CN102125859B - Preparation method of p-NiO/n-CdS/TiO2 composite semiconductor photochemical catalyst - Google Patents

Preparation method of p-NiO/n-CdS/TiO2 composite semiconductor photochemical catalyst Download PDF

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CN102125859B
CN102125859B CN2010106077615A CN201010607761A CN102125859B CN 102125859 B CN102125859 B CN 102125859B CN 2010106077615 A CN2010106077615 A CN 2010106077615A CN 201010607761 A CN201010607761 A CN 201010607761A CN 102125859 B CN102125859 B CN 102125859B
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cds
tio
nio
cadmium
nickel
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CN102125859A (en
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刘福生
刘忠祥
李振
卢南
刘恋恋
朱涛
方婷
李玲
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Nanjing Forestry University
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Nanjing Forestry University
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Abstract

The invention discloses a preparation method of a p-NiO/n-CdS/TiO2 composite semiconductor photochemical catalyst, which comprises the steps of: firstly, with titanate, alcohol, acid, thiocarbamide and deionized water as raw materials, preparing TiO2 gel; secondly, with the prepared TiO2 gel, a cadmium salt, thiocarbamide and deionized water as raw materials, sequentially carrying out treatments such as reaction, ultrasonic dispersion, decompression distillation, washing, ultrasonic dispersion, filtering, drying, roasting, grinding and the like to obtain CdS/TiO2 solid powder; and thirdly, with the obtained CdS/TiO2 solid powder, a nickel salt, ammonia water and deionized water as raw materials, sequentially carrying out treatments such as reaction, ultrasonic dispersion, decompression distillation, washing, ultrasonic dispersion, filtering, drying, roasting, grinding and the like to obtain the p-NiO/n-CdS/TiO2 composite semiconductor photochemical catalyst. Through compounding a p-type semiconductor NiO with n-type semiconductors CdS and TiO2, the light corrosion rate of the CdS is decreased; photoproduced electronics are effectively separated from the holes, thus the service life of the CdS is prolonged, and the photochemical catalysis efficiency of the p-NiO/n-CdS/TiO2 composite semiconductor photochemical catalyst is increased. The method is simple, convenient and practical, and is beneficial to popularization.

Description

A kind of p-NiO/n-CdS/TiO 2The preparation method of composite semiconductor light-catalyst
Technical field
The present invention relates to a kind of p-NiO/n-CdS/TiO 2The preparation method of composite semiconductor light-catalyst belongs to field of photocatalytic material.
Background technology
Along with the intensification day by day of energy crisis and environmental crisis, the development and use regenerative resource becomes the common focus of paying close attention in the whole world.Solar energy is the human the abundantest available energy; Being the energy that inexhaustible, nexhaustible, pollution-free, cheap, global various countries all can freely utilize peacefully, also is bases of other energy such as various regenerative resources such as biomass energy, wind energy, ocean energy, water ability.For this reason, national governments all attach great importance to the development and use of solar energy, and the development and use of solar energy become the popular research field that national governments drop into energetically.
Photochemical catalyst is one type of indispensable semi-conducting material of development and use solar energy.In three more than ten years in the past, scientists study the photocatalysis performance of many semiconductor light-catalysts, like TiO 2, RuO 2, ZnO, Fe 2O 3, CdS, SrTiO 3, CoO/SrTiO 3, NiO/SrTiO 3And Sr 3Ti 2O 7Deng.In numerous semiconductor light-catalysts, TiO 2With CdS be the semiconductor light-catalyst that receives much concern.
TiO 2Becoming with characteristics such as stable height, fast light burn into environmental friendliness and application cost are low has one of photochemical catalyst of application prospect most.But because TiO 2Band gap up to 3.2eV, can only the absorbing ultraviolet light hydrogen production by water decomposition, can not visible light be converted into chemical energy, therefore, use TiO separately 2Photocatalyst utilizes solar energy not have practical significance.
CdS is as a kind of narrow bandgap semiconductor material, and energy gap is about 2.4eV, and energy level and solar spectrum mate very much, considers it is a kind of very desirable photochemical catalyst from energy level.But a large amount of existing results of study show; Though simple CdS semiconductor has certain photocatalysis performance as photochemical catalyst; Because energy gap is narrow, the electron-hole pair easy compound that produces after the illumination makes its photocatalysis efficiency low; And receive the oxidation generation photoetch effect in hole easily, influence its service life.Because CdS is prone to take place the photoetch reaction, has shortened the service life of CdS greatly, even has lost photocatalytic activity, thereby limited the application of CdS.For this reason, the home and abroad scholar has carried out a large amount of research work aspect the modification of CdS, to improve the photocatalysis efficiency of CdS, reduces the photoetch of CdS, prolongs the service life of CdS.At present, the method to the CdS modification mainly contains: 1. noble metal loading; 2. compound with wide bandgap semiconductor (like CdS and TiO 2Compound, CdS and ZnO are compound); 3. carrier loadedly (load on SiO like CdS 2On) etc., but effect is all not obvious.
For reducing the photoetch effect of CdS, effectively improve the photocatalysis efficiency of CdS, the present invention is with p type semiconductor N iO and n type CdS semiconductor and TiO 2Compound, prepared p-n composite semiconductor p-NiO/n-CdS/TiO 2Photochemical catalyst.Prepared p-NiO/n-CdS/TiO 2Photochemical catalyst is under visible radiation, by p-NiO/n-CdS/TiO 2N type CdS semiconductor in the composite semiconductor absorbs visible light and produces electron-hole pair, i.e. electron transition on the CdS valence band stays the hole simultaneously to conduction band on the CdS valence band.Because p type semiconductor N iO is the hole transport semiconductor, therefore, p-NiO/n-CdS/TiO 2Hole in the composite semiconductor on the CdS valence band can be transferred on the NiO, makes CdS effectively avoid the oxidation in hole, reduces the photoetch effect of CdS; Simultaneously, the electron transition on the CdS conduction band is to TiO 2Conduction band can be imitated and improve the right separative efficiency in light induced electron-hole, thereby effectively improved p-NiO/n-CdS/TiO 2Photocatalysis efficiency.
The present invention is through p type semiconductor N iO and n type CdS semiconductor and TiO 2Compound, can effectively avoid the oxidation of hole to CdS, reduce the photoetch effect of CdS, also can make light induced electron-hole to obtaining more effective separation, both prolonged the service life of CdS, improved the photocatalysis efficiency of CdS again.This method improves the photocatalysis efficiency of CdS for prolonging the service life of CdS photochemical catalyst, has opened up a new way, has explored a kind of new method, has important and practical meanings.
Summary of the invention
A kind of p-NiO/n-CdS/TiO of the present invention 2The preparation method of composite semiconductor light-catalyst provides a kind of and both can prolong CdS service life, can improve the new method of CdS photocatalysis efficiency again.
A kind of p-NiO/n-CdS/TiO of the present invention 2The preparation method of composite semiconductor light-catalyst, prepared p-NiO/n-CdS/TiO 2Composite semiconductor light-catalyst is under the condition of light source at ultraviolet light, visible light and sunshine, can be used for photocatalysis degradation organic contaminant, photocatalytic hydrogen production by water decomposition.
A kind of p-NiO/n-CdS/TiO of the present invention 2The preparation method of composite semiconductor light-catalyst, one of purpose reduce the photoetch effect of CdS, have prolonged the service life of CdS, and its basic principle is the p-n composite semiconductor p-NiO/n-CdS/TiO that makes 2Photochemical catalyst is under radiation of visible light; Absorb visible light by n type CdS semiconductor, the electron transition on the CdS valence band is stayed next hole simultaneously to the CdS conduction band on the CdS valence band; Because p type semiconductor N iO is the hole transport semiconductor; Make hole transport on the CdS valence band to the NiO particle, reduced the oxidation of hole, reach the purpose of effective reduction CdS photoetch effect CdS.
A kind of p-NiO/n-CdS/TiO of the present invention 2The preparation method of composite semiconductor light-catalyst, two of purpose are through p-NiO, n-CdS and TiO 2The three is compound, improves the photocatalysis efficiency of CdS, and its basic principle is the p-n composite semiconductor p-NiO/n-CdS/TiO that makes 2Photochemical catalyst absorbs visible light by CdS semiconductor under radiation of visible light, the electron transition on the CdS valence band is to the CdS conduction band, and the electronics on the CdS conduction band transits to TiO again 2Conduction band, thus the right separative efficiency in light induced electron-hole effectively improved, reach the purpose of effective raising CdS photocatalysis efficiency.
A kind of p-NiO/n-CdS/TiO of the present invention 2The preparation method of composite semiconductor light-catalyst, adopt following technical scheme and step:
1, TiO 2The preparation of colloidal sol: the mass percent according to titanate esters, alcohol, acid and deionized water is (0.001%～70%): (0.001%～99%): (0.001%～90%): the ratio of (0.001%～90%); After titanate esters, alcohol, acid and deionized water mixing; 0 ℃～100 ℃ following stirring reaction 1～30h use frequency to be 20KH again Z～1MH Z, power is that the ultrasonic disperser of 30W～15KW disperses 0.1h～10h, makes TiO 2Colloidal sol;
2, CdS/TiO 2The preparation of pressed powder: according to the TiO that makes 2The mass percent of colloidal sol, cadmium salt, thiocarbamide and deionized water is (0.001%～90%): (0.001%～70%): (0.001%～90%): the ratio of (0.001%～90%), and with TiO 2Colloidal sol, cadmium salt, thiocarbamide mix with deionized water, are 20KH in frequency Z～1MH Z, power is under the ultrasonic dispersing of 30W～15KW, in 0 ℃～160 ℃ reaction 0.1h～30h, filter then and obtain the solid muffin; The solid muffin adds in the deionized water of 1～30 times of its quality, through washing, ultrasonic dispersion, filtration and drying, so behind the triplicate; The solid muffin is 200 ℃～250 ℃ roasting 0.1h～10h under nitrogen protection again; 300 ℃～350 ℃ following roasting 0.1h～10h, 400 ℃～480 ℃ following roasting 0.1h～10h, the cooling back is ground and is obtained CdS/TiO 2Pressed powder;
3, p-NiO/n-CdS/TiO 2The preparation of composite semiconductor light-catalyst: according to CdS/TiO 2The mass percent of pressed powder, nickel salt, ammoniacal liquor and deionized water is (0.001%～90%): (0.001%～70%): (0.001%～90%): the ratio of (O.001%～90%); Nickel salt, ammoniacal liquor and deionized water hybrid reaction are made nickel-ammonia complex ion solution, add CdS/TiO again 2Pressed powder, stir into suspension after, use frequency to be 20KH Z～1MH Z, power is that the ultrasonic disperser of 30W～15KW disperses 0.1h～10h, removes moisture and volatile ammonia 50 ℃～100 ℃ following decompression distillation, again 150 ℃～300 ℃ heat treatment 1h～10h under nitrogen protection; Material cooling back adds in the deionized water of 1～30 times of its quality; Through washing, ultrasonic dispersion, filtration and drying, so behind the triplicate, the solid muffin is 200 ℃～250 ℃ roasting 0.1h～10h under nitrogen protection again; 300 ℃～350 ℃ following roasting 0.1h～10h; 400 ℃～450 ℃ following roasting 0.1h～10h, 500 ℃～600 ℃ following roasting 0.1h～10h, the cooling back is ground and is obtained p-NiO/n-CdS/TiO 2Composite semiconductor light-catalyst.
A kind of p-NiO/n-CdS/TiO of the present invention 2The preparation method of composite semiconductor light-catalyst has following characteristics:
1, through p type semiconductor N iO and n type CdS semiconductor and TiO 2Compound, make p-n composite semiconductor p-NiO/n-CdS/TiO 2Photochemical catalyst makes p-NiO/n-CdS/TiO 2Photochemical catalyst is under radiation of visible light; Absorb visible light by n type CdS semiconductor, the electron transition on the CdS valence band is stayed next hole to the CdS conduction band on the CdS valence band; Because p type semiconductor N iO is the hole transport semiconductor; Make hole transport on the CdS valence band to the NiO particle, reduced the oxidation of hole, reached the purpose of effective reduction CdS photoetch effect CdS; Simultaneously, the electronics on the CdS conduction band can migrate to TiO 2Conduction band, also can effectively improve the right separative efficiency in light induced electron-hole, reach effective raising p-NiO/n-CdS/TiO 2The purpose of photocatalysis efficiency;
2, at TiO 2The colloidal sol preparatory phase, the employing frequency is 20KH Z～1MH Z, power is to react under the situation of ultrasonic disperser sonicated of 30W～15KW, purpose is to reduce TiO 2Sol particles is reunited, and helps controlling TiO 2Grain diameter, improve p-NiO/n-CdS/TiO 2Photocatalysis efficiency;
3, at CdS/TiO 2Pressed powder preparatory phase, frequency of utilization are 20KH Z～1MH Z, power is to react under the situation of ultrasonic disperser sonicated of 30W～15KW, purpose is to reduce the CdS particle that generates between the stage of reaction to reunite, and helps controlling the grain diameter of CdS, raising p-NiO/n-CdS/TiO 2Photocatalysis efficiency;
4, at CdS/TiO 2The pressed powder preparatory phase adopts under the different temperatures method of roasting stage by stage, promptly under nitrogen protection, and 200 ℃～250 ℃ roasting 0.1～10h, 300 ℃～350 ℃ following roasting 0.1～10h, 400 ℃～480 ℃ following roasting 0.1～10h, purpose is to make CdS/TiO 2The degree of crystallinity of pressed powder improves, and helps improving p-NiO/n-CdS/TiO 2Photocatalysis efficiency;
5, at p-NiO/n-CdS/TiO 2The composite semiconductor light-catalyst preparatory phase, the employing frequency is 20KH Z～1MH Z, power is that the ultrasonic disperser of 30W～15KW is handled 0.1～10h, purpose is to make CdS/TiO 2Pressed powder is uniformly dispersed, and can remove CdS/TiO 2The gas that adsorbs in the pressed powder micropore helps the NiO uniform load at CdS/TiO 2In the time of the pressed powder surface, also can make the NiO uniform load to CdS/TiO 2In the micropore of pressed powder, improve p-NiO/n-CdS/TiO 2NiO dispersed uniform property in the composite semiconductor light-catalyst improves p-NiO/n-CdS/TiO 2Photocatalysis efficiency;
6, at p-NiO/n-CdS/TiO 2The composite semiconductor light-catalyst preparatory phase adopts under the different temperatures method of roasting stage by stage, promptly under nitrogen protection; 200 ℃～250 ℃ roasting 0.1h～10h; 300 ℃～350 ℃ following roasting 0.1h～10h, 400 ℃～450 ℃ following roasting 0.1h～10h, 500 ℃～600 ℃ following roasting 0.1h～10h; Purpose is that the degree of crystallinity of NiO is improved, and makes NiO and CdS/TiO 2In conjunction with tightr, help improving p-NiO/n-CdS/TiO 2Photocatalysis efficiency.
A kind of p-NiO/n-CdS/TiO of the present invention 2The preparation method of composite semiconductor light-catalyst reacts used titanate esters and is in butyl titanate, metatitanic acid four isobutyl esters, metatitanic acid four n-propyls, tetraisopropyl titanate, tetraethyl titanate, the metatitanic acid tetramethyl ester any one or more.
A kind of p-NiO/n-CdS/TiO of the present invention 2The preparation method of composite semiconductor light-catalyst is (0.001%～70%) in the mass percent of titanate esters, alcohol, acid and deionized water: (0.001%～99%): (0.001%～90%): the ratio of (0.001%～90%), the TiO that reaction makes 2Colloidal sol, gained TiO 2TiO in the colloidal sol 2Shared mass percent is 0.001%～70%.
A kind of p-NiO/n-CdS/TiO of the present invention 2The preparation method of composite semiconductor light-catalyst reacts used alcohol and is in methyl alcohol, ethanol, normal propyl alcohol, the isopropyl alcohol any one or more.
A kind of p-NiO/n-CdS/TiO of the present invention 2The preparation method of composite semiconductor light-catalyst reacts used acid and is in hydrochloric acid, sulfuric acid, the nitric acid any one or more.
A kind of p-NiO/n-CdS/TiO of the present invention 2The preparation method of composite semiconductor light-catalyst reacts used cadmium salt and is in anhydrous slufuric acid cadmium, anhydrous nitric acid cadmium, anhydrous chlorides of rase cadmium, anhydrous cadmium bromide, anhydrous formic acid cadmium, anhydrous acetic acid cadmium, anhydrous tartaric acid cadmium, anhydrous citric acid cadmium, crystalline sulfuric acid cadmium, crystallization cadmium nitrate, crystallization caddy, crystallization cadmium bromide, crystallization formic acid cadmium, crystallization cadmium acetate, crystallization tartaric acid cadmium, the crystallization citric acid cadmium any one or more.
A kind of p-NiO/n-CdS/TiO of the present invention 2The preparation method of composite semiconductor light-catalyst reacts used nickel salt and is in anhydrous nickel sulfate, anhydrous nitric acid nickel, anhydrous chlorides of rase nickel, anhydrous nickelous bromide, anhydrous formic acid nickel, anhydrous acetic acid nickel, anhydrous tartaric acid nickel, anhydrous citric acid nickel, crystalline sulfuric acid nickel, crystallization nickel nitrate, crystallization nickel chloride, crystallization nickelous bromide, crystallization nickel formate, crystallization nickel acetate, crystallization tartaric acid nickel, the crystallization citric acid nickel any one or more.
A kind of p-NiO/n-CdS/TiO of the present invention 2The preparation method of composite semiconductor light-catalyst, the power that reacts used microwave reactor is 30W～15KW.
A kind of p-NiO/n-CdS/TiO of the present invention 2The preparation method of composite semiconductor light-catalyst, the frequency of used ultrasonic disperser is 20KH in the preparation process of photochemical catalyst Z～1MH Z, power is 30W～15KW.
The specific embodiment
Be a kind of p-NiO/n-CdS/TiO of the present invention below 2The preparation method's of composite semiconductor light-catalyst non-limiting example.Providing of these instances only is for illustrative purposes, can not be interpreted as qualification of the present invention.Because without departing from the spirit and scope of the present invention, can carry out many conversion to the present invention.In these embodiment, unless stated otherwise, all percentage all is meant mass percent.
Embodiment 1
TiO 2The preparation of colloidal sol
Butyl titanate: 21.25%
Absolute ethyl alcohol: 63.75%
35% hydrochloric acid: 5%
Deionized water: 10%
TiO 2The preparation of colloidal sol: according to above-mentioned mass percent, after butyl titanate, absolute ethyl alcohol, 35% hydrochloric acid and deionized water mixing, stirring reaction 20h under the room temperature uses frequency to be 30KH again Z, power is that the ultrasonic disperser of 800W disperses 2h, makes TiO 2Colloidal sol;
CdS/TiO 2The preparation of pressed powder:
The TiO that makes 2Colloidal sol: 60%
Anhydrous chlorides of rase cadmium: 1.3%
Thiocarbamide: 1%
Deionized water: 37.7%
CdS/TiO 2The preparation of pressed powder: according to above-mentioned mass percent, with the TiO that makes 2Colloidal sol, anhydrous chlorides of rase cadmium, thiocarbamide mix with deionized water, are 30KH in frequency Z, power is under the ultrasonic dispersing of 800W, in 80 ℃ of reaction 10h, filter then and obtain the solid muffin; The solid muffin adds in the deionized water of 1～30 times of its quality, through washing, ultrasonic dispersion, filtration and drying, so behind the triplicate; The solid muffin is 250 ℃ of roasting 3h under nitrogen protection again; 350 ℃ of following roasting 3h, 450 ℃ of following roasting 8h, the cooling back is ground and is obtained CdS/TiO 2Pressed powder;
P-NiO/n-CdS/TiO 2The preparation of composite semiconductor light-catalyst:
The CdS/TiO that makes 2Pressed powder: 20%
Acetic anhydride nickel: 1%
25% ammoniacal liquor: 2%
Deionized water: 67%
P-NiO/n-CdS/TiO 2The preparation of composite semiconductor light-catalyst: according to above-mentioned mass percent, acetic anhydride nickel, 25% ammoniacal liquor and deionized water hybrid reaction are made nickel-ammonia complex ion solution, add the CdS/TiO that makes again 2Pressed powder, stir into suspension after, use frequency to be 30KH Z, power is that the ultrasonic disperser of 1000W disperses 0.5h, removes moisture and volatile ammonia 80 ℃ of following decompression distillation, again 200 ℃ of heat treatment 2h under nitrogen protection; Material cooling back adds in the deionized water of 15 times of its quality, through washing, ultrasonic dispersion, filtration and drying, so behind the triplicate; The solid muffin is 250 ℃ of roasting 3h under nitrogen protection again, 350 ℃ of following roasting 3h, 450 ℃ of following roasting 3h; 550 ℃ of following roasting 8h, the cooling back is ground and is obtained p-NiO/n-CdS/TiO 2Pressed powder;
Embodiment 2
TiO 2The preparation of colloidal sol
Tetraisopropyl titanate: 39%
Isopropyl alcohol: 40%
65% nitric acid: 5%
Deionized water: 16%
TiO 2The preparation of colloidal sol: according to above-mentioned mass percent, after tetraisopropyl titanate, isopropyl alcohol, 65% nitric acid and deionized water mixing, stirring reaction 20h under the room temperature uses frequency to be 30KH again Z, power is that the ultrasonic disperser of 800W disperses 2h, makes TiO 2Colloidal sol;
CdS/TiO 2The preparation of pressed powder:
The TiO that makes 2Colloidal sol: 45.5%
Anhydrous cadmium bromide: 1.6%
Thiocarbamide: 1%
Deionized water: 51.9%
CdS/TiO 2The preparation of pressed powder: according to above-mentioned mass percent, with the TiO that makes 2Colloidal sol, anhydrous cadmium bromide, thiocarbamide mix with deionized water, are 30KH in frequency Z, power is under the ultrasonic dispersing of 800W, in 80 ℃ of reaction 10h, filter then and obtain the solid muffin; The solid muffin adds in the deionized water of 1～30 times of its quality, through washing, ultrasonic dispersion, filtration and drying, so behind the triplicate; The solid muffin is 250 ℃ of roasting 3h under nitrogen protection again; 350 ℃ of following roasting 3h, 450 ℃ of following roasting 8h, the cooling back is ground and is obtained CdS/TiO 2Pressed powder;
P-NiO/n-CdS/TiO 2The preparation of composite semiconductor light-catalyst:
The CdS/TiO that makes 2Pressed powder: 30%
Anhydrous nickel sulfate: 155 0.6%
25% ammoniacal liquor: 1.6%
Deionized water: 67.8%
P-NiO/n-CdS/TiO 2The preparation of composite semiconductor light-catalyst: according to above-mentioned mass percent, anhydrous nickel sulfate, 25% ammoniacal liquor and deionized water hybrid reaction are made nickel-ammonia complex ion solution, add the CdS/TiO that makes again 2Pressed powder, stir into suspension after, use frequency to be 30KH Z, power is that the ultrasonic disperser of 1000W disperses 0.5h, removes moisture and volatile ammonia 80 ℃ of following decompression distillation, again 200 ℃ of heat treatment 2h under nitrogen protection; Material cooling back adds in the deionized water of 15 times of its quality, through washing, ultrasonic dispersion, filtration and drying, so behind the triplicate; The solid muffin is 250 ℃ of roasting 3h under nitrogen protection again, 350 ℃ of following roasting 3h, 450 ℃ of following roasting 3h; 550 ℃ of following roasting 8h, the cooling back is ground and is obtained p-NiO/n-CdS/TiO 2Pressed powder;
Embodiment 3
TiO 2The preparation of colloidal sol
Metatitanic acid four n-propyls: 284 24.9%
Absolute ethyl alcohol: 44.1%
Isopropyl alcohol: 10%
Sulfuric acid: 3%
Deionized water: 18%
TiO 2The preparation of colloidal sol: according to above-mentioned mass percent, after metatitanic acid four n-propyls, absolute ethyl alcohol, isopropyl alcohol, sulfuric acid and deionized water mixing, stirring reaction 20h under the room temperature uses frequency to be 30KH again Z, power is that the ultrasonic disperser of 800W disperses 2h, makes TiO 2Colloidal sol;
CdS/TiO 2The preparation of pressed powder:
The TiO that makes 2Colloidal sol: 50%
Anhydrous slufuric acid cadmium: 1.3%
Thiocarbamide: 1.4%
Deionized water: 47.3%
CdS/TiO 2The preparation of pressed powder: according to above-mentioned mass percent, with the TiO that makes 2Colloidal sol, anhydrous slufuric acid cadmium, thiocarbamide mix with deionized water, are 30KH in frequency Z, power is under the ultrasonic dispersing of 800W, in 80 ℃ of reaction 10h, filter then and obtain the solid muffin; The solid muffin adds in the deionized water of 1～30 times of its quality, through washing, ultrasonic dispersion, filtration and drying, so behind the triplicate; The solid muffin is 250 ℃ of roasting 3h under nitrogen protection again; 350 ℃ of following roasting 3h, 450 ℃ of following roasting 8h, the cooling back is ground and is obtained CdS/TiO 2Pressed powder;
P-NiO/n-CdS/TiO 2The preparation of composite semiconductor light-catalyst:
The CdS/TiO that makes 2Pressed powder: 25%
Anhydrous nickelous bromide: 219 2.2%
25% ammoniacal liquor: 5%
Deionized water: 67.8%
P-NiO/n-CdS/TiO 2The preparation of composite semiconductor light-catalyst: according to above-mentioned mass percent, anhydrous nickelous bromide, 25% ammoniacal liquor and deionized water hybrid reaction are made nickel-ammonia complex ion solution, add the CdS/TiO that makes again 2Pressed powder, stir into suspension after, use frequency to be 30KH Z, power is that the ultrasonic disperser of 1000W disperses 0.5h, removes moisture and volatile ammonia 80 ℃ of following decompression distillation, again 200 ℃ of heat treatment 2h under nitrogen protection; Material cooling back adds in the deionized water of 15 times of its quality, through washing, ultrasonic dispersion, filtration and drying, so behind the triplicate; The solid muffin is 250 ℃ of roasting 3h under nitrogen protection again, 350 ℃ of following roasting 3h, 450 ℃ of following roasting 3h; 550 ℃ of following roasting 8h, the cooling back is ground and is obtained p-NiO/n-CdS/TiO 2Pressed powder;
Embodiment 4
TiO 2The preparation of colloidal sol
Tetraethyl titanate: 25.7%
Isopropyl alcohol: 52.3%
35% hydrochloric acid: 5%
Sulfuric acid: 2%
Deionized water: 15%
TiO 2The preparation of colloidal sol: according to above-mentioned mass percent, after tetraethyl titanate, isopropyl alcohol, 35% hydrochloric acid, sulfuric acid and deionized water mixing, stirring reaction 20h under the room temperature uses frequency to be 30KH again Z, power is that the ultrasonic disperser of 800W disperses 2h, makes TiO 2Colloidal sol;
CdS/TiO 2The preparation of pressed powder:
The TiO that makes 2Colloidal sol: 55.6%
Acetic anhydride cadmium: 230 1.6%
Thiocarbamide: 1%
Deionized water: 41.8%
CdS/TiO 2The preparation of pressed powder: according to above-mentioned mass percent, with the TiO that makes 2Colloidal sol, acetic anhydride cadmium, thiocarbamide mix with deionized water, are 30KH in frequency Z, power is under the ultrasonic dispersing of 800W, in 80 ℃ of reaction 10h, filter then and obtain the solid muffin; The solid muffin adds in the deionized water of 1～30 times of its quality, through washing, ultrasonic dispersion, filtration and drying, so behind the triplicate; The solid muffin is 250 ℃ of roasting 3h under nitrogen protection again; 350 ℃ of following roasting 3h, 450 ℃ of following roasting 8h, the cooling back is ground and is obtained CdS/TiO 2Pressed powder;
P-NiO/n-CdS/TiO 2The preparation of composite semiconductor light-catalyst:
The CdS/TiO that makes 2Pressed powder: 28%
Anhydrous chlorides of rase nickel: 130 1.5%
25% ammoniacal liquor: 5%
Deionized water: 65.5%
P-NiO/n-CdS/TiO 2The preparation of composite semiconductor light-catalyst: according to above-mentioned mass percent, four water acetic acid nickel, 25% ammoniacal liquor and deionized water hybrid reaction are made nickel-ammonia complex ion solution, add the CdS/TiO that makes again 2Pressed powder, stir into suspension after, use frequency to be 30KH Z, power is that the ultrasonic disperser of 1000W disperses 0.5h, removes moisture and volatile ammonia 80 ℃ of following decompression distillation, again 200 ℃ of heat treatment 2h under nitrogen protection; Material cooling back adds in the deionized water of 15 times of its quality, through washing, ultrasonic dispersion, filtration and drying, so behind the triplicate; The solid muffin is 250 ℃ of roasting 3h under nitrogen protection again, 350 ℃ of following roasting 3h, 450 ℃ of following roasting 3h; 550 ℃ of following roasting 8h, the cooling back is ground and is obtained p-NiO/n-CdS/TiO 2Pressed powder.

Claims (8)

1. p-NiO/n-CdS/TiO 2The preparation method of composite semiconductor light-catalyst is characterized in that adopting following technical scheme and step to prepare:
1. TiO 2The preparation of colloidal sol is (0.001%～70%) according to the mass percent of titanate esters, alcohol, acid and deionized water: (0.001%～99%): (0.001%～90%): the ratio of (0.001%～90%); After titanate esters, alcohol, acid and deionized water mixing; 0 ℃～100 ℃ following stirring reaction 1～30h use frequency to be 20KH again Z～1MH Z, power is that the ultrasonic disperser of 30W～15KW disperses 0.1h～10h, makes TiO 2Colloidal sol;
2. CdS/TiO 2The preparation of pressed powder is according to the TiO that makes 2The mass percent of colloidal sol, cadmium salt, thiocarbamide and deionized water is (0.001%～90%): (0.001%～70%): (0.001%～90%): the ratio of (0.001%～90%), and with TiO 2Colloidal sol, cadmium salt, thiocarbamide mix with deionized water, are 20KH in frequency Z～1MH Z, power is under the ultrasonic dispersing of 30W～15KW, in 0 ℃～160 ℃ reaction 0.1h～30h, filter then and obtain the solid muffin; The solid muffin adds in the deionized water of 1～30 times of its quality, through washing, ultrasonic dispersion, filtration and drying, so behind the triplicate; The solid muffin is 200 ℃～250 ℃ roasting 0.1h～10h under nitrogen protection again; 300 ℃～350 ℃ following roasting 0.1h～10h, 400 ℃～480 ℃ following roasting 0.1h～10h, the cooling back is ground and is obtained CdS/TiO 2Pressed powder;
3. p-NiO/n-CdS/TiO 2The preparation of composite semiconductor light-catalyst is according to the CdS/TiO that makes 2The mass percent of pressed powder, nickel salt, ammoniacal liquor and deionized water is (0.001%～90%): (0.001%～70%): (0.001%～90%): the ratio of (0.001%～90%); Nickel salt, ammoniacal liquor and deionized water hybrid reaction are made nickel-ammonia complex ion solution, add the CdS/TiO that makes again 2Pressed powder, stir into suspension after, use frequency to be 20KH Z～1MH Z, power is that the ultrasonic disperser of 30W～15KW disperses 0.1h～10h, removes moisture and volatile ammonia 50 ℃～100 ℃ following decompression distillation, again 150 ℃～300 ℃ heat treatment 1h～10h under nitrogen protection; Material cooling back adds in the deionized water of 1～30 times of its quality; Through washing, ultrasonic dispersion, filtration and drying, so behind the triplicate, the solid muffin is 200 ℃～250 ℃ roasting 0.1h～10h under nitrogen protection again; 300 ℃～350 ℃ following roasting 0.1h～10h; 400 ℃～450 ℃ following roasting 0.1h～10h, 500 ℃～600 ℃ following roasting 0.1h～10h, the cooling back is ground and is obtained p-NiO/n-CdS/TiO 2Composite semiconductor light-catalyst.
2. preparation method as claimed in claim 1 is characterized in that preparing p-NiO/n-CdS/TiO 2The method of composite semiconductor light-catalyst has following characteristics:
1. through p type semiconductor N iO and n type CdS semiconductor and TiO 2Compound, make p-n composite semiconductor p-NiO/n-CdS/TiO 2Photochemical catalyst makes p-NiO/n-CdS/TiO 2Photochemical catalyst is under radiation of visible light; Absorb visible light by n type CdS semiconductor, the electron transition on the CdS valence band is stayed next hole to the CdS conduction band on the CdS valence band; Because p type semiconductor N iO is the hole transport semiconductor; Make hole transport on the CdS valence band to the NiO particle, reduced the oxidation of hole, reached the purpose of effective reduction CdS photoetch effect CdS; Simultaneously, the electronics on the CdS conduction band can migrate to TiO 2Conduction band, also can effectively improve the right separative efficiency in light induced electron-hole, reach effective raising p-NiO/n-CdS/TiO 2The purpose of photocatalysis efficiency;
2. at TiO 2The colloidal sol preparatory phase, the employing frequency is 20KH Z～1MH Z, power is to react under the situation of ultrasonic disperser sonicated of 30W～15KW, purpose is to reduce TiO 2Sol particles is reunited, and helps controlling TiO 2Grain diameter, improve p-NiO/n-CdS/TiO 2Photocatalysis efficiency;
3. at CdS/TiO 2Pressed powder preparatory phase, frequency of utilization are 20KH Z～1MH Z, power is to react under the situation of ultrasonic disperser sonicated of 30W～15KW, purpose is to reduce the CdS particle that generates between the stage of reaction to reunite, and helps controlling the grain diameter of CdS, raising p-NiO/n-CdS/TiO 2Photocatalysis efficiency;
4. at CdS/TiO 2The pressed powder preparatory phase adopts under the different temperatures method of roasting stage by stage, promptly under nitrogen protection, and 200 ℃～250 ℃ roasting 0.1～10h, 300 ℃～350 ℃ following roasting 0.1～10h, 400 ℃～480 ℃ following roasting 0.1～10h, purpose is to make CdS/TiO 2The degree of crystallinity of pressed powder improves, and helps improving p-NiO/n-CdS/TiO 2Photocatalysis efficiency;
5. at p-NiO/n-CdS/TiO 2The composite semiconductor light-catalyst preparatory phase, the employing frequency is 20KH Z～1MH Z, power is that the ultrasonic disperser of 30W～15KW is handled 0.1～10h, purpose is to make CdS/TiO 2Pressed powder is uniformly dispersed, and can remove CdS/TiO 2The gas that adsorbs in the pressed powder micropore helps the NiO uniform load at CdS/TiO 2In the time of the pressed powder surface, also can make the NiO uniform load to CdS/TiO 2In the micropore of pressed powder, improve p-NiO/n-CdS/TiO 2NiO dispersed uniform property in the composite semiconductor light-catalyst improves p-NiO/n-CdS/TiO 2Photocatalysis efficiency;
6. at p-NiO/n-CdS/TiO 2The composite semiconductor light-catalyst preparatory phase adopts under the different temperatures method of roasting stage by stage, promptly under nitrogen protection; 200 ℃～250 ℃ roasting 0.1h～10h; 300 ℃～350 ℃ following roasting 0.1h～10h, 400 ℃～450 ℃ following roasting 0.1h～10h, 500 ℃～600 ℃ following roasting 0.1h～10h; Purpose is that the degree of crystallinity of NiO is improved, and makes NiO and CdS/TiO 2In conjunction with tightr, help improving p-NiO/n-CdS/TiO 2Photocatalysis efficiency.
3. preparation method as claimed in claim 1 is characterized in that the titanate esters of reacting used is any one or more in butyl titanate, metatitanic acid four isobutyl esters, metatitanic acid four n-propyls, tetraisopropyl titanate, tetraethyl titanate, the metatitanic acid tetramethyl ester.
4. preparation method as claimed in claim 1; It is characterized in that being (0.001%～70%) in the mass percent of titanate esters, alcohol, acid and deionized water: (0.001%～99%): (0.001%～90%): the ratio of (0.001%～90%), reaction makes TiO 2Colloidal sol, gained TiO 2TiO in the colloidal sol 2Shared mass percent is 0.001%～70%.
5. preparation method as claimed in claim 1 is characterized in that the alcohol that reacts used is any one or more in methyl alcohol, ethanol, normal propyl alcohol, the isopropyl alcohol.
6. preparation method as claimed in claim 1 is characterized in that the acid of reacting used is any one or more in hydrochloric acid, sulfuric acid, the nitric acid.
7. preparation method as claimed in claim 1 is characterized in that the cadmium salt that reacts used is any one or more in anhydrous slufuric acid cadmium, anhydrous nitric acid cadmium, anhydrous chlorides of rase cadmium, anhydrous cadmium bromide, anhydrous formic acid cadmium, anhydrous acetic acid cadmium, anhydrous tartaric acid cadmium, anhydrous citric acid cadmium, crystalline sulfuric acid cadmium, crystallization cadmium nitrate, crystallization caddy, crystallization cadmium bromide, crystallization formic acid cadmium, crystallization cadmium acetate, crystallization tartaric acid cadmium, the crystallization citric acid cadmium.
8. preparation method as claimed in claim 1 is characterized in that the nickel salt that reacts used is any one or more in anhydrous nickel sulfate, anhydrous nitric acid nickel, anhydrous chlorides of rase nickel, anhydrous nickelous bromide, anhydrous formic acid nickel, anhydrous acetic acid nickel, anhydrous tartaric acid nickel, anhydrous citric acid nickel, crystalline sulfuric acid nickel, crystallization nickel nitrate, crystallization nickel chloride, crystallization nickelous bromide, crystallization nickel formate, crystallization nickel acetate, crystallization tartaric acid nickel, the crystallization citric acid nickel.
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