CN111715247A - Silver sulfide/cobalt phosphide composite photocatalyst and preparation method thereof - Google Patents
Silver sulfide/cobalt phosphide composite photocatalyst and preparation method thereof Download PDFInfo
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- CN111715247A CN111715247A CN202010563636.2A CN202010563636A CN111715247A CN 111715247 A CN111715247 A CN 111715247A CN 202010563636 A CN202010563636 A CN 202010563636A CN 111715247 A CN111715247 A CN 111715247A
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- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 50
- 229910052946 acanthite Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 18
- 239000010941 cobalt Substances 0.000 title claims abstract description 18
- 229940056910 silver sulfide Drugs 0.000 title claims abstract description 10
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 title claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 27
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 claims abstract description 25
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 20
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 20
- 239000004094 surface-active agent Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000012467 final product Substances 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 10
- 235000005074 zinc chloride Nutrition 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 7
- 229940043267 rhodamine b Drugs 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 4
- 235000019800 disodium phosphate Nutrition 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- PGWMQVQLSMAHHO-UHFFFAOYSA-N sulfanylidenesilver Chemical class [Ag]=S PGWMQVQLSMAHHO-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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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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
- C02F2101/38—Organic compounds containing nitrogen
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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 silver sulfide/cobalt phosphide composite photocatalyst and a preparation method thereof2P, then the obtained Co2Adding P into the mixed solution of ethylenediamine and water containing zinc source compound and sulfur source compound, and performing a second hydrothermal reaction to obtain ZnS/Co2P, then adding the silver nitrate into silver nitrate solution, and reacting at a certain temperature to obtain Ag2S/Co2P, Ag prepared by the above method2S/Co2P composite photocatalyst material, and Ag2Compared with S photocatalyst, the photocatalyst can obviously improve the photocatalytic performance and has the function of treating organic pollutants in wastewaterGood degradation capability.
Description
Technical Field
The invention relates to the field of photocatalytic materials, in particular to a silver sulfide/cobalt phosphide composite photocatalyst and a preparation method thereof.
Background
The increasingly prominent energy crisis and industrialization bring about serious environmental pollution problems, which have important influence on the development of social economy, and the search for the research and development of new equipment, new technology and new production process is an urgent task for solving the current problems. The green, high-efficiency and secondary pollution-free photocatalysis technology becomes one of important means for solving energy and environmental problems for human beings, and has very important practical significance.
Ag2S is taken as a typical narrow-forbidden-band-width semiconductor material, silver sulfide has special response to illumination conditions, silver sulfide quantum dots also show special near-infrared luminescence characteristics, and the semiconductor material has low toxicity and good biocompatibilityHas the characteristics of good application prospect in practical application. But the single use of Ag is found in practical application2S is not very high in photocatalytic performance, researchers compound S with other photocatalysts and form heterojunction with silver sulfide and other photocatalysts to improve the photocatalytic performance of S, such as Ag2S/Ag3VO4，Ag3PO4/Ag2S/g-C3N4And the like to further improve the performance of the photocatalyst. However, the photocatalytic activity is not improved significantly, so that further improvement of Ag is urgently required2The composite photocatalyst of the S photocatalyst improves the degradation capability on organic pollutants and further expands the types of the photocatalysts.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide an Ag alloy for overcoming the above-mentioned shortcomings in the prior art2S/Co2P composite photocatalyst and preparation method thereof, and Ag2S/Co2P composite photocatalyst and Ag2Compared with S photocatalyst, the photocatalyst can obviously improve the photocatalytic performance and has good degradation capability on organic pollutants in wastewater.
The invention adopts the following technical scheme:
ag2S/Co2The preparation method of the P composite photocatalyst comprises the following steps:
(1): dissolving a cobalt source compound, a phosphorus source compound and a surfactant in a certain amount of deionized water in sequence, and stirring to uniformly mix the cobalt source compound, the phosphorus source compound and the surfactant;
(2) transferring the solution obtained in the step 1) into a polytetrafluoroethylene reaction kettle, reacting for 2-5 h at 180-240 ℃, naturally cooling to room temperature, washing and drying the obtained product to obtain a final product Co2P；
(3) Dissolving a zinc source compound and a sulfur source compound in a mixed solution of ethylenediamine and water, and dissolving the Co obtained in the step (2)2Adding P into the mixed solution, and performing hydrothermal reaction at the temperature of 150-2A P composite material;
(4) ZnS/Co obtained in the step (3)2Uniformly mixing the P composite material with a silver nitrate solution, reacting for 4-5 h at 80-110 ℃, filtering, washing and drying to obtain Ag2S/Co2P composite photocatalyst.
Preferably, in the step (1), the cobalt source compound is selected from one or more of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt acetate; the phosphorus source compound is selected from one or more of sodium hypophosphite, sodium hydrogen phosphate, disodium hydrogen phosphate and ammonium hydrogen phosphate; the surfactant is one or more selected from PVP, sodium dodecyl benzene sulfonate and polyethylene glycol-400.
Preferably, in the step (1), the molar ratio of the cobalt source compound to the phosphorus source compound is 1: 13-18, and the addition amount ratio of the cobalt source compound to the surfactant is 1 mmol: 0.05 to 0.2 g.
Preferably, in the step (2), the detergent is ethanol and/or deionized water, the washing times are 2-3 times, and the drying is performed at 50-70 ℃ for 10-14 h.
Preferably, in the step (3), the volume ratio of the ethylenediamine to the water is 13-16: 1; the zinc source compound is selected from one or more of zinc acetate, zinc chloride and zinc nitrate, the sulfur source compound is thiourea, and the molar ratio of the zinc source compound to the sulfur source compound is 1: 2.
Preferably, in the step (4), the molar ratio of the ZnS to the silver nitrate is 1: 1-2; the Ag is2S and the Co2The molar ratio of P is 1: 1-3.
Preferably, the washing is centrifugal washing with dilute hydrochloric acid and deionized water respectively, and the drying is drying at 50-70 ℃ for 10-14 h.
The other technical scheme of the invention is that the Ag prepared based on the preparation method2S/Co2P composite photocatalyst, said Co2P is microspherical, in Co2Ag with sheet structure on P microsphere surface2S。
Another technical scheme of the invention is based on the Ag2S/Co2Application of P composite photocatalyst and photocatalystAg as described above2S/Co2The P composite photocatalyst is used for photocatalytic degradation of organic pollutants in organic wastewater.
Preferably, the organic pollutant is rhodamine B or methyl orange.
The Ag provided by the invention is adopted2S/Co2The P composite photocatalyst and the preparation method thereof have the following technical effects:
(1) the application firstly prepares Co by a hydrothermal method2P microspheres, then Co is added2P is dispersed in a mixed solution of ethylenediamine containing a zinc source and a sulfur source and water, and then subjected to hydrothermal reaction in Co2ZnS nanosheets grow on the surfaces of the P microspheres, and then Ag is formed through ion replacement of Ag and Zn2S nanosheet loaded to Co2The specific surface area of the composite material is increased by the method, so that the contact area of the composite material and the composite material is increased, and the Ag is increased2The photocatalytic performance of the S photocatalyst.
(2) By Ag2S and Co2P is compounded, a heterojunction structure is formed between the P and the P, the separation efficiency of photoproduction electrons and photoproduction holes is accelerated, and the photocatalysis performance is improved.
(3) The preparation method is simple, easy to control and beneficial to industrial production.
In conclusion, the Ag prepared by the invention2S/Co2The P composite photocatalyst has excellent photocatalytic performance, has good degradation capability on organic pollutants in wastewater, and is an ideal material.
Drawings
FIG. 1 is an activity diagram of photodegradation of rhodamine B in example 1 and comparative examples 1-2
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the present invention generally shown may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Ag2S/Co2The preparation method of the P composite photocatalyst comprises the following steps:
(1): 1.5mmol of cobalt chloride, 22.5mmol of sodium hypophosphite and 0.3g of surface active agent PVP are sequentially dissolved in 100mL of deionized water, and the mixture is stirred for 30min to be uniformly mixed;
(2) transferring the solution obtained in the step 1) into a polytetrafluoroethylene reaction kettle, reacting for 4h at 200 ℃, naturally cooling to room temperature, washing the obtained product with deionized water for 3 times, and drying for 12h at 60 ℃ to obtain the final product Co2P；
(3) Dissolving 0.75mmol of zinc chloride and 1.5mmol of thiourea in a mixed solution of 30mL of ethylenediamine and 2mL of water, and adding the Co obtained in the step (2)2P is added into the mixed solution and then undergoes a hydrothermal reaction for 12 hours at 160 ℃ to obtain ZnS/Co2A P composite material;
(4) ZnS/Co obtained in the step (3)2Uniformly mixing the P composite material with 30mL of silver nitrate solution with the concentration of 0.05M, reacting for 4h at 100 ℃, centrifugally filtering, respectively centrifugally washing by using dilute hydrochloric acid and deionized water, and drying for 12h at 70 ℃ to obtain Ag2S/Co2P composite photocatalyst.
Example 2
Ag2S/Co2The preparation method of the P composite photocatalyst comprises the following steps:
(1): dissolving 3mmol of cobalt acetate, 54mmol of sodium hydrogen phosphate and 0.4g of polyethylene glycol-400 in 100mL of deionized water in sequence, and stirring for 40min to mix uniformly;
(2) transferring the solution obtained in the step 1) into a polytetrafluoroethylene reaction kettle, reacting for 5 hours at 180 ℃,naturally cooling to room temperature, washing the obtained product with ethanol for 2 times, and drying at 70 ℃ for 10h to obtain the final product Co2P；
(3) Dissolving 0.5mmol of zinc chloride and 1mmol of thiourea in a mixed solution of 32mL of ethylenediamine and 2mL of water, and adding the Co obtained in the step (2)2P is added into the mixed solution and then undergoes a hydrothermal reaction for 10 hours at 170 ℃ to obtain ZnS/Co2A P composite material;
(4) ZnS/Co obtained in the step (3)2Uniformly mixing the P composite material with 20mL of silver nitrate solution with the concentration of 0.05M, reacting for 4h at 100 ℃, centrifugally filtering, respectively centrifugally washing with dilute hydrochloric acid and deionized water, and drying for 14h at 50 ℃ to obtain Ag2S/Co2P composite photocatalyst.
Example 3
Ag2S/Co2The preparation method of the P composite photocatalyst comprises the following steps:
(1): 1.5mmol of cobalt sulfate, 22.5mmol of sodium hypophosphite and 0.3g of surface active agent PVP are sequentially dissolved in 100mL of deionized water, and the mixture is stirred for 30min to be uniformly mixed;
(2) transferring the solution obtained in the step 1) into a polytetrafluoroethylene reaction kettle, reacting for 4h at 200 ℃, naturally cooling to room temperature, washing the obtained product with deionized water for 3 times, and drying for 12h at 60 ℃ to obtain the final product Co2P；
(3) Dissolving 0.75mmol of zinc chloride and 1.5mmol of thiourea in a mixed solution of 30mL of ethylenediamine and 2mL of water, and adding the Co obtained in the step (2)2P is added into the mixed solution and then undergoes a hydrothermal reaction for 12 hours at 160 ℃ to obtain ZnS/Co2A P composite material;
(4) ZnS/Co obtained in the step (3)2Uniformly mixing the P composite material with 30mL of silver nitrate solution with the concentration of 0.05M, reacting for 4h at 100 ℃, centrifugally filtering, respectively centrifugally washing by using dilute hydrochloric acid and deionized water, and drying for 12h at 70 ℃ to obtain Ag2S/Co2P composite photocatalyst.
Example 4
Ag2S/Co2Of P-type composite photocatalystThe preparation method comprises the following steps:
(1): 1.5mmol of cobalt nitrate, 22.5mmol of sodium hypophosphite and 0.3g of surface active agent PVP are sequentially dissolved in 100mL of deionized water, and the mixture is stirred for 30min to be uniformly mixed;
(2) transferring the solution obtained in the step 1) into a polytetrafluoroethylene reaction kettle, reacting for 4h at 200 ℃, naturally cooling to room temperature, washing the obtained product with deionized water for 3 times, and drying for 12h at 60 ℃ to obtain the final product Co2P；
(3) Dissolving 0.75mmol of zinc chloride and 1.5mmol of thiourea in a mixed solution of 30mL of ethylenediamine and 2mL of water, and adding the Co obtained in the step (2)2P is added into the mixed solution and then undergoes a hydrothermal reaction for 12 hours at 160 ℃ to obtain ZnS/Co2A P composite material;
(4) ZnS/Co obtained in the step (3)2Uniformly mixing the P composite material with 30mL of silver nitrate solution with the concentration of 0.05M, reacting for 4h at 100 ℃, centrifugally filtering, respectively centrifugally washing by using dilute hydrochloric acid and deionized water, and drying for 12h at 70 ℃ to obtain Ag2S/Co2P composite photocatalyst.
Example 5
Ag2S/Co2The preparation method of the P composite photocatalyst comprises the following steps:
(1): 1.5mmol of cobalt acetate, 22.5mmol of sodium hypophosphite and 0.3g of surface active agent PVP are sequentially dissolved in 100mL of deionized water, and the mixture is stirred for 30min to be uniformly mixed;
(2) transferring the solution obtained in the step 1) into a polytetrafluoroethylene reaction kettle, reacting for 4h at 200 ℃, naturally cooling to room temperature, washing the obtained product with deionized water for 3 times, and drying for 12h at 60 ℃ to obtain the final product Co2P；
(3) Dissolving 0.75mmol of zinc chloride and 1.5mmol of thiourea in a mixed solution of 30mL of ethylenediamine and 2mL of water, and adding the Co obtained in the step (2)2P is added into the mixed solution and then undergoes a hydrothermal reaction for 12 hours at 160 ℃ to obtain ZnS/Co2A P composite material;
(4) ZnS/Co obtained in the step (3)2P composite and 30mL concentration ofMixing 0.05M silver nitrate solution, reacting at 100 deg.C for 4 hr, centrifuging, filtering, washing with dilute hydrochloric acid and deionized water, and drying at 70 deg.C for 12 hr to obtain Ag2S/Co2P composite photocatalyst.
Example 6
Ag2S/Co2The preparation method of the P composite photocatalyst comprises the following steps:
(1): 1.5mmol of cobalt chloride, 22.5mmol of sodium hydrogen phosphate and 0.3g of surface active agent PVP are sequentially dissolved in 100mL of deionized water, and the mixture is stirred for 30min to be uniformly mixed;
(2) transferring the solution obtained in the step 1) into a polytetrafluoroethylene reaction kettle, reacting for 4h at 200 ℃, naturally cooling to room temperature, washing the obtained product with deionized water for 3 times, and drying for 12h at 60 ℃ to obtain the final product Co2P；
(3) Dissolving 0.75mmol of zinc chloride and 1.5mmol of thiourea in a mixed solution of 30mL of ethylenediamine and 2mL of water, and adding the Co obtained in the step (2)2P is added into the mixed solution and then undergoes a hydrothermal reaction for 12 hours at 160 ℃ to obtain ZnS/Co2A P composite material;
(4) ZnS/Co obtained in the step (3)2Uniformly mixing the P composite material with 30mL of silver nitrate solution with the concentration of 0.05M, reacting for 4h at 100 ℃, centrifugally filtering, respectively centrifugally washing by using dilute hydrochloric acid and deionized water, and drying for 12h at 70 ℃ to obtain Ag2S/Co2P composite photocatalyst.
Example 7
Ag2S/Co2The preparation method of the P composite photocatalyst comprises the following steps:
(1): 1.5mmol of cobalt chloride, 22.5mmol of disodium hydrogen phosphate and 0.3g of surface active agent PVP are sequentially dissolved in 100mL of deionized water, and the mixture is stirred for 30min to be uniformly mixed;
(2) transferring the solution obtained in the step 1) into a polytetrafluoroethylene reaction kettle, reacting for 4h at 200 ℃, naturally cooling to room temperature, washing the obtained product with deionized water for 3 times, and drying for 12h at 60 ℃ to obtain the final product Co2P；
(3) Dissolving 0.75mmol of zinc chloride and 1.5mmol of thiourea in a mixed solution of 30mL of ethylenediamine and 2mL of water, and adding the Co obtained in the step (2)2P is added into the mixed solution and then undergoes a hydrothermal reaction for 12 hours at 160 ℃ to obtain ZnS/Co2A P composite material;
(4) ZnS/Co obtained in the step (3)2Uniformly mixing the P composite material with 30mL of silver nitrate solution with the concentration of 0.05M, reacting for 4h at 100 ℃, centrifugally filtering, respectively centrifugally washing by using dilute hydrochloric acid and deionized water, and drying for 12h at 70 ℃ to obtain Ag2S/Co2P composite photocatalyst.
Example 8
Ag2S/Co2The preparation method of the P composite photocatalyst comprises the following steps:
(1): 1.5mmol of cobalt chloride, 22.5mmol of ammonium hydrogen phosphate and 0.3g of surface active agent PVP are sequentially dissolved in 100mL of deionized water, and the mixture is stirred for 30min to be uniformly mixed;
(2) transferring the solution obtained in the step 1) into a polytetrafluoroethylene reaction kettle, reacting for 4h at 200 ℃, naturally cooling to room temperature, washing the obtained product with deionized water for 3 times, and drying for 12h at 60 ℃ to obtain the final product Co2P；
(3) Dissolving 0.75mmol of zinc chloride and 1.5mmol of thiourea in a mixed solution of 30mL of ethylenediamine and 2mL of water, and adding the Co obtained in the step (2)2P is added into the mixed solution and then undergoes a hydrothermal reaction for 12 hours at 160 ℃ to obtain ZnS/Co2A P composite material;
(4) ZnS/Co obtained in the step (3)2Uniformly mixing the P composite material with 30mL of silver nitrate solution with the concentration of 0.05M, reacting for 4h at 100 ℃, centrifugally filtering, respectively centrifugally washing by using dilute hydrochloric acid and deionized water, and drying for 12h at 70 ℃ to obtain Ag2S/Co2P composite photocatalyst.
The photocatalysts of examples 1 to 8 were used in photocatalytic degradation experiments. The specific method comprises the following steps:
adding 20mg of photocatalyst into the rhodamine B aqueous solution (the concentration is 10)-5M), stirring for 20min in the dark, and then stirring under a xenon lamp(350W) stirring under irradiation, taking out 5ml of solution at intervals, centrifuging, taking supernatant fluid to test the photocatalytic performance of the solution, pouring the taken out solution back after the test is finished, and repeatedly testing until the color of the rhodamine B fades and no characteristic peak of the rhodamine B exists.
Specific test results are shown in table 1:
comparative example 1
Preparation of Co alone, as in example 12P。
Comparative example 2.
Preparation of only Ag, the same preparation method and conditions as in example 12S。
Specific photodegradation experiments for example 1 and comparative examples 1-2 were as follows:
adding 20mg of photocatalyst into the rhodamine B aqueous solution (the concentration is 10)-5M), stirring for 20min under the dark condition, then stirring under the irradiation of a xenon lamp (350W), taking out 5ml of solution at intervals, centrifuging, taking supernatant, and testing the photocatalytic performance, wherein the specific test result is shown in figure 1.
As can be seen from the attached figure 1, the Ag prepared by the invention2S/Co2The P composite photocatalyst has excellent photocatalytic performance and good degradation capability on organic pollutants in wastewater, and the comparison between the example 1 and the comparative examples 1-2 shows that Ag is used2S and Co2P-recombination can now increase Ag2Photocatalytic property of S, and Ag can be seen2S and Co2P has a synergistic effect, and the performance of the photocatalyst is obviously improved due to the synergistic effect of the two.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a silver sulfide/cobalt phosphide composite photocatalyst is characterized by comprising the following steps: the method comprises the following steps:
(1): dissolving a cobalt source compound, a phosphorus source compound and a surfactant in a certain amount of deionized water in sequence, and stirring to uniformly mix the cobalt source compound, the phosphorus source compound and the surfactant;
(2) transferring the solution obtained in the step 1) into a polytetrafluoroethylene reaction kettle, reacting for 2-5 h at 180-240 ℃, naturally cooling to room temperature, washing and drying the obtained product to obtain a final product Co2P；
(3) Dissolving a zinc source compound and a sulfur source compound in a mixed solution of ethylenediamine and water, and dissolving the Co obtained in the step (2)2Adding P into the mixed solution, and performing hydrothermal reaction at the temperature of 150-2A P composite material;
(4) ZnS/Co obtained in the step (3)2Uniformly mixing the P composite material with a silver nitrate solution, reacting for 4-5 h at 80-110 ℃, filtering, washing and drying to obtain Ag2S/Co2P composite photocatalyst.
2. The method of claim 1, wherein: in the step (1), the cobalt source compound is selected from one or more of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt acetate; the phosphorus source compound is selected from one or more of sodium hypophosphite, sodium hydrogen phosphate, disodium hydrogen phosphate and ammonium hydrogen phosphate; the surfactant is one or more selected from PVP, sodium dodecyl benzene sulfonate and polyethylene glycol-400.
3. The production method according to claim 1 or 2, characterized in that: the molar ratio of the cobalt source compound to the phosphorus source compound in the step (1) is 1: 13-18, and the addition ratio of the cobalt source compound to the surfactant is 1 mmol: 0.05 to 0.2 g.
4. The production method according to claim 1 or 2, characterized in that: in the step (2), the detergent is ethanol and/or deionized water, the washing times are 2-3 times, and the drying is performed at 50-70 ℃ for 10-14 h.
5. The method of claim 1, wherein: in the step (3), the volume ratio of the ethylenediamine to the water is 13-16: 1; the zinc source compound is selected from one or more of zinc acetate, zinc chloride and zinc nitrate, the sulfur source compound is thiourea, and the molar ratio of the zinc source compound to the sulfur source compound is 1: 2.
6. The method of claim 1, wherein: in the step (4), the molar ratio of the ZnS to the silver nitrate is 1: 1-2; the Ag is2S and the Co2The molar ratio of P is 1: 1-3.
7. The method of claim 1, wherein: the washing is centrifugal washing by dilute hydrochloric acid and deionized water respectively, and the drying is drying for 10-14 h at 50-70 ℃.
8. The silver sulfide/cobalt phosphide composite photocatalyst prepared by the preparation method according to any one of claims 1 to 7, which is characterized in that: the Co2P is microspherical, in Co2Ag with nano-sheet structure on surface of P microsphere2S。
9. The use of the silver sulfide/cobalt phosphide composite photocatalyst as defined in claim 8, wherein: the silver sulfide/cobalt phosphide composite photocatalyst is used for photocatalytic degradation of organic pollutants in organic wastewater.
10. Use according to claim 9, characterized in that: the organic pollutant is rhodamine B or methyl orange.
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