CN108097268B - CdCoS2/CuCo2O4/TiO2Photocatalyst and preparation method thereof - Google Patents
CdCoS2/CuCo2O4/TiO2Photocatalyst and preparation method thereof Download PDFInfo
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- 229910016506 CuCo2O4 Inorganic materials 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 101
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 91
- XKMAKWPZGDBONG-UHFFFAOYSA-N [Co].[Cd] Chemical compound [Co].[Cd] XKMAKWPZGDBONG-UHFFFAOYSA-N 0.000 claims abstract description 58
- DAWJJMYZJQJLPZ-UHFFFAOYSA-N 2-sulfanylprop-2-enoic acid Chemical compound OC(=O)C(S)=C DAWJJMYZJQJLPZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000011941 photocatalyst Substances 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 37
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008279 sol Substances 0.000 claims abstract description 32
- 229910000531 Co alloy Inorganic materials 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 65
- 238000005406 washing Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 21
- 238000000227 grinding Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 17
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 17
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229940011182 cobalt acetate Drugs 0.000 claims description 14
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 14
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 6
- 229960005150 glycerol Drugs 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910016507 CuCo Inorganic materials 0.000 description 4
- -1 cadmium mercapto acrylate Chemical compound 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- 241000218691 Cupressaceae Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- KSSNXJHPEFVKHY-UHFFFAOYSA-N phenol;hydrate Chemical compound O.OC1=CC=CC=C1 KSSNXJHPEFVKHY-UHFFFAOYSA-N 0.000 description 1
- 229940068984 polyvinyl alcohol Drugs 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 229940045136 urea Drugs 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a CdCoS2/CuCo2O4/TiO2Photocatalyst, preparation method thereof and CdCoS2/CuCo2O4/TiO2The raw material components of the photocatalyst comprise: cadmium cobalt precursor and CuCo2O4/TiO2Wherein, the cadmium cobalt precursor and CuCo2O4/TiO2The mass of (2) is 3: (87-96), and mixing the cadmium-cobalt precursor with the cobalt precursor according to the mass ratio of 10: (155-180): (34-45): (46-58): (33-46) reacting the cadmium-cobalt alloy powder, the mercapto-acrylic acid sol, urea, glycerol and polyethylene glycol 600. CdCoS of the invention2/CuCo2O4/TiO2The photocatalyst has excellent photocatalytic wastewater degradation performance and strong adaptability, and is suitable for treatment of various organic wastewater; the stability is good, and the material can be repeatedly used; the preparation is simple and easy to operate.
Description
Technical Field
The invention relates to a CdCoS2/CuCo2O4/TiO2A photocatalyst and a preparation method thereof, belonging to the field of photocatalysts.
Background
Wastewater treatment (wastewater treatment methods) is to treat wastewater by physical, chemical and biological methods, so that the wastewater is purified and pollution is reduced, and the wastewater is recycled and reused, and water resources are fully utilized. Among them, chemical treatment is widely used because of high treatment efficiency.
Nano TiO 22Has obvious effects in the aspects of quantum size effect, surface effect, macroscopic quantum tunneling effect, volume effect and the likeAdvantageously, therefore, the nano TiO2Is widely applied to the fields of ultraviolet absorbers, water treatment, photoelectronic devices, catalyst carriers, water treatment and the like.
At present, TiO2The performance of the photocatalyst is required to be further improved when the photocatalyst is used for degrading waste water.
Disclosure of Invention
In order to solve the problem of TiO in the prior art2The invention provides a CdCoS which has the defects of poor performance and the like when being used for photocatalytic degradation of wastewater2/CuCo2O4/TiO2The photocatalyst has excellent performance of photocatalytic degradation of wastewater.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
CdCoS2/CuCo2O4/TiO2The photocatalyst comprises the following raw material components: cadmium cobalt precursor and CuCo2O4/TiO2Wherein, the cadmium cobalt precursor and CuCo2O4/TiO2The mass of (2) is 3: (87-96), and mixing the cadmium-cobalt precursor with the cobalt precursor according to the mass ratio of 10: (155-180): (34-45): (46-58): (33-46) reacting the cadmium-cobalt alloy powder, the mercapto-acrylic acid sol, urea, glycerol and polyethylene glycol 600.
One of the purposes of the urea is to reduce the content of CuCo in the mercapto acrylic acid2O4/TiO2The corrosiveness of (2).
CdCoS of the present application2/CuCo2O4/TiO2The photocatalyst has excellent performance of photocatalytic degradation of wastewater.
Preferably, CuCo2O4/TiO2Prepared from copper oxalate, cobalt acetate, acrylamide, alcohol and TiO2Reacting with water to obtain the product, wherein the product is prepared from cupric oxalate, cobalt acetate, acrylamide, ethanol and TiO2And water in a mass ratio of 15: (20-30): (11-20): (65-83): (85-98): (98-115). This can further improve the photocatalytic efficiency of the resulting catalyst.
One of the purposes of acrylamide is to increase CuCo2O4In TiO2The dispersibility of the surface and the uniformity of the particle size are controlled; TiO 22One of the purposes of (1) is to reduce CuCo2O4Recombination of surface electron-hole pairs and shortening of the transport distance of electron-hole pairs.
In order to further improve the catalytic efficiency of the photocatalyst, the mercaptoacrylic acid sol is preferably prepared by reacting mercaptoacrylic acid, glycerol, polyethylene glycol 200, polyethylene glycol 400 and a polyvinyl alcohol aqueous solution with the mass concentration of 10%, wherein the mass ratio of the mercaptoacrylic acid, the glycerol, the polyethylene glycol 200, the polyethylene glycol 400 and the polyvinyl alcohol aqueous solution with the mass concentration of 10% is 100: (65-80): (32-45): (23-37): (10-25).
One of the purposes of the mercapto acrylic acid is to improve the wettability to solid materials and serve as a sulfur source, the mercapto acrylic acid has excellent corrosion performance, and the urea belongs to an alkaline material and can reduce and relieve the corrosion rate of the mercapto acrylic acid to the cadmium cobalt alloy powder. The mercapto acrylic acid has the corrosivity of acrylic acid, can corrode the cadmium-cobalt alloy powder and simultaneously form cadmium mercapto acrylate and cobalt mercapto acrylate, and after the cadmium mercapto acrylate and the cobalt mercapto acrylate are subjected to hydrothermal reaction and high-temperature roasting treatment, the CdCoS2Uniformly deposited on CuCo2O4/TiO2Surface, formation of CdCos2/CuCo2O4/TiO2Photocatalyst, CdCoS2/CuCo2O4/TiO2The photocatalyst can not only reduce CdCoS2Recombination of surface electron-hole pairs, shortening of transmission distance of electron-hole pairs and improvement of CdCoS2And CuCo2O4/TiO2Photocatalytic activity of (1).
In order to further improve the catalytic efficiency of the photocatalyst, the preferable particle size of the cadmium-cobalt alloy powder is 15-30 nm, and the mass ratio of cadmium to cobalt in the cadmium-cobalt alloy powder is 95.7: 4.3.
The dCoS2/CuCo2O4/TiO2The preparation method of the photocatalyst comprises the steps of preparing a cadmium cobalt precursor and CuCo2O4/TiO2According to the mass ratio of 3: (87-96) adding the mixture into a hydrothermal reaction kettle at the temperatureReacting for 15 +/-1 h at the temperature of 210 +/-10 ℃, sequentially roasting, washing and drying the obtained product, and grinding to obtain the CdCoS2/CuCo2O4/TiO2A photocatalyst.
In order to further improve the use stability and the catalytic efficiency of the catalyst, the roasting is carried out for 2 plus or minus 0.1h at 200 plus or minus 5 ℃, 2 plus or minus 0.1h at 300 plus or minus 5 ℃, 2 plus or minus 0.1h at 400 plus or minus 5 ℃ and 2 plus or minus 0.1h at 500 plus or minus 5 ℃ in sequence under the protection of nitrogen, and then the catalyst is naturally cooled to room temperature; washing with 10% acetic acid water solution for 3 + -1 times, and then washing with ethanol for 3 + -1 times; the drying is carried out at 60 + -5 deg.C and vacuum degree of-0.09 + -0.01 MPa for 1 + -0.1 h.
In order to further improve the catalytic activity of the photocatalyst, the preparation method of the cadmium cobalt precursor comprises the following steps: mixing cadmium-cobalt alloy powder, mercapto-acrylic acid sol, urea, glycerol and polyethylene glycol 600 according to the weight ratio of 10: (155-180): (34-45): (46-58): (33-46) and reacting for 0.5-1 h at the stirring speed of 35-51 r/min and the temperature of 20-29 ℃ to obtain the cadmium-cobalt precursor.
In order to further improve the catalytic activity and the use stability of the photocatalyst, the preparation method of the mercapto acrylic acid sol comprises the following steps: mixing mercaptoacrylic acid, glycerol, polyethylene glycol 200, polyethylene glycol 400 and 10% polyvinyl alcohol aqueous solution according to the mass concentration of 100: (65-80): (32-45): (23-37): (10-25) adding the mixture into a reactor according to the mass ratio, and reacting for 0.3-0.9 h under the conditions that the stirring speed is 120-145 r/min and the temperature is 37-53 ℃ to obtain the mercapto acrylic acid sol.
The mercaptoacrylic acid has excellent fluidity and excellent wettability to solid materials, and in the hydrothermal reaction process, the glycerol, the polyethylene glycol 200, the polyethylene glycol 400, the polyethylene glycol 600 and a 10% polyvinyl alcohol aqueous solution are used as excellent dispersing aids, so that the CdCoS can be improved2In the presence of CuCo2O4/TiO2The dispersion property of the surface is improved, thereby improving the CdCoS2/CuCo2O4/TiO2The photocatalytic activity of the photocatalyst.
To further provideCatalytic activity and stability in use of high gloss catalyst, CuCo2O4/TiO2The preparation method comprises the following steps: adding copper oxalate, cobalt acetate, acrylamide, ethanol and TiO2And water according to 15: (20-30): (11-20): (65-83): (85-98): (98-115) adding the mixture into a hydrothermal reaction kettle in a mass ratio, reacting for 10 +/-1 h at the temperature of 150 +/-5 ℃, sequentially carrying out reduced pressure distillation, roasting, washing and drying on the obtained product, and grinding to obtain CuCo2O4/TiO2(ii) a The reduced pressure distillation is carried out for 0.5 plus or minus 0.1h under the conditions that the temperature is 105 plus or minus 5 ℃ and the vacuum degree is minus 0.08 plus or minus 0.01 MPa; the roasting is sequentially roasting at 200 +/-5 ℃ for 2 +/-0.1 h, at 300 +/-5 ℃ for 2 +/-0.1 h, at 400 +/-5 ℃ for 2 +/-0.1 h, at 500 +/-5 ℃ for 2 +/-0.1 h, at 600 +/-5 ℃ for 2 +/-0.1 h, and then naturally cooling to room temperature; washing with water for 3 + -1 times, and then washing with ethanol for 3 + -1 times; the drying is carried out at 70 + -5 deg.C and-0.06 + -0.01 MPa for 1 + -0.1 h.
Acrylamide can be spontaneously polymerized to generate polyacrylamide under the heated condition, materials can be uniformly dispersed in the polyacrylamide super absorbent resin, and after high-temperature roasting, the polyacrylamide is decomposed and simultaneously CuCo is used2O4Gradually generated and uniformly deposited on TiO2Surface, forming CuCo2O4/TiO2Photocatalyst, CuCo2O4/TiO2The photocatalyst can not only reduce CuCo2O4Recombination of surface electron-hole pairs, shortening of transmission distance of electron-hole pairs, and improvement of CuCo2O4And TiO2Photocatalytic activity of (1).
After the catalyst is used, the catalyst is filtered out of the system, washed by water and dried, and then the catalyst can be used continuously.
The prior art is referred to in the art for techniques not mentioned in the present invention.
CdCoS of the invention2/CuCo2O4/TiO2The photocatalyst has excellent photocatalytic wastewater degradation performance and strong adaptability, and is suitable for treatment of various organic wastewater; the structure has high strength and good stability, and can be repeatedly used; simple preparationSimple and easy to operate.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The following raw material manufacturers were used: copper oxalate, guangdong wengjiang chemical reagents ltd; cobalt acetate, Jining Baichuan chemical Co., Ltd; acrylamide, ethanol, TiO2Glycerin, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, urea, polyvinyl alcohol (1799pva100-27), thiourea, Shandong Bai Qian chemical Co., Ltd; mercaptoacrylic acid, jingle (tianjin) chemical products marketing limited; cadmium cobalt alloy powder was prepared according to the following documents: the authors of the new preparation method of Pb-Sb-Cd alloy for positive plate of accumulator: roche can be cypress, periodical: during the preparation of the electric bicycle in 2011, at the 07 th stage, lead and antimony are replaced by cobalt, the obtained particle size is 15-30 nm, and the mass ratio of cadmium to cobalt in the cadmium-cobalt alloy powder is 95.7: 4.3.
Example 1
CdCoS2/CuCo2O4/TiO2The preparation method of the photocatalyst comprises the following steps:
(1) weighing 15 parts of copper oxalate, 25 parts of cobalt acetate, 16 parts of acrylamide, 75 parts of ethanol and 93 parts of TiO2Adding 106 parts of water into a hydrothermal reaction kettle, reacting at 150 ℃ for 10 hours, distilling the product at 105 ℃ and-0.08 MPa under reduced pressure for 0.5 hour, then roasting at 200 ℃ for 2 hours, roasting at 300 ℃ for 2 hours, roasting at 400 ℃ for 2 hours, roasting at 500 ℃ for 2 hours, roasting at 600 ℃ for 2 hours, naturally cooling to room temperature, washing with 500mL of water for 3 times (the water consumption for each washing is 500mL, other similar expressions are similar, the meanings are similar), washing with 500mL of ethanol for 3 times, drying at 70 ℃ and-0.06 MPa in vacuum for 1 hour, and grinding to obtain CuCo2O4/TiO2；
(2) Weighing 100 parts of mercaptoacrylic acid, 73 parts of glycerol, 39 parts of polyethylene glycol 200, 27 parts of polyethylene glycol 400 and 17 parts of polyvinyl alcohol aqueous solution with the mass concentration of 10%, adding into a reactor, and reacting for 0.6h under the conditions that the stirring speed is 135r/min and the system temperature is maintained at 45 ℃ to obtain mercaptoacrylic acid sol;
(3) weighing 10 parts of cadmium-cobalt alloy powder, 167 parts of mercapto-acrylic acid sol, 43 parts of urea, 49 parts of glycerol and 37 parts of polyethylene glycol 600, adding into a reactor, and reacting for 0.6h under the conditions that the stirring speed is 45r/min and the system temperature is maintained at 27 ℃, so as to obtain a cadmium-cobalt precursor;
(4) weighing 3 parts of cadmium-cobalt precursor and 91 parts of CuCo2O4/TiO2Adding the mixture into a hydrothermal reaction kettle, reacting for 15 hours at the reaction temperature of 210 ℃, roasting the product for 2 hours at the temperature of 200 ℃, roasting for 2 hours at the temperature of 300 ℃, roasting for 2 hours at the temperature of 400 ℃ and roasting for 2 hours at the temperature of 500 ℃, then naturally cooling to room temperature, washing for 3 times by using 500mL of 10% acetic acid aqueous solution, washing for 3 times by using 500mL of ethanol, then drying for 1 hour in vacuum at the temperature of 60 ℃ and under the pressure of-0.09 MPa, and grinding to obtain the CdCoS2/CuCo2O4/TiO2A photocatalyst.
Example 2
CdCoS2/CuCo2O4/TiO2The preparation method of the photocatalyst comprises the following steps:
(1) weighing 15 parts of copper oxalate, 20 parts of cobalt acetate, 11 parts of acrylamide, 65 parts of ethanol and 85 parts of TiO2Adding 98 parts of water into a hydrothermal reaction kettle, reacting at 150 ℃ for 10 hours, distilling the product at 105 ℃ and-0.08 MPa under reduced pressure for 0.5 hour, then roasting at 200 ℃ for 2 hours, roasting at 300 ℃ for 2 hours, roasting at 400 ℃ for 2 hours, roasting at 500 ℃ for 2 hours, roasting at 600 ℃ for 2 hours, naturally cooling to room temperature, washing with 500mL of water for 3 times, washing with 500mL of ethanol for 3 times, drying at 70 ℃ and-0.06 MPa in vacuum for 1 hour, and grinding to obtain CuCo2O4/TiO2；
(2) Weighing 100 parts of mercaptoacrylic acid, 65 parts of glycerol, 32 parts of polyethylene glycol 200, 23 parts of polyethylene glycol 400 and 10 parts of polyvinyl alcohol aqueous solution with the mass concentration of 10%, adding into a reactor, and reacting for 0.3h under the conditions that the stirring speed is 120r/min and the system temperature is maintained at 37 ℃ to obtain mercaptoacrylic acid sol;
(3) weighing 10 parts of cadmium-cobalt alloy powder, 155 parts of mercapto-acrylic acid sol, 34 parts of urea, 46 parts of glycerol and 33 parts of polyethylene glycol 600, adding into a reactor, and reacting for 0.5h under the conditions that the stirring speed is 35r/min and the system temperature is maintained at 20 ℃ to obtain a cadmium-cobalt precursor;
(4) weighing 3 parts of cadmium-cobalt precursor and 87 parts of CuCo2O4/TiO2Adding the mixture into a hydrothermal reaction kettle, reacting for 15 hours at the reaction temperature of 210 ℃, roasting the product for 2 hours at the temperature of 200 ℃, roasting for 2 hours at the temperature of 300 ℃, roasting for 2 hours at the temperature of 400 ℃ and roasting for 2 hours at the temperature of 500 ℃, then naturally cooling to room temperature, washing for 3 times by using 500mL of 10% acetic acid aqueous solution, washing for 3 times by using 500mL of ethanol, drying for 1 hour in vacuum at the temperature of 60 ℃ and under the pressure of-0.09 MPa, and grinding to obtain the CdCoS2/CuCo2O4/TiO2A photocatalyst.
Example 3
CdCoS2/CuCo2O4/TiO2The preparation method of the photocatalyst comprises the following steps:
(1) weighing 15 parts of copper oxalate, 30 parts of cobalt acetate, 20 parts of acrylamide, 83 parts of ethanol and 98 parts of TiO2Adding 115 parts of water into a hydrothermal reaction kettle, reacting for 10 hours at the reaction temperature of 150 ℃, distilling the product at 105 ℃ and-0.08 MPa under reduced pressure for 0.5 hour, then roasting for 2 hours at 200 ℃, 2 hours at 300 ℃, 2 hours at 400 ℃, 2 hours at 500 ℃, 2 hours at 600 ℃, naturally cooling to room temperature, washing with 500mL of water for 3 times, washing with 500mL of ethanol for 3 times, drying at 70 ℃ and-0.06 MPa in vacuum for 1 hour, and grinding to obtain CuCo2O4/TiO2；
(2) Weighing 100 parts of mercaptoacrylic acid, 80 parts of glycerol, 45 parts of polyethylene glycol 200, 37 parts of polyethylene glycol 400 and 25 parts of polyvinyl alcohol aqueous solution with the mass concentration of 10%, adding into a reactor, and reacting for 0.9h under the conditions that the stirring speed is 145r/min and the system temperature is maintained at 53 ℃ to obtain mercaptoacrylic acid sol;
(3) weighing 10 parts of cadmium-cobalt alloy powder, 180 parts of mercapto-acrylic acid sol, 45 parts of urea, 58 parts of glycerol and 46 parts of polyethylene glycol 600, adding into a reactor, and reacting for 1h under the conditions that the stirring speed is 51r/min and the system temperature is kept at 29 ℃ to obtain a cadmium-cobalt precursor;
(4) weighing 3 parts of cadmium-cobalt precursor,96 parts of CuCo2O4/TiO2Adding the mixture into a hydrothermal reaction kettle, reacting for 15 hours at the reaction temperature of 210 ℃, roasting the product for 2 hours at the temperature of 200 ℃, roasting for 2 hours at the temperature of 300 ℃, roasting for 2 hours at the temperature of 400 ℃ and roasting for 2 hours at the temperature of 500 ℃, then naturally cooling to room temperature, washing for 3 times by using 500mL of 10% acetic acid aqueous solution, washing for 3 times by using 500mL of ethanol, drying for 1 hour in vacuum at the temperature of 60 ℃ and under the pressure of-0.09 MPa, and grinding to obtain the CdCoS2/CuCo2O4/TiO2A photocatalyst.
Example 4
CdCoS2/CuCo2O4/TiO2The preparation method of the photocatalyst comprises the following steps:
(1) weighing 15 parts of copper oxalate, 27 parts of cobalt acetate, 15 parts of acrylamide, 70 parts of ethanol and 90 parts of TiO2Adding 100 parts of water into a hydrothermal reaction kettle, reacting at 150 ℃ for 10 hours, distilling the product at 105 ℃ and-0.08 MPa under reduced pressure for 0.5 hour, then roasting at 200 ℃ for 2 hours, roasting at 300 ℃ for 2 hours, roasting at 400 ℃ for 2 hours, roasting at 500 ℃ for 2 hours, roasting at 600 ℃ for 2 hours, naturally cooling to room temperature, washing with 500mL of water for 3 times, washing with 500mL of ethanol for 3 times, drying at 70 ℃ and-0.06 MPa in vacuum for 1 hour, and grinding to obtain CuCo2O4/TiO2；
(2) Weighing 100 parts of mercaptoacrylic acid, 70 parts of glycerol, 35 parts of polyethylene glycol 200, 25 parts of polyethylene glycol 400 and 15 parts of polyvinyl alcohol aqueous solution with the mass concentration of 10%, adding into a reactor, and reacting for 0.5h under the conditions that the stirring speed is 130r/min and the system temperature is maintained at 40 ℃ to obtain mercaptoacrylic acid sol;
(3) weighing 10 parts of cadmium-cobalt alloy powder, 160 parts of mercapto-acrylic acid sol, 39 parts of urea, 50 parts of glycerol and 35 parts of polyethylene glycol 600, adding into a reactor, and reacting for 0.7h under the conditions that the stirring speed is 40r/min and the system temperature is maintained at 25 ℃ to obtain a cadmium-cobalt precursor;
(4) weighing 3 parts of cadmium-cobalt precursor and 90 parts of CuCo2O4/TiO2Adding into a hydrothermal reaction kettle, reacting at 210 deg.C for 15 hr, roasting the product at 200 deg.C for 2 hr, roasting at 300 deg.C for 2 hr, roasting at 400 deg.C for 2 hr, and cooling to 500 deg.C under the protection of nitrogenRoasting for 2h, naturally cooling to room temperature, washing with 500mL 10% acetic acid water solution for 3 times, washing with 500mL ethanol for 3 times, vacuum drying at 60 deg.C under-0.09 MPa for 1h, and grinding to obtain CdCoS2/CuCo2O4/TiO2A photocatalyst.
Example 5
CdCoS2/CuCo2O4/TiO2The preparation method of the photocatalyst comprises the following steps:
(1) weighing 15 parts of copper oxalate, 23 parts of cobalt acetate, 19 parts of acrylamide, 68 parts of ethanol and 87 parts of TiO2Adding 99 parts of water into a hydrothermal reaction kettle, reacting at 150 ℃ for 10 hours, distilling the product at 105 ℃ and-0.08 MPa under reduced pressure for 0.5 hour, then roasting at 200 ℃ for 2 hours, roasting at 300 ℃ for 2 hours, roasting at 400 ℃ for 2 hours, roasting at 500 ℃ for 2 hours, roasting at 600 ℃ for 2 hours, naturally cooling to room temperature, washing with 500mL of water for 3 times, washing with 500mL of ethanol for 3 times, drying at 70 ℃ and-0.06 MPa in vacuum for 1 hour, and grinding to obtain CuCo2O4/TiO2；
(2) Weighing 100 parts of mercaptoacrylic acid, 69 parts of glycerol, 37 parts of polyethylene glycol 200, 26 parts of polyethylene glycol 400 and 18 parts of polyvinyl alcohol aqueous solution with the mass concentration of 10%, adding into a reactor, and reacting for 0.8h under the conditions that the stirring speed is 136r/min and the system temperature is maintained at 46 ℃ to obtain mercaptoacrylic acid sol;
(3) weighing 10 parts of cadmium-cobalt alloy powder, 173 parts of mercapto-acrylic acid sol, 40 parts of urea, 55 parts of glycerol and 37 parts of polyethylene glycol 600, adding into a reactor, and reacting for 0.8h under the conditions that the stirring speed is 41r/min and the system temperature is maintained at 23 ℃ to obtain a cadmium-cobalt precursor;
(4) weighing 3 parts of cadmium-cobalt precursor and 91 parts of CuCo2O4/TiO2Adding the mixture into a hydrothermal reaction kettle, reacting for 15 hours at the reaction temperature of 210 ℃, roasting the product for 2 hours at the temperature of 200 ℃, roasting for 2 hours at the temperature of 300 ℃, roasting for 2 hours at the temperature of 400 ℃ and roasting for 2 hours at the temperature of 500 ℃, then naturally cooling to room temperature, washing for 3 times by using 500mL of 10% acetic acid aqueous solution, washing for 3 times by using 500mL of ethanol, drying for 1 hour in vacuum at the temperature of 60 ℃ and under the pressure of-0.09 MPa, and grinding to obtain the CdCoS2/CuCo2O4/TiO2A photocatalyst.
Example 6
CdCoS2/CuCo2O4/TiO2The preparation method of the photocatalyst comprises the following steps:
(1) weighing 15 parts of copper oxalate, 28 parts of cobalt acetate, 14 parts of acrylamide, 83 parts of ethanol and 96 parts of TiO2Adding 112 parts of water into a hydrothermal reaction kettle, reacting at 150 ℃ for 10 hours, distilling the product at 105 ℃ and-0.08 MPa under reduced pressure for 0.5 hour, then roasting at 200 ℃ for 2 hours, roasting at 300 ℃ for 2 hours, roasting at 400 ℃ for 2 hours, roasting at 500 ℃ for 2 hours, roasting at 600 ℃ for 2 hours, naturally cooling to room temperature, washing with 500mL of water for 3 times, washing with 500mL of ethanol for 3 times, drying at 70 ℃ and-0.06 MPa in vacuum for 1 hour, and grinding to obtain CuCo2O4/TiO2；
(2) Weighing 100 parts of mercaptoacrylic acid, 76 parts of glycerol, 43 parts of polyethylene glycol 200, 29 parts of polyethylene glycol 400 and 19 parts of polyvinyl alcohol aqueous solution with the mass concentration of 10%, adding into a reactor, and reacting for 0.7h under the conditions that the stirring speed is 143r/min and the system temperature is maintained at 52 ℃ to obtain mercaptoacrylic acid sol;
(3) weighing 10 parts of cadmium-cobalt alloy powder, 170 parts of mercapto-acrylic acid sol, 36 parts of urea, 49 parts of glycerol and 45 parts of polyethylene glycol 600, adding into a reactor, and reacting for 0.7h under the conditions that the stirring speed is 50r/min and the system temperature is maintained at 23 ℃ to obtain a cadmium-cobalt precursor;
(4) weighing 3 parts of cadmium-cobalt precursor and 92 parts of CuCo2O4/TiO2Adding the mixture into a hydrothermal reaction kettle, reacting for 15 hours at the reaction temperature of 210 ℃, roasting the product for 2 hours at the temperature of 200 ℃, roasting for 2 hours at the temperature of 300 ℃, roasting for 2 hours at the temperature of 400 ℃ and roasting for 2 hours at the temperature of 500 ℃, then naturally cooling to room temperature, washing for 3 times by using 500mL of 10% acetic acid aqueous solution, washing for 3 times by using 500mL of ethanol, drying for 1 hour in vacuum at the temperature of 60 ℃ and under the pressure of-0.09 MPa, and grinding to obtain the CdCoS2/CuCo2O4/TiO2A photocatalyst.
Example 7
CdCoS2/CuCo2O4/TiO2Photocatalyst and process for producing the sameThe preparation method comprises the following steps:
(1) weighing 15 parts of copper oxalate, 27 parts of cobalt acetate, 19 parts of acrylamide, 76 parts of ethanol and 93 parts of TiO2Adding 112 parts of water into a hydrothermal reaction kettle, reacting at 150 ℃ for 10 hours, distilling the product at 105 ℃ and-0.08 MPa under reduced pressure for 0.5 hour, then roasting at 200 ℃ for 2 hours, roasting at 300 ℃ for 2 hours, roasting at 400 ℃ for 2 hours, roasting at 500 ℃ for 2 hours, roasting at 600 ℃ for 2 hours, naturally cooling to room temperature, washing with 500mL of water for 3 times, washing with 500mL of ethanol for 3 times, drying at 70 ℃ and-0.06 MPa in vacuum for 1 hour, and grinding to obtain CuCo2O4/TiO2；
(2) Weighing 100 parts of mercaptoacrylic acid, 77 parts of glycerol, 44 parts of polyethylene glycol 200, 35 parts of polyethylene glycol 400 and 23 parts of a polyvinyl alcohol aqueous solution with the mass concentration of 10%, adding into a reactor, and reacting for 0.7h under the conditions that the stirring speed is 129r/min and the system temperature is maintained at 41 ℃ to obtain mercaptoacrylic acid sol;
(3) weighing 10 parts of cadmium-cobalt alloy powder, 176 parts of mercapto-acrylic acid sol, 43 parts of urea, 51 parts of glycerol and 40 parts of polyethylene glycol 600, adding into a reactor, and reacting for 0.8h under the conditions that the stirring speed is 46r/min and the system temperature is maintained at 26 ℃ to obtain a cadmium-cobalt precursor;
(4) weighing 3 parts of cadmium-cobalt precursor and 95 parts of CuCo2O4/TiO2Adding the mixture into a hydrothermal reaction kettle, reacting for 15 hours at the reaction temperature of 210 ℃, roasting the product for 2 hours at the temperature of 200 ℃, roasting for 2 hours at the temperature of 300 ℃, roasting for 2 hours at the temperature of 400 ℃ and roasting for 2 hours at the temperature of 500 ℃, then naturally cooling to room temperature, washing for 3 times by using 500mL of 10% acetic acid aqueous solution, washing for 3 times by using 500mL of ethanol, drying for 1 hour in vacuum at the temperature of 60 ℃ and under the pressure of-0.09 MPa, and grinding to obtain the CdCoS2/CuCo2O4/TiO2A photocatalyst.
Example 8
CdCoS2/CuCo2O4/TiO2The preparation method of the photocatalyst comprises the following steps:
(1) weighing 15 parts of copper oxalate, 21 parts of cobalt acetate, 17 parts of acrylamide, 78 parts of ethanol and 95 parts of TiO2And 114 parts of water are added to the hydrothermal reactionReaction is carried out in a kettle at the reaction temperature of 150 ℃ for 10h, the product is decompressed and distilled for 0.5h under the temperature of 105 ℃ and the pressure of-0.08 MPa, then is roasted for 2h at the temperature of 200 ℃, roasted for 2h at the temperature of 300 ℃, roasted for 2h at the temperature of 400 ℃, roasted for 2h at the temperature of 500 ℃ and roasted for 2h at the temperature of 600 ℃, then is naturally cooled to the room temperature, is washed for 3 times by 500mL of water, is washed for 3 times by 500mL of ethanol, is dried for 1h under the vacuum condition of 70 ℃ and the pressure of-0.06 MPa2O4/TiO2；
(2) Weighing 100 parts of mercaptoacrylic acid, 73 parts of glycerol, 41 parts of polyethylene glycol 200, 35 parts of polyethylene glycol 400 and 17 parts of polyvinyl alcohol aqueous solution with the mass concentration of 10%, adding into a reactor, and reacting for 0.8h under the conditions that the stirring speed is 136r/min and the system temperature is maintained at 51 ℃ to obtain mercaptoacrylic acid sol;
(3) weighing 10 parts of cadmium-cobalt alloy powder, 171 parts of mercapto-acrylic acid sol, 36 parts of urea, 50 parts of glycerol and 41 parts of polyethylene glycol 600, adding into a reactor, and reacting for 0.7h under the conditions that the stirring speed is 46r/min and the system temperature is maintained at 26 ℃ to obtain a cadmium-cobalt precursor;
(4) weighing 3 parts of cadmium-cobalt precursor and 91 parts of CuCo2O4/TiO2Adding the mixture into a hydrothermal reaction kettle, reacting for 15 hours at the reaction temperature of 210 ℃, roasting the product for 2 hours at the temperature of 200 ℃, roasting for 2 hours at the temperature of 300 ℃, roasting for 2 hours at the temperature of 400 ℃ and roasting for 2 hours at the temperature of 500 ℃, then naturally cooling to room temperature, washing for 3 times by using 500mL of 10% acetic acid aqueous solution, washing for 3 times by using 500mL of ethanol, drying for 1 hour in vacuum at the temperature of 60 ℃ and under the pressure of-0.09 MPa, and grinding to obtain the CdCoS2/CuCo2O4/TiO2A photocatalyst.
Comparative example 1
In this comparative example, CuCo was not added2O4/TiO2Other components and preparation methods were the same as in example 1.
Comparative example 2
In this comparative example, the mercaptoacrylic sol was not added, and the other components and preparation method were the same as in example 1.
Comparative example 3
In the comparative example, the cadmium cobalt precursor was not added, and the other components and preparation methods were the same as in example 1.
Comparative example 4
In the comparative example, ordinary TiO was selected for the formulation2Alternative to CuCo in example 12O4/TiO2Other components and preparation methods were the same as in example 1.
Comparative example 5
In the comparison example, common thiourea is selected in the formula to replace the mercapto acrylic acid sol in the example 1, and other components and the preparation method are the same as the example 1.
Comparative example 6
In the comparison example, the cadmium-cobalt alloy powder in the example 1 is replaced by the common cadmium acetate and the common cobalt acetate in the formula, and other components and the preparation method are the same as those in the example 1.
TABLE 1 CdCoS prepared in examples 1-82/CuCo2O4/TiO2Performance parameters of the photocatalyst
TABLE 2 CdCoS obtained in example 1 and comparative examples 1 to 62/CuCo2O4/TiO2Performance parameters of the photocatalyst
| Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| Phenol content/g/L | 0.09 | 1.36 | 2.47 | 2.47 | 1.66 | 1.53 | 1.09 |
The waste water liquid is 2.5g/L phenol water solution; the dosage of the photocatalyst is 3 g/L; illuminating for 4 hours by using a 350W xenon lamp light source;
phenol content test was performed according to GB 22574-2008.
Claims (7)
1. CdCoS2/CuCo2O4/TiO2A photocatalyst, characterized in that: the raw material components comprise: cadmium cobalt precursor and CuCo2O4/TiO2Wherein, the cadmium cobalt precursor and CuCo2O4/TiO2The mass of (2) is 3: (87-96), and mixing the cadmium-cobalt precursor with the cobalt precursor according to the mass ratio of 10: (155-180): (34-45): (46-58): (33-46) reacting the cadmium-cobalt alloy powder, the mercapto-acrylic acid sol, urea, glycerol and polyethylene glycol 600 to obtain the cadmium-cobalt alloy powder;
the mercaptoacrylic acid sol is prepared by reacting mercaptoacrylic acid, glycerol, polyethylene glycol 200, polyethylene glycol 400 and a polyvinyl alcohol aqueous solution with the mass concentration of 10%, wherein the mass ratio of the mercaptoacrylic acid to the glycerol to the polyethylene glycol 200 to the polyethylene glycol 400 to the polyvinyl alcohol aqueous solution with the mass concentration of 10% is 100: (65-80): (32-45): (23-37): (10-25);
CuCo2O4/TiO2the preparation method comprises the following steps: adding copper oxalate, cobalt acetate, acrylamide, ethanol and TiO2And water according to 15: (20-30): (11-20): (65-83): (85-98): (98-115) adding the mixture into a hydrothermal reaction kettle in a mass ratio, reacting for 10 +/-1 h at the temperature of 150 +/-5 ℃, sequentially carrying out reduced pressure distillation, roasting, washing and drying on the obtained product, and grinding to obtain CuCo2O4/TiO2(ii) a The reduced pressure distillation is carried out for 0.5 plus or minus 0.1h under the conditions that the temperature is 105 plus or minus 5 ℃ and the vacuum degree is minus 0.08 plus or minus 0.01 MPa; the roasting is sequentially roasting at 200 +/-5 ℃ for 2 +/-0.1 h, at 300 +/-5 ℃ for 2 +/-0.1 h, at 400 +/-5 ℃ for 2 +/-0.1 h, at 500 +/-5 ℃ for 2 +/-0.1 h, at 600 +/-5 ℃ for 2 +/-0.1 h, and then naturally cooling to room temperature; washing with water for 3 + -1 times, and then washing with ethanol for 3 + -1 times; drying at 70 + -5 deg.C and vacuum degree of-0.06 + -0.01 MPa for 1 + -0.1 h;
cadmium cobalt precursor and CuCo2O4/TiO2According to the mass ratio of 3: (87-96) adding the mixture into a hydrothermal reaction kettle, reacting for 15 +/-1 h at the temperature of 210 +/-10 ℃, roasting, washing and drying the obtained product in sequence, and grinding to obtain the CdCoS2/CuCo2O4/TiO2A photocatalyst.
2. The CdCoS of claim 12/CuCo2O4/TiO2A photocatalyst, characterized in that: the particle size of the cadmium-cobalt alloy powder is 15-30 nm, and the mass ratio of cadmium to cobalt in the cadmium-cobalt alloy powder is 95.7: 4.3.
3. The CdCoS of claim 1 or 22/CuCo2O4/TiO2The preparation method of the photocatalyst is characterized by comprising the following steps: the calcination of the photocatalyst is sequentially carried out for 2 plus or minus 0.1h at 200 plus or minus 5 ℃, 2 plus or minus 0.1h at 300 plus or minus 5 ℃, 2 plus or minus 0.1h at 400 plus or minus 5 ℃ and 2 plus or minus 0.1h at 500 plus or minus 5 ℃ under the protection of nitrogen, and then the photocatalyst is naturally cooled to room temperature; the washing is carried out firstlyWashing with 10% acetic acid water solution for 3 + -1 times, and washing with ethanol for 3 + -1 times; the drying is carried out at 60 + -5 deg.C and vacuum degree of-0.09 + -0.01 MPa for 1 + -0.1 h.
4. The CdCoS of claim 1 or 22/CuCo2O4/TiO2The preparation method of the photocatalyst is characterized by comprising the following steps: the preparation method of the cadmium cobalt precursor comprises the following steps: mixing cadmium-cobalt alloy powder, mercapto-acrylic acid sol, urea, glycerol and polyethylene glycol 600 according to the weight ratio of 10: (155-180): (34-45): (46-58): (33-46) and reacting for 0.5-1 h at the stirring speed of 35-51 r/min and the temperature of 20-29 ℃ to obtain the cadmium-cobalt precursor.
5. The method of claim 3, wherein: the preparation method of the cadmium cobalt precursor comprises the following steps: mixing cadmium-cobalt alloy powder, mercapto-acrylic acid sol, urea, glycerol and polyethylene glycol 600 according to the weight ratio of 10: (155-180): (34-45): (46-58): (33-46) and reacting for 0.5-1 h at the stirring speed of 35-51 r/min and the temperature of 20-29 ℃ to obtain the cadmium-cobalt precursor.
6. The method of claim 4, wherein: the preparation method of the mercapto acrylic acid sol comprises the following steps: mixing mercaptoacrylic acid, glycerol, polyethylene glycol 200, polyethylene glycol 400 and 10% polyvinyl alcohol aqueous solution according to the mass concentration of 100: (65-80): (32-45): (23-37): (10-25) adding the mixture into a reactor according to the mass ratio, and reacting for 0.3-0.9 h under the conditions that the stirring speed is 120-145 r/min and the temperature is 37-53 ℃ to obtain the mercapto acrylic acid sol.
7. The method of claim 5, wherein: the preparation method of the mercapto acrylic acid sol comprises the following steps: mixing mercaptoacrylic acid, glycerol, polyethylene glycol 200, polyethylene glycol 400 and 10% polyvinyl alcohol aqueous solution according to the mass concentration of 100: (65-80): (32-45): (23-37): (10-25) adding the mixture into a reactor according to the mass ratio, and reacting for 0.3-0.9 h under the conditions that the stirring speed is 120-145 r/min and the temperature is 37-53 ℃ to obtain the mercapto acrylic acid sol.
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| CN102085480A (en) * | 2010-12-28 | 2011-06-08 | 湖南理工学院 | Application of semiconductor nano-composite material as visible light photocatalytic bactericide |
| CN103736502A (en) * | 2014-01-08 | 2014-04-23 | 南京工业职业技术学院 | Composite semiconductor photocatalyst and application thereof |
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| CN102085480A (en) * | 2010-12-28 | 2011-06-08 | 湖南理工学院 | Application of semiconductor nano-composite material as visible light photocatalytic bactericide |
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