
Preparation method of the present invention, wherein described titanium dioxide nanocrystalline film can also be that tin ash nano-crystal is thin
Film or zinc oxide nano-crystal thin-film.
The present invention further discloses the nano-crystal titanium dioxide of the polyase 13-hexyl thiophene modification prepared using the above method
Titanium film, the application in terms of photocatalytic degradation organic matter.Practice result is proved：3-hexyl thiophene polymerization prepared by the present invention
There is clear superiority in the nano-crystal titanium dioxide film of thing modification, degradation rate faster, is degraded in terms of photocatalytic degradation organic matter
Rate is higher.
The main innovative point of the present invention is to be showed on nano-crystal titanium dioxide film by thiophene monomer using chemical polymerization process
Field polymerization obtains P3HT/TiO2Laminated film, the polymer of surface modification can promote titanium dioxide photoproduction electronics and point in hole
From, reach improve titanium dioxide nanocrystalline film photocatalysis degradation organic contaminant purpose.It is main compared with prior art
It is to solve the problem of Titanium Dioxide efficiency is too low.
Semi-conducting material determines that it can be as photochemical catalyst because of the photoelectric characteristic of itself.Semiconductor particle has can band
Structure, the high level conduction band of the general valence band (Valence band, VB) and sky by filling up electronics of these band structures
(conduction Band, CB) is constituted, and there is forbidden band between valence band and conduction band, when energy is equal to or more than the light of energy gap
When being irradiated to semiconductor, after semiconductor absorber light, the electronics in valence band, which is excited, transits to conduction band formation high activity light induced electron
（e-）, hole is produced in valence band（h+）, and then form redox system.Electronics and hole are distinguished in the case where energy drives effect
Move to the diverse location of particle surface.Hole（h+）There is strong oxidizing property with extremely strong electronic capability, and light induced electron
（e-）Easily captured by materials such as oxygen in water, with strong reducing property.Hole in valence band can make organic pollution
Oxidation reaction.The process mechanism that it produces some high mars free radicals is as follows：
By polymerizeing the 3- hexyl thiophene monomers of various concentrations, three kinds of P3HT/ titanium deoxid films can be obtained, by it
It is positioned in 20 μm of ol/L methyl orange solutions, causes substrate to reach adsorption saturation under dark condition, uviol lamp is then opened again
Photocatalytic degradation is carried out, sampling at regular intervals is determined in methyl orange maximum absorption wave strong point with ultraviolet-uisible spectrophotometer
Absorbance, calculate the residual concentration of substrate to be degraded.Experimental data shows, thin by the titanium dioxide nanocrystalline for modifying P3HT
Film allows it to efficiently separate the hole pair of light induced electron one, reduces the probability of the hole-recombination of electronics one, substantially increases its light and urge
Change performance.
The present invention is subject to further instruction using thiophene, titanium dioxide nanocrystalline film as exemplary:
The present invention uses chemical catalysis synthetic method with FeCl3The nano-crystal titanium dioxide of 3-hexyl thiophene of catalytic polymerization modification
Titanium film, mainly includes：
（1）Substrate of glass processing：Glass cut-parts are cleaned with cleaning solution, are then cleaned by ultrasonic with distilled water, after drying
Each in acetone, ethanol solution to be cleaned by ultrasonic 15 minutes, the glass cleaned up is placed on 24 hours of immersion in aqueous isopropanol
It is standby above.The processing of substrate is not limited only to substrate of glass using substrate of glass as representative.Also include electro-conductive glass FTO, ITO；
Plastic-substrates；Metallic substrates etc..
（2）The preparation of titanium dioxide nanocrystalline film：Take the P25 titania nanoparticles powder of a small amount of commercialization to be placed in grind
In alms bowl, add 5 and drip triton x-100 and 8 mL n-butanols, grind 3 hours；Ground colloidal tio 2 is utilized into knife coating
Then blade coating is calcined 30 minutes at 450 DEG C in atmosphere in the substrate of glass of wash clean.Described nano-crystal sull with
Titanium dioxide nanocrystalline film is representative, but is not limited only to titanium dioxide nanocrystalline film.It is also possible to be tin ash nano-crystal thin-film, oxygen
Change zinc nano-crystal thin-film etc..
（3）Poly- 3- hexyl thiophenes compound（P3HT）Preparation：A liquid：Weigh 5.1904 g FeCl3Solid, is dissolved in 10
In mL ether, the mol/L HCl solutions of 4 mL 1 are added, ultrasonic agitation 15 minutes stands, takes supernatant liquor.
B liquid：Weigh 0.10 g-0.20 g 3- hexyl thiophene monomers to be dissolved in 6 mL diethyl ether solutions, shake, mix it
Uniformly.Wherein P3HT/TiO2The preparation of film.Scene chemical polymerization thiophene list direct on nano-crystal titanium dioxide film surface
Body.
Titanium deoxid film is first put into A liquid 2 minutes, taken out, be put into B liquid after being cleaned in diethyl ether solution, take within 10 minutes
Go out, dried up with hair-dryer.
（4）Photocatalysis performance is evaluated：It is placed in 20 μM of methyl orange solutions, under dark condition substrate is reached
To adsorption saturation, the nm low pressure ultraviolet lamps of 28 W 254 are then opened again and carry out photocatalytic degradation, sampling at regular intervals is purple
Outer visible spectrophotometer is determined in methyl orange maximum absorption wavelength（ 517 nm ）The absorbance at place, calculates substrate to be degraded
Residual concentration.Described polymer is not limited only to polythiophene using polythiophene as representative.It is polyaniline to be also possible to, polypyrrole
Deng.
The photocatalytic oxide nano-crystal thin-film of new structure disclosed by the invention has advantages below and beneficial effect：
（1）The present invention allows it to efficiently separate the hole pair of light induced electron one by modifying P3HT titanium deoxid film,
The probability of the hole-recombination of electronics one is reduced, its photocatalysis performance is substantially increased.
（2）Present invention process is simple, and chemical catalysis prepare P3HT/TiO2Film, low cost, raw material is easy to get, pollution-free,
Be conducive to the industrially scalable application in future.
Brief description of the drawings：
Fig. 1 is the UV-Vis absorption spectrums of different ultra violet lamp times under the concentration of embodiment 1；
Fig. 2 is the UV-Vis absorption spectrums of different ultra violet lamp times under the concentration of embodiment 2；
Fig. 3 is the UV-Vis absorption spectrums of different ultra violet lamp times under the concentration of embodiment 3；
Fig. 4 is the UV-Vis absorption spectrums of the different ultra violet lamp times of comparative example 1；
Fig. 5 is the-ln (C/C of embodiment 1,2,3 and comparative example 10) and irradiation time t graphs of a relation；
Fig. 6 is the C/C of embodiment 1,2,3 and comparative example 10With irradiation time t graphs of a relation.
Embodiment：
With reference to specific embodiment, the present invention will be further described, following each embodiments be merely to illustrate the present invention and
Not limitation of the present invention.Wherein used chemical reagent is commercially available, used 3- hexyl thiophenes monomer, methyl orange dye
Material is also commercially available.
Embodiment 1
One kind uses chemical catalysis synthetic method with FeCl3The nano titanium oxide of 3-hexyl thiophene of catalytic polymerization modification
Film, is carried out by the steps：
（1）Substrate of glass processing：Glass cut-parts are cleaned with cleaning solution, are then cleaned by ultrasonic with distilled water, after drying
Each in acetone, ethanol solution to be cleaned by ultrasonic 15 minutes, the glass cleaned up is placed on 24 hours of immersion in aqueous isopropanol
It is standby above.
（2）The preparation of titanium dioxide substrate：Take a small amount of P25 to be placed in mortar, add 5 and dripping triton x-100 and 8 ml just
Butanol, grinds 3 hours；Ground colloidal tio 2 is scratched on the electro-conductive glass of wash clean using knife coating, then 450
DEG C roasting 30 min.
（3）Poly- 3- hexyl thiophenes compound（P3HT）Preparation：A liquid：Weigh 5.1904 g FeCl3Solid, is dissolved in 10
In mL ether, the mol/L HCl solutions of 4 mL 1 are added, ultrasonic agitation 15 minutes stands, takes supernatant liquor.
B liquid：0.10 g 3- hexyl thiophene monomers are weighed to be dissolved in 6 mL diethyl ether solutions（C=0.097 mol/L）, concussion,
It is well mixed it.Titanium deoxid film is first put into A liquid 2 minutes, taken out, B liquid, 10 points are put into after being cleaned in diethyl ether solution
Clock takes out, and is dried up with hair-dryer.
Embodiment 2
One kind uses chemical catalysis synthetic method with FeCl3The nano titanium oxide of 3-hexyl thiophene of catalytic polymerization modification
Film, its step is same as Example 1, and difference is：
The preparation of polythiophene compound film：A liquid：Weigh 5.1904 gFeCl3Solid, is dissolved in 10 mL ether, plus
Enter the mol/L HCl solutions of 4 mL 1, the min of ultrasonic agitation 15 stands, takes supernatant liquor.
B liquid：0.15 g 3- hexyl thiophene monomers are weighed to be dissolved in 6 mL diethyl ether solutions（C=0.146 mol/L）, concussion,
It is well mixed it.Titanium deoxid film is first put into A liquid 2 minutes, taken out, B liquid, 10 points are put into after being cleaned in diethyl ether solution
Clock takes out, and is dried up with hair-dryer.
Embodiment 3
One kind uses chemical catalysis synthetic method with FeCl3The nano titanium oxide of 3-hexyl thiophene of catalytic polymerization modification
Film, its step and embodiment 1,2 is identical, and difference is：
The preparation of polythiophene compound film：A liquid：Weigh 5.1904 g FeCl3Solid, is dissolved in 10 mL ether,
4 mL 1mol/L HCl solutions are added, ultrasonic agitation 15 minutes stands, takes supernatant liquor.
B liquid：0.20 g 3- hexyl thiophene monomers are weighed to be dissolved in 6 mL diethyl ether solutions（C=0.194 mol/L）, concussion,
It is well mixed it.Titanium deoxid film is first put into A liquid 2 minutes, taken out, B liquid, 10 points are put into after being cleaned in diethyl ether solution
Clock takes out, and is dried up with hair-dryer.
Comparative example 1
This comparative example provides unmodified P3HT titanium deoxid film preparation method, and its concrete operations is：
（1）Substrate of glass processing：Glass cut-parts are cleaned with cleaning solution, are then cleaned by ultrasonic with distilled water, after drying
Each in acetone, ethanol solution to be cleaned by ultrasonic 15 minutes, the glass cleaned up is placed on 24 hours of immersion in aqueous isopropanol
It is standby above.
（2）The preparation of titanium dioxide substrate：Take a small amount of P25 to be placed in mortar, add 5 and dripping triton x-100 and 8 mL just
Butanol, grinds 3 hours；Ground colloidal tio 2 is scratched on the electro-conductive glass of wash clean using knife coating, then 450
DEG C roasting 30 minutes.
Subordinate list 1
It can be seen from accompanying drawing 5Illustrate that degraded of the above film to methyl orange is to belong to t linear relationship
First order reaction.
It can be drawn by subordinate list 1, under same concentrations substrate and same illumination time conditions, the degradation rate of embodiment 2
Highest.
From accompanying drawing 6 as can be seen that the laminated film of embodiment 2 is better to the photocatalytic degradation effect of methyl orange in solution.
In 210 min, pure TiO2The methyl orange of film degradation about 37.26%, and add 0.15 g (C=0.146 mol/L) 3- hexyl thiophenes
P3HT/TiO made from thiophene monomer2Its degradation rate is brought up to 80.20% by porous membrane, reaches highest.And add 0.10 g (C
=0.097 mol/L) P3HT/TiO made from 3- hexyl thiophene monomers2 Its degradation rate is brought up to 68.11% by porous membrane, and
Add 0.20 g (C=0.194 mol/L) P3HT/TiO made from 3- hexyl thiophene monomers2Porous membrane improves its degradation rate
To 71.71%.
Conclusion：
Use the 3-hexyl thiophene of the invention prepared polymer-modified nano-crystal titanium dioxide film and ordinary titanium dioxide
Nano-crystal thin-film compares, and there is clear superiority in terms of photocatalytic degradation organic matter, faster, degradation rate is higher for degradation rate.This hair
Bright innovative point is using chemical polymerization process to obtain P3HT/TiO by thiophene monomer polymerized in-situ on nano-crystal titanium dioxide film2
Laminated film, the polymer of surface modification can promote the separation in titanium dioxide photoproduction electronics and hole, reach raising titanium dioxide
The purpose of nano-crystal thin-film photocatalysis degradation organic contaminant.
Claims (3)
1. a kind of TiO for being modified poly- 3- hexyl thiophenes compound2Porous nano-crystal thin-film, it is characterised in that it be by poly- 3- oneself
Base thiophene/TiO2Film is attached on glass and constituted；
3-hexyl thiophene structural formula：
Wherein, the TiO for being modified poly- 3- hexyl thiophenes compound2Porous nano-crystal thin-film is prepared by the steps：
（1）Substrate of glass processing：Glass cut-parts are cleaned with cleaning solution, are then cleaned by ultrasonic with distilled water, third after drying
It is each in ketone, ethanol solution to be cleaned by ultrasonic 15 minutes, the glass cleaned up be placed in aqueous isopropanol soak 24 hours with
It is upper standby；
（2）The preparation of titanium dioxide nanocrystalline film：The P25 titania nanoparticles powder of 1.00 g commercializations is taken to be placed in mortar
In, add 5 and drip triton x-100 and 8 mL n-butanols, grind 3 hours；Ground colloidal tio 2 is scraped using knife coating
It is coated in the substrate of glass of wash clean, is then calcined 30 minutes at 450 DEG C in atmosphere；
（3）It has been modified the TiO of poly- 3- hexyl thiophenes compound2The preparation of porous nano-crystal thin-film：
A liquid：Weigh 5.1904 g FeCl3Solid, is dissolved in 10 mL ether, adds the mol/L HCl solutions of 4 mL 1, ultrasound
Stirring 15 minutes, stands, takes supernatant liquor；
B liquid：Weigh 0.10 g-0.20g 3- hexyl thiophene monomers to be dissolved in 6 mL diethyl ether solutions, shake, be well mixed it；
By step（2）The 1 titanium dioxide nanocrystalline film prepared is first put into A liquid 2 minutes, takes out, after being cleaned in diethyl ether solution
B liquid is put into, takes out within 10 minutes, is dried up with hair-dryer.
2. the TiO for being modified poly- 3- hexyl thiophenes compound described in claim 12The preparation method of porous nano-crystal thin-film, its
It is characterised by carrying out by the steps：
（1）Substrate of glass processing：Glass cut-parts are cleaned with cleaning solution, are then cleaned by ultrasonic with distilled water, third after drying
It is each in ketone, ethanol solution to be cleaned by ultrasonic 15 minutes, the glass cleaned up be placed in aqueous isopropanol soak 24 hours with
It is upper standby；
（2）The preparation of titanium dioxide nanocrystalline film：The P25 titania nanoparticles powder of 1.00 g commercializations is taken to be placed in mortar
In, add 5 and drip triton x-100 and 8 mL n-butanols, grind 3 hours；Ground colloidal tio 2 is scraped using knife coating
It is coated in the substrate of glass of wash clean, is then calcined 30 minutes at 450 DEG C in atmosphere；
（3）The preparation of poly- 3- hexyl thiophenes compound：
A liquid：Weigh 5.1904 g FeCl3Solid, is dissolved in 10 mL ether, adds the mol/L HCl solutions of 4 mL 1, ultrasound
Stirring 15 minutes, stands, takes supernatant liquor；
B liquid：Weigh 0.10 g-0.20g 3- hexyl thiophene monomers to be dissolved in 6 mL diethyl ether solutions, shake, be well mixed it；
By step（2）The 1 titanium dioxide nanocrystalline film prepared is first put into A liquid 2 minutes, takes out, after being cleaned in diethyl ether solution
B liquid is put into, takes out within 10 minutes, is dried up with hair-dryer.
3. the TiO for being modified polyase 13-hexyl thiophene of claim 12Porous nano-crystal thin-film is in the organic object space of photocatalytic degradation
The application in face.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101234344A (en) * | 2008-03-06 | 2008-08-06 | 四川大学 | Composite photo-catalytic material with visible light catalytic activity and preparation thereof |
| CN103753926A (en) * | 2014-01-16 | 2014-04-30 | 中科院广州化学有限公司 | High-conductivity polythiophene conductive coating layer and preparation method and application thereof |
-
2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101234344A (en) * | 2008-03-06 | 2008-08-06 | 四川大学 | Composite photo-catalytic material with visible light catalytic activity and preparation thereof |
| CN103753926A (en) * | 2014-01-16 | 2014-04-30 | 中科院广州化学有限公司 | High-conductivity polythiophene conductive coating layer and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| In situ 3-hexylthiophene polymerization onto surface of TiO2 based hybrid solar cells;Shengli Lu，et al.;《J Mater Sci: Mater Electron》;20090919;第21卷;2.Experimental * |
| Synthesis and photocatalytic activity of poly(3-hexylthiophene)/TiO2 composites;B.Muktha，et al.;《Journal of Solid State Chemistry》;20070807;第180卷;2.Experimental * |
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