CN100560203C - One-dimensional CdS/TiO 2Composite semiconductor photocatalysis nano material and preparation method thereof - Google Patents
One-dimensional CdS/TiO 2Composite semiconductor photocatalysis nano material and preparation method thereof Download PDFInfo
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- CN100560203C CN100560203C CNB2007101160370A CN200710116037A CN100560203C CN 100560203 C CN100560203 C CN 100560203C CN B2007101160370 A CNB2007101160370 A CN B2007101160370A CN 200710116037 A CN200710116037 A CN 200710116037A CN 100560203 C CN100560203 C CN 100560203C
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Abstract
The present invention relates to one-dimensional CdS/TiO
2Composite semiconductor photocatalysis nano material and preparation method thereof belongs to field of inorganic nano-material preparation.One-dimensional CdS/TiO
2The preparation method of composite semiconductor photocatalysis nano material comprises the synthetic of homogeneous CdS nano wire and coats legal system being equipped with one-dimensional CdS/TiO
2Core/shell structure, the present invention is reasonable in design, and is simple to operate, easy control of reaction, good reproducibility; The products therefrom thing is mutually pure, and the average diameter of CdS semiconductor nano wire is about 40 nanometers, the several approximately microns of length, TiO
2The average thickness of shell is about 8 nanometers.This type of one-dimentional structure material is compared with common nano thin-film, nano particle, and its performance is more superior, and preparation method is simple, and cost is cheaper.
Description
Technical field
The present invention relates to one-dimensional CdS/TiO
2Composite semiconductor photocatalysis nano material and preparation method thereof belongs to field of inorganic nano-material preparation.
Background technology
In recent ten years, the conductor photocatalysis technology is rapid in the application study development of environmental protection, health care, anti-caking mist and aspects such as automatically cleaning figure layer, photocatalysis chemical synthesis, and nano-photo catalytic becomes one of most active research field in the world.Fujishima in 1972 and Honda are at n-type semiconductor TiO
2Find the photocatalysis Decomposition effect of water on the electrode, opened the prelude (Nature, 1972,238,37.) of photocatalysis technology research.Garey TiO in 1976
2Photochemical catalyst has removed the chlorine in the Polychlorinated biphenyls (Bull.Environ.Contam.Toxical., 1976,16,697.), Frank photochemical catalytic oxidation CN-in 1977 is OCN-(J.Phys.Chem., 1977,81,1484.), the application study of photocatalysis technology aspect environmental protection begins to start.
Titanium dioxide is as a kind of typical semi-conducting material, and (it is strong to absorb the ultraviolet light performance owing to its photocatalytic activity height; Energy gap between forbidden band and the conduction band is big, and the reproducibility and the oxidisability in light induced electron and hole are strong), chemical property is stablized (acid and alkali-resistance and photochemical corrosion), and to biological nontoxic, advantage such as raw material sources are abundant, inexpensive is considered to one of the most promising photochemical catalyst.At present; the titanium dioxide that is applied to above purposes generally exists with the form of nano particle or film; in use there are problems such as separation, recovery difficulty in nano particle; and titanium deoxid film not only has the preparation temperature height; shortcomings such as cost height; and because device can only utilize skin effect, reduce so sensitivity is compared with monodimension nanometer material greatly with performance, can not apply in many instances.
TiO
2Semi-conductive energy gap is 3.2eV, can only absorb ultraviolet light, and quantum efficiency lower (about 10%); The right transfer velocity in photic electronics and hole is slow in the actual application, and the recombination rate height causes the photocatalysis quantum efficiency low.Recent research finds that other cheap semi-conducting material and TiO mix
2Carry out compoundly, can improve the photocatalytic activity of catalyst effectively, become and study more a kind of method in recent years.Preparation is based on TiO
2The compound semiconductor photocatalytic material of nanostructured can be regarded the modification of a kind of nanostructured to another kind of nanostructured in essence as, and its method of modifying comprises that simple combination, doping, sandwich construction and out-phase combination, intercalation are compound etc.The semi-conductive forbidden band of CdS is narrower, and conduction level compares TiO
2Height because crossovers take place in two kinds of semi-conductive forbidden bands, at visible wavelength range, electron transition takes place after, the valence band of CdS is stayed in the hole that optical excitation produces, electronics then transits to TiO
2Conduction band on, thereby improve the separation of charge rate of photochemical catalyst, photoactivate TiO
2Low-gap semiconductor CdS and TiO
2Carry out compoundly, prepare surface or body phase compound, its visible light-responded performance is given full play in expectation, improves activity of such catalysts under the daylight; One dimension semiconductor CdS nanostructured is widely used in preparing very sensitive device, but easily photoetch takes place, and influences service life, as with TiO
2Can suppress the generation of photoetch after compound, aspect practical application, have the meaning of particular importance.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of substep and prepare one-dimensional CdS/TiO
2The method of composite semiconductor photocatalysis nano material is to expand its response range and raising quantum efficiency to visible light.
One-dimensional CdS/TiO
2The preparation method of composite semiconductor photocatalysis nano material comprises the synthetic of homogeneous CdS nano wire and coats legal system being equipped with one-dimensional CdS/TiO
2The composite semiconductor photocatalysis nano material core/shell structure, step is as follows:
(1) preparation scale homogeneous CdS nano wire
Take by weighing 0.4g CdCl
22.5H
2O and 0.8g DDTC are dissolved in respectively in the 20mL water, and the two mixes, and stir under the room temperature 10-30 minute, filter to collect to obtain white product, after the white product room temperature water is given a baby a bath on the third day after its birth time, place 70 ℃ of dry 10-15 of electric heating constant temperature heating cabinet hours.Getting above-mentioned gained sample 1g places in the stainless steel cauldron of the inner liner polytetrafluoroethylene that the 45mL organic solvent is housed, reactor is tightened in sealing, under 100 ℃~300 ℃ constant temperatures, react 24~72h, after reaction finishes, naturally cool to room temperature, with washing respectively under the products therefrom room temperature, alcohol washes twice, centrifugation and at 70 ℃ of dry 10-15 hours then promptly obtains yardstick homogeneous CdS nano wire.
(2) coat legal system and be equipped with one-dimensional CdS/TiO
2Composite semiconductor photocatalysis nano material
Get ultrasonic being distributed in the conical flask that the 20mL absolute ethyl alcohol is housed of homogeneous CdS nano wire of 0.03g step (1) preparation, dropwise add the 20mL absolute ethyl alcohol that is dissolved with the 1-3mL butyl titanate, sealing, isothermal reaction 2~30h under 40~100 ℃ of conditions, after reaction finishes, naturally cool to room temperature, absolute ethyl alcohol under the products therefrom room temperature is washed twice, the centrifugation room temperature was placed 15-40 hour, then at 70 ℃ of dry 10-15 hours, the powder that obtains is cool to room temperature behind 300~500 ℃ of insulation 1-3h, promptly obtains one-dimensional CdS/TiO
2Composite semiconductor photocatalysis nano material.
Isothermal reaction described in the above-mentioned steps (1) is that reactor is placed in the baking oven of energy accurate temperature controlling.
Organic solvent described in the above-mentioned steps (1) can be any in ethylenediamine, diethylamine, ethylene glycol, pyridine, the benzene.
Isothermal reaction described in the above-mentioned steps (2) is that conical flask is placed in the water bath of energy accurate temperature controlling.
Insulating process described in the above-mentioned steps (2) is that product is placed in the tubular electric furnace of energy accurate temperature controlling.
All feed the N2 protection in insulation described in the above-mentioned steps (2) and the follow-up cooling procedure.
Absolute ethyl alcohol described in the above-mentioned steps (2) can replace by spent glycol.
The present invention is reasonable in design, and is simple to operate, easy control of reaction, good reproducibility; The products therefrom thing is mutually pure, and the average diameter of CdS semiconductor nano wire is about 40 nanometers, the several approximately microns of length, TiO
2The average thickness of shell is about 8 nanometers.
The pattern of product shows by transmission electron microscope photo (TEM), adopts Hitachi model H-700 transmission electron microscope, and accelerating potential is 100kV.
Fig. 1 a is the panorama TEM photo of CdS nano wire, and as can be seen from the figure product is made up of the homogeneous nano wire of diameter 30~40 nanometers, a length hundreds of micron.Find out on the surface of CdS nano wire from Fig. 1 b and fully to have coated one deck TiO
2Shell, shell thickness are about 8 nanometers, do not find free TiO by observing
2The existence of nano particle.
The present invention is on the basis of synthetic homogeneous CdS nano wire, by the method that coats, successfully with itself and TiO
2Different but the close semi-conducting material of these two kinds of energy gaps carries out compound, has expanded photocatalysis TiO
2Semiconductor has improved its quantum efficiency to the response range of visible light, and has suppressed the photoetch of CdS.This type of one-dimentional structure material is compared with common nano thin-film, nano particle, and its performance is more superior, and preparation method is simple, and cost is cheaper.
Description of drawings
Fig. 1 is typical CdS nano wire and one-dimensional CdS/TiO
2The transmission electron microscope photo (TEM) of composite semiconductor photocatalysis nano material.
The specific embodiment
The present invention will be further described below in conjunction with embodiment, but be not limited thereto.
Embodiment 1: above-mentioned one-dimensional CdS/TiO
2The preparation method of composite semiconductor photocatalysis nano material comprises the synthetic of homogeneous CdS nano wire, and coats legal system on this basis and be equipped with one-dimensional CdS/TiO
2The composite semiconductor photocatalysis nano material core/shell structure, the processing step of concrete preparation is as follows:
(1) takes by weighing 0.4g CdCl
22.5H
2O and 0.8g DDTC are dissolved in respectively in the 20mL water, and the two mixes, and stir under the room temperature 10 minutes, filter to collect to obtain white product, after the white product room temperature water is given a baby a bath on the third day after its birth time, place 70 ℃ of dryings of electric heating constant temperature heating cabinet 10 hours.Getting above-mentioned gained sample 1g places in the stainless steel cauldron of the inner liner polytetrafluoroethylene that the 45mL ethylenediamine is housed, reactor is tightened in sealing, in the baking oven of energy accurate temperature controlling, react 50h under 200 ℃ of constant temperatures, after reaction finishes, naturally cool to room temperature, with washing respectively under the products therefrom room temperature, alcohol washes twice, centrifugation and 70 ℃ of dryings 10 hours then promptly obtains yardstick homogeneous CdS nano wire.
(2) coat legal system and be equipped with one-dimensional CdS/TiO
2Composite semiconductor photocatalysis nano material is got ultrasonic being distributed in the conical flask that the 20mL absolute ethyl alcohol is housed of homogeneous CdS nano wire of 0.03g step (1) preparation, dropwise add the 20mL ethanol solution that is dissolved with the 2mL butyl titanate, sealing, isothermal reaction 12h under 40 ℃ of conditions in water bath that can accurate temperature controlling, after reaction finishes, naturally cool to room temperature, absolute ethyl alcohol under the products therefrom room temperature is washed twice, the centrifugation room temperature was placed 24 hours, then 70 ℃ of dryings 10 hours, the powder that obtains is incubated cool to room temperature behind the 1h in 500 ℃ of tubular electric furnaces, all feed N in insulation and the follow-up cooling procedure
2Protection promptly obtains one-dimensional CdS/TiO
2Composite semiconductor photocatalysis nano material.
Embodiment 2: preparation process is with example 1, and difference is: preparation CdS nano wire isothermal reaction 30h under 150 ℃ of conditions.
Embodiment 3: preparation process is with example 1, and difference is: preparation CdS nano wire isothermal reaction 30h under 250 ℃ of conditions.
Embodiment 4: preparation process is with example 1, and difference is: preparation CdS nano wire is that diethylamine is made solvent, isothermal reaction 30h under 150 ℃ of conditions.
Embodiment 5: preparation process is with example 1, and difference is: preparation CdS nano wire is that ethylene glycol is made solvent, isothermal reaction 30h under 150 ℃ of conditions.
Embodiment 6: preparation process is with example 1, and difference is: preparation CdS nano wire is that pyridine is made solvent, isothermal reaction 30h under 150 ℃ of conditions.
Embodiment 7: preparation process is with example 1, and difference is: preparation CdS nano wire is that benzene is made solvent, under 150 ℃ of conditions, and isothermal reaction 30h.
Embodiment 8: preparation process is with example 1, and difference is: dropwise add the 20mL ethanol solution that is dissolved with the 1mL butyl titanate.
Embodiment 9: preparation process is with example 1, and difference is: dropwise add the 20mL ethanol solution that is dissolved with the 3mL butyl titanate.
Embodiment 10: preparation process is with example 1, and difference is; Preparation one-dimensional CdS/TiO
2Composite semiconductor photocatalysis nano material in ethylene glycol solvent, isothermal reaction 30h under 40 ℃ of conditions.
Embodiment 11: preparation process is with example 1, and difference is: preparation one-dimensional CdS/TiO
2Composite semiconductor photocatalysis nano material is isothermal reaction 30h under 80 ℃ of conditions.
Embodiment 12: preparation process is with example 1, and difference is: preparation one-dimensional CdS/TiO
2Composite semiconductor photocatalysis nano material is isothermal reaction 30h under 100 ℃ of conditions.
Claims (7)
1, one-dimensional CdS/TiO
2The preparation method of composite semiconductor photocatalysis nano material comprises the synthetic of homogeneous CdS nano wire and coats legal system being equipped with one-dimensional CdS/TiO
2The composite semiconductor photocatalysis nano material core/shell structure, step is as follows:
(1) preparation scale homogeneous CdS nano wire
Take by weighing 0.4g CdCl
22.5H
2O and 0.8g DDTC are dissolved in respectively in the 20mL water, and the two mixes, and stir under the room temperature 10-30 minute, filter to collect to obtain white product, after the white product room temperature water is given a baby a bath on the third day after its birth time, place 70 ℃ of dry 10-15 of electric heating constant temperature heating cabinet hours; Getting above-mentioned gained sample 1g places in the stainless steel cauldron of the inner liner polytetrafluoroethylene that the 45mL organic solvent is housed, reactor is tightened in sealing, isothermal reaction 24~72h under 100 ℃~300 ℃ conditions, after reaction finishes, naturally cool to room temperature, with washing respectively under the products therefrom room temperature, alcohol washes twice, centrifugation and at 70 ℃ of dry 10-15 hours then promptly obtains yardstick homogeneous CdS nano wire;
(2) coat legal system and be equipped with one-dimensional CdS/TiO
2Composite semiconductor photocatalysis nano material
Get ultrasonic being distributed in the conical flask that the 20mL absolute ethyl alcohol is housed of homogeneous CdS nano wire of 0.03g step (1) preparation, dropwise add the 20mL absolute ethyl alcohol that is dissolved with the 1-3mL butyl titanate, sealing, isothermal reaction 2~30h under 40~100 ℃ of conditions, after reaction finishes, naturally cool to room temperature, absolute ethyl alcohol under the products therefrom room temperature is washed twice, the centrifugation room temperature was placed 15-40 hour, then at 70 ℃ of dry 10-15 hours, the powder that obtains is cool to room temperature behind 300~500 ℃ of insulation 1-3h, promptly obtains one-dimensional CdS/TiO
2Composite semiconductor photocatalysis nano material.
2, one-dimensional CdS/TiO as claimed in claim 1
2The preparation method of composite semiconductor photocatalysis nano material is characterized in that, the isothermal reaction described in the step (1) is that reactor is placed in the baking oven of energy accurate temperature controlling.
3, one-dimensional CdS/TiO as claimed in claim 1
2The preparation method of composite semiconductor photocatalysis nano material is characterized in that, the organic solvent described in the step (1) can be any in ethylenediamine, diethylamine, ethylene glycol, pyridine, the benzene.
4, one-dimensional CdS/TiO as claimed in claim 1
2The preparation method of composite semiconductor photocatalysis nano material is characterized in that, the isothermal reaction described in the step (2) is that conical flask is placed in the water bath of energy accurate temperature controlling.
5, one-dimensional CdS/TiO as claimed in claim 1
2The preparation method of composite semiconductor photocatalysis nano material is characterized in that, the insulating process described in the step (2) is that product is placed in the tubular electric furnace of energy accurate temperature controlling.
6, one-dimensional CdS/TiO as claimed in claim 1
2The preparation method of composite semiconductor photocatalysis nano material is characterized in that, all feeds N in insulation described in the step (2) and the follow-up cooling procedure
2Protection.
7, one-dimensional CdS/TiO as claimed in claim 1
2The preparation method of composite semiconductor photocatalysis nano material is characterized in that, the absolute ethyl alcohol described in the step (2) can replace by spent glycol.
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CN101618329B (en) * | 2009-07-31 | 2011-07-20 | 黑龙江省科学院石油化学研究院 | Preparation method of composite photocatalyst CdS/n-TiO2 for catalyzing and decomposing H2S to prepare hydrogen |
CN102019190B (en) * | 2009-09-21 | 2012-12-05 | 同济大学 | Method for preparing photochemical catalyst applied to degradation of environmental pollutants by using solar energy |
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CN103173764A (en) * | 2013-03-22 | 2013-06-26 | 天津大学 | TiO2 through hole nanotube and CdS compound array film and preparation method thereof |
CN104549270B (en) * | 2013-10-15 | 2017-02-22 | 中国科学院金属研究所 | Heterogeneous p-n knot nano composite material and preparation method and application thereof |
CN103566953B (en) * | 2013-11-28 | 2015-06-24 | 中国石油大学(华东) | One-dimensional nanometer photocatalyst as well as preparation method and application thereof |
CN104689834A (en) * | 2015-03-10 | 2015-06-10 | 聊城大学 | CdS-loaded Bi2WO6/CdS nano composite material as well as preparation method and application thereof |
CN104923261A (en) * | 2015-05-14 | 2015-09-23 | 南开大学 | Method for prolonging service life of CdS nano photocatalyst |
CN105727997A (en) * | 2016-01-29 | 2016-07-06 | 上海师范大学 | Cadmium sulfide/sodium titanate supported type compound visible-light-driven photocatalyst and preparation method and application thereof |
CN106622293B (en) * | 2016-12-30 | 2018-11-27 | 哈尔滨工业大学 | A kind of H-TiO2/CdS/Cu2-xThe preparation method of S nanobelt |
CN108579766B (en) * | 2018-04-17 | 2020-10-20 | 华东理工大学 | Preparation method of cadmium sulfide-based composite catalyst capable of treating industrial wastewater |
CN108842159B (en) * | 2018-06-19 | 2020-08-04 | 上海师范大学 | Preparation method and application of cadmium sulfide nanowire and carbon nanotube composite flexible electrode with high hydrogen production activity |
CN109225263B (en) * | 2018-07-27 | 2021-04-23 | 广东工业大学 | CdS/TiO2Nano heterojunction photocatalytic material and preparation method and application thereof |
CN109647437B (en) * | 2019-01-24 | 2022-05-06 | 广东石油化工学院 | CuS doped nano TiO2Photocatalyst, preparation method and application thereof |
CN115746615B (en) * | 2022-12-05 | 2023-12-01 | 贵州电网有限责任公司 | CdS/TiO 2 Preparation method and application of core-shell structure nanocomposite |
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