CN108686681B - graphene/ZnS-MoS with visible light catalytic activity2Nano solid solution photocatalyst - Google Patents
graphene/ZnS-MoS with visible light catalytic activity2Nano solid solution photocatalyst Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 66
- 239000006104 solid solution Substances 0.000 title claims abstract description 52
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 43
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 53
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 41
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 150000003751 zinc Chemical class 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 239000011684 sodium molybdate Substances 0.000 claims description 7
- 235000015393 sodium molybdate Nutrition 0.000 claims description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical group CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 230000031700 light absorption Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 239000005083 Zinc sulfide Substances 0.000 description 5
- 229910052984 zinc sulfide Inorganic materials 0.000 description 5
- 239000010842 industrial wastewater Substances 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
-
- B01J35/39—
-
- 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
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/61—
-
- 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
-
- 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
Abstract
The invention discloses a synthesis method of a graphene/ZnS-MoS 2 nano solid solution photocatalyst with visible light catalytic activity. And then taking inorganic zinc salt, inorganic molybdenum salt and a sulfur source as raw materials, sequentially dissolving the inorganic zinc salt, the inorganic molybdenum salt and the sulfur source into an organic solution, adding a graphene solution prepared in advance, reacting at the temperature of 180-220 ℃, and uniformly attaching a nano solid solution ZnS-MoS2 on the graphene film to form the chemically bonded rGO/ZnS-MoS2 nano solid solution photocatalyst. When the content of graphene is 5-14%, the rGO/ZnS-MoS2 nano solid solution photocatalyst has excellent visible light catalytic capability. The invention is characterized in that the synthesized rGO/ZnS-MoS2 nano solid solution photocatalyst has larger specific surface area, narrower forbidden bandwidth which can be continuously adjusted, can effectively promote the separation and migration of photo-generated electrons and holes, and has stronger light absorption and photocatalytic activity under visible light.
Description
Technical Field
The invention relates to graphene/ZnS-MoS with visible light catalytic activity2A method for preparing a nano solid solution photocatalyst.
Background
In recent years, the rapid development of the industry in China brings serious pollution to industrial wastewater. The industrial wastewater is characterized by complex components, high concentration of refractory organic pollutants, high chromaticity and poor biodegradability, and has negative effects on environmental quality, ecosystem safety and human health. Therefore, how to effectively treat industrial wastewater to reach wastewater discharge standards is an important goal of environmental protection. At present, the industrial wastewater treatment methods mainly comprise an adsorption method, a membrane treatment method, an electrochemical method, an activated sludge method, an ozone oxidation method and a photocatalytic degradation method. The photocatalytic degradation technology is regarded as a promising and sustainable wastewater treatment technology due to the advantages of simple treatment equipment, high efficiency, easy popularization and the like.
Solid solutions refer to a single, homogeneous crystalline solid formed by solute atoms dissolved into the solvent lattice and still retaining the solvent-type alloy phase. The solid solution semiconductor material is a solid solution material having semiconductor properties formed by dissolving some element semiconductors or compound semiconductors, and is also called a mixed crystal semiconductor or an alloy semiconductor. If the ionic radii of the two compounds are similar and the lattice structures of the two compounds are similar, the visible light responding photocatalyst with continuously changed band gaps can be prepared by adjusting the proportion. Sulfide semiconductors have attracted much attention in recent years because of their advantages such as narrow band gaps and high stability. Zinc sulfide (ZnS) is a typical type ii-vi semiconductor material and has received much attention due to its excellent oxidation ability and low secondary pollution. However, ZnS is active only in the ultraviolet region due to its wide direct band gap (3.6eV), and its photocatalytic efficiency is not high enough due to the fast photo-generated electron-hole recombination rate. The construction of a heterojunction with a narrow bandgap semiconductor is an effective way to broaden the visible light absorption and photocatalytic performance of a wide bandgap semiconductor. MoS2As a novel photocatalyst, the method has the characteristics of narrow forbidden band, complex edge structure, large specific surface area, high unsaturated property and the like, and the ZnS-MoS is synthesized2The heterojunction photocatalyst can inhibit the recombination of photo-generated electrons and holes, thereby improving the photocatalytic activity. However, the lattice and band structures of the heterojunction are poorly matched. The semiconductor heterojunction solid solution can adjust the lattice constant of the solid solution and the energy band structure matched with the energy band structure, and is an effective way for avoiding interface stress caused by lattice mismatch. Therefore, the subject is combined into a series of ZnS-MoS2Solid solutions with photocatalytic activity much higher than pure ZnS and MoS2But due to ZnS-MoS2Solid solutions have poor photocatalytic activity and their properties are still not ideal. Thus, for ZnS-MoS2It is essential that the solid solution photocatalyst is modified to improve the photocatalytic efficiency.
The graphene is represented by sp2A two-dimensional (2D) periodic honeycomb lattice structure consisting of hybridized benzene six-membered rings is the most ideal two-dimensional nano material at present. At room temperature the graphene hasCan promote ZnS-MoS in excellent charge carrier, excellent thermal conductivity, high specific surface area, good chemical stability and the like2Separation, transfer and migration of solid solution photo-generated electrons-holes inhibit the recombination of photo carriers; in addition, the graphene can adsorb a large amount of pollutants, provide more and more ideal reaction sites for photocatalytic reaction, and can inhibit ZnS-MoS2The nano particles are agglomerated and uniformly grow on the graphene film, so that the advantages of solid solution and the excellent performance of graphene are combined, and a novel rGO/ZnS-MoS is prepared by attempting2Ternary solid solutions promote charge separation and enhance stability.
Disclosure of Invention
ZnS-MoS2The invention aims to provide a one-step solvothermal method for preparing rGO/ZnS-MoS with visible light catalytic activity aiming at the existing defects that nano particles are large, are tightly contacted, are easy to agglomerate, have small specific surface area, provide few reactive active sites and contain limited pollutant molecules so as to cause low photocatalysis efficiency2The introduction of the nano solid solution photocatalyst can be used as an electron carrier to promote the separation, transfer and migration of photo-generated electrons and holes on one hand, so that the recombination rate of the photo-carrier is inhibited; on the other hand, the addition of the graphene can inhibit ZnS-MoS2Polymerization of nanoparticles to ZnS-MoS2The nano particles can be uniformly grown on the graphene film, and more ideal reaction sites are provided for photocatalytic reaction. Furthermore, such rGO/ZnS-MoS2The nano solid solution photocatalyst has a narrow forbidden band width, a large specific surface area, strong light absorption and photocatalysis capacity under visible light, high light utilization efficiency, and high stability and regeneration capacity.
The invention is realized by the following technical scheme. graphene/ZnS-MoS with visible light catalytic activity2The method of the nano solid solution photocatalyst comprises the following steps:
graphene/ZnS-MoS with visible light catalytic activity2The method of the nano solid solution photocatalyst is characterized by comprising the following steps:
1) firstly, preparing graphene oxide by using an improved Hummers method, then dispersing the graphene oxide in an organic solvent, and carrying out ultrasonic treatment for 30-60min to obtain a uniform solution;
2) dissolving inorganic zinc salt, inorganic molybdenum salt and a sulfur source into an organic solution by taking the inorganic zinc salt, the inorganic molybdenum salt and the sulfur source as raw materials, and adding a graphene solution prepared in advance;
3) transferring the mixed solution into a reaction kettle, and reacting for 24 hours at the temperature of 180 ℃ and 220 ℃;
4) after the reaction is finished, washing and centrifuging the reactant by deionized water and absolute ethyl alcohol for several times respectively, and drying the obtained product in vacuum for 6-24 hours at the temperature of 60-100 ℃ to obtain the rGO/ZnS-MoS with visible light catalytic activity2A nano solid solution photocatalyst.
The inorganic zinc salt is one or more of zinc acetate, zinc chloride, zinc nitrate and zinc sulfate.
The inorganic molybdenum salt is one or more of sodium molybdate, ammonium molybdate and phosphomolybdic acid.
The sulfur source is thioacetamide, thiourea and Na2One or more of S.
The organic solvent is one or more of ethanol, propanol, butanol, N-dimethylformamide, N-dimethylacetamide, ethylene glycol, propylene glycol or butanediol.
The molar ratio of the inorganic zinc salt to the inorganic molybdenum salt is 20: 1-40: 1.
The molar ratio of the inorganic zinc salt to the sulfur source is 1: 2-1: 8.
The graphene and ZnS-MoS2The mass percentage of (B) is 5-14%.
graphene/ZnS-MoS prepared by the invention2The nano solid solution photocatalyst is used for treating wastewater under the irradiation of visible light.
The invention prepares rGO/ZnS-MoS2The advantages of the nano solid solution photocatalyst are:
(1) the rGO/ZnS-MoS prepared by the preparation method of the invention2The nano solid solution photocatalyst has unique surface structure and appearance.
(2) The one-step solvothermal method of the inventionPreparing graphene/ZnS-MoS with visible light catalytic activity2The nano solid solution photocatalyst is fluffy, has larger specific surface area, is narrower, has a continuously adjustable forbidden band width, can effectively separate and transfer photoproduction electrons and holes, has stronger light absorption and photocatalysis capability under visible light, has higher stability and regeneration performance, can efficiently treat actual wastewater under the irradiation of the visible light, and has the removal rate of 74.05 percent.
Drawings
FIG. 1 shows rGO/ZnS-MoS prepared in example 1 of the present invention2Nano solid solution photocatalyst (a) and pure ZnS-MoS2The XRD pattern of the comparative sample (b) shows that rGO/ZnS-MoS2And ZnS-MoS2The X-ray diffraction data are consistent, and the result shows that the load of the graphene does not influence ZnS-MoS2The diffraction peak of the graphene does not appear, which shows that the ordered arrangement structure of the graphene is disturbed due to the modification of the zinc sulfide/molybdenum sulfide on the graphene sheet layer.
FIG. 2 shows rGO/ZnS-MoS prepared in example 1 of the present invention2SEM image showing ZnS-MoS2The nano particles can uniformly grow on the graphene film and form a shape, so that graphene and ZnS-MoS are realized2Efficient bonding between nanoparticles.
FIG. 3 shows rGO/ZnS-MoS prepared in example 1 of the present invention2Nano solid solution photocatalyst (a) and pure ZnS-MoS2The nitrogen adsorption-desorption isotherm of sample (b) showed that rGO/ZnS-MoS2And pure ZnS-MoS2The nitrogen adsorption-desorption isotherms of (A) all belong to the type IV in the IUPAC classification, the H3 hysteresis loop, but rGO/ZnS-MoS2The specific surface area of the solid solution photocatalyst is close to 31.6m2Pure ZnS-MoS/g2Has a specific surface area of 18.7m2/g，rGO/ZnS-MoS2The specific surface area of the nano solid solution photocatalyst is far larger than that of pure ZnS-MoS2Specific surface area of (2).
FIG. 4 shows rGO/ZnS-MoS prepared in example 1 of the present invention2Nano solid solution photocatalyst (a) and pure ZnS-MoS2(b) The curve of photodegradation o-nitrophenol can be known from the figure, rGO-ZnS-MoS2The catalytic activity of the solid solution photocatalyst is higher than that of pure ZnS-MoS2。
FIG. 5 shows rGO/ZnS-MoS prepared in example 1 of the present invention2The curve of the nano solid solution photocatalyst for treating the actual drug wastewater under the irradiation of visible light can be seen from the figure, wherein the curve is rGO/ZnS-MoS2The solid solution photocatalyst can efficiently treat actual drug wastewater, and the removal rate of COD of the actual drug wastewater under visible light is as high as 74.05%.
Detailed Description
The following examples are intended to illustrate the invention but not to further limit the invention.
Example 1
(1) Graphite powder is used as a raw material, graphene oxide is synthesized by a Hummers method, and then 0.06787g of graphene oxide is put into 10mL of N, N-dimethylformamide solution and is subjected to ultrasonic treatment for 30min for later use.
(2) Adding 6.0mmol of zinc acetate, 0.2mmol of sodium molybdate and 13.3mmol of thioacetamide into 40mL of N, N-dimethylformamide solution, stirring until the solution is transparent, and adding the graphene solution.
(3) The solution was transferred to a 100mL autoclave at 210 ℃ for 24 hours.
(4) The reacted sample was centrifuged and washed several times with deionized water and ethanol, and the resulting sample was vacuum dried at 60 ℃ for 12 hours and then ground. The obtained product is rGO/ZnS-MoS2A nano solid solution photocatalyst.
Example 2
(1) Graphite powder is used as a raw material, graphene oxide is synthesized by a Hummers method, and then 0.04936g of graphite oxide is weighed into 10mL of glycol solution, and ultrasonic treatment is carried out for 40min for later use.
(2) Adding 6.0mmol of zinc chloride, 0.2mmol of sodium molybdate and 13.3mmol of thioacetamide into 40mL of glycol solution, stirring until the solution is transparent, and adding the graphene solution.
(3) The solution was transferred to a 100mL autoclave at 200 ℃ for 24 hours.
(4) Centrifuging the reacted sample and washing with deionized water and ethanol for several times to obtain a sampleThe product was dried under vacuum at 60 ℃ for 12 hours and then ground. The obtained product is rGO/ZnS-MoS2A nano solid solution photocatalyst.
Example 3
(1) Graphite powder is used as a raw material, graphene oxide is synthesized by a Hummers method, then 0.06787g of graphene oxide is weighed and dispersed in 10mL of ethanol solution, and ultrasonic treatment is carried out for 60min for standby.
(2) Adding 5.0mmol of zinc nitrate, 0.25mmol of sodium molybdate and 11.5mmol of sodium sulfide into 40mL of ethanol solution, stirring until the solution is transparent, and adding the graphene solution.
(3) The solution was transferred to a 100mL autoclave at 220 ℃ for 24 hours.
(4) The reacted sample was centrifuged and washed several times with deionized water and ethanol, and the resulting sample was vacuum dried at 60 ℃ for 12 hours and then ground. The obtained product is rGO/ZnS-MoS2A nano solid solution photocatalyst.
Example 4
(1) Graphite powder is used as a raw material, graphene oxide is synthesized by a Hummers method, then 0.04936g of graphene oxide is dispersed into 10mL of butanol solution, and ultrasonic treatment is carried out for 30min for standby.
(2) Adding 5.0mmol of zinc nitrate, 0.25mmol of sodium phosphate and 11.5mmol of sodium sulfide into 40mL of butanol solution, stirring until the solution is transparent, and adding the graphene solution.
(3) The solution was transferred to a 100mL autoclave at 200 ℃ for 24 hours.
(4) The reacted sample was centrifuged and washed several times with deionized water and ethanol, and the resulting sample was vacuum dried at 60 ℃ for 12 hours and then ground. The obtained product is rGO/ZnS-MoS2A nano solid solution photocatalyst.
Example 5
(1) Graphite powder is used as a raw material, graphene oxide is synthesized by a Hummers method, then 0.04936g of graphene oxide is weighed and dispersed in 10mL of butanol solution, and ultrasonic treatment is carried out for 40min for standby.
(2) Adding 6.0mmol of zinc nitrate, 0.2mmol of sodium molybdate and 13.3mmol of thiourea into 40mL of butanol solution, stirring until the solution is transparent, and adding the graphene solution.
(3) The solution was transferred to a 100mL autoclave at 220 ℃ for 24 hours.
(4) The reacted sample was centrifuged and washed several times with deionized water and ethanol, and the resulting sample was vacuum dried at 100 ℃ for 8 hours and then ground. The obtained product is rGO/ZnS-MoS2A nano solid solution photocatalyst.
Example 6
(1) Graphite powder is used as a raw material, graphene oxide is synthesized by a Hummers method, then 0.05553g of graphene oxide is dispersed into 10mL of butanol solution, and ultrasonic treatment is carried out for 50min for standby.
(2) Adding 5.0mmol of zinc acetate, 0.14mmol of sodium molybdate and 11mmol of sodium sulfide into 40mL of butanol solution, stirring until the solution is transparent, and adding the graphene solution.
(3) The solution was transferred to a 100mL autoclave at 210 ℃ for 24 hours.
(4) The reacted sample was centrifuged and washed several times with deionized water and ethanol, and the resulting sample was vacuum dried at 100 ℃ for 8 hours and then ground. The obtained product is rGO/ZnS-MoS2A nano solid solution photocatalyst.
Example 7
(1) Graphite powder is used as a raw material, graphene oxide is synthesized by a Hummers method, then 0.05553g of graphene oxide is weighed and dispersed in a 10mLN, N-dimethylformamide solution, and ultrasonic treatment is carried out for 30min for later use.
(2) Adding 6.0mmol of zinc acetate, 0.2mmol of molybdenum phosphate and 13.3mmol of sodium sulfide into 40mL of N, N-dimethylformamide solution, stirring until the solution is transparent, and adding the graphene solution.
(3) The solution was transferred to a 100mL autoclave at 200 ℃ for 24 hours.
(4) The reacted sample was centrifuged and washed several times with deionized water and ethanol, and the resulting sample was vacuum dried at 100 ℃ for 8 hours and then ground. The obtained product is rGO/ZnS-MoS2A nano solid solution photocatalyst.
Example 8
(1) Graphite powder is used as a raw material, graphene oxide is synthesized by a Hummers method, and then 0.04936g of graphene oxide is dispersed into a 10mLN, N-dimethylacetamide solution and subjected to ultrasonic treatment for 40min for later use.
(2) Adding 5.0mmol of zinc sulfate, 0.25mmol of molybdenum phosphate and 11.5mmol of thiourea into 40mL of N, N-dimethylacetamide solution, stirring until the solution is transparent, and adding the graphene solution.
(3) The solution was transferred to a 100mL autoclave at 210 ℃ for 24 hours.
(4) The reacted sample was centrifuged and washed several times with deionized water and ethanol, and the resulting sample was vacuum dried at 100 ℃ for 8 hours and then ground. The obtained product is rGO/ZnS-MoS2A nano solid solution photocatalyst.
Example 9
(1) Graphite powder is used as a raw material, graphene oxide is synthesized by a Hummers method, then 0.05553g of graphene oxide is dispersed into 10mL of propylene glycol solution, and ultrasonic treatment is carried out for 30min for standby.
(2) Adding 6.0mmol of zinc chloride, 0.2mmol of ammonium molybdate and 13.3mmol of thiourea into 40mL of propylene glycol solution, stirring until the solution is transparent, and adding the graphene solution.
(3) The solution was transferred to a 100mL autoclave at 200 ℃ for 24 hours.
(4) The reacted sample was centrifuged and washed several times with deionized water and ethanol, and the resulting sample was vacuum dried at 100 ℃ for 8 hours and then ground. The obtained product is rGO/ZnS-MoS2A nano solid solution photocatalyst.
Without being limited thereto, any changes or substitutions that are not thought of through the inventive work should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
Claims (5)
1. graphene/ZnS-MoS with visible light catalytic activity2The preparation method of the nano solid solution photocatalyst is characterized by comprising the following steps:
firstly, preparing graphene oxide by using an improved Hummers method, then dispersing the graphene oxide in an organic solvent, and carrying out ultrasonic treatment for 30-60min to obtain a uniform solution;
inorganic zinc salt, inorganic molybdenum salt and sulfur source are used as raw materials, wherein the sulfur source is thioacetamide, thiourea and Na2One or more of S, the molar ratio of the inorganic zinc salt to the inorganic molybdenum salt is 20: 1-40: 1, the molar ratio of the inorganic zinc salt to the sulfur source is 1: 2-1: 8,
dissolving the graphene oxide and the graphene oxide into an organic solution, and adding a prepared graphene solution in advance;
finally transferring the mixed solution into a reaction kettle, and reacting for 24 hours at the temperature of 180 ℃ and 220 ℃;
after the reaction is finished, washing and centrifuging the reactant by deionized water and absolute ethyl alcohol for several times respectively, and drying the obtained product in vacuum for 6-24 hours at the temperature of 60-100 ℃ to obtain the graphene/ZnS-MoS with visible light catalytic activity2Nano solid solution photocatalyst in which graphene and ZnS-MoS2The mass percentage of the solid solution is 5-14%.
2. The graphene/ZnS-MoS having visible light catalytic activity according to claim 12The preparation method of the nano solid solution photocatalyst is characterized by comprising the following steps: the inorganic zinc salt is one or more of zinc acetate, zinc chloride, zinc nitrate and zinc sulfate.
3. The graphene/ZnS-MoS having visible light catalytic activity according to claim 12The preparation method of the nano solid solution photocatalyst is characterized by comprising the following steps: the inorganic molybdenum salt is one or more of sodium molybdate, ammonium molybdate and phosphomolybdic acid.
4. The graphene/ZnS-MoS having visible light catalytic activity according to claim 12The preparation method of the nano solid solution photocatalyst is characterized by comprising the following steps: the organic solvent is one or more of ethanol, propanol, butanol, N-dimethylformamide, N-dimethylacetamide, ethylene glycol, propylene glycol or butanediol.
5. The graphene/ZnS-MoS having visible light catalytic activity according to claim 12The preparation method of the nano solid solution photocatalyst is characterized by comprising the following steps: the wastewater treatment is carried out under the irradiation of visible light.
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| CN110052278B (en) * | 2019-06-12 | 2021-05-04 | 河南大学 | ZnS @ C @ MoS with core-shell structure2Preparation method and application of catalyst |
| CN112516987B (en) * | 2020-12-16 | 2021-09-10 | 中南大学 | Use method of catalyst with CeZrK/rGO nano solid solution as main component |
| CN115196669B (en) * | 2022-06-06 | 2024-01-19 | 桂林电子科技大学 | Zinc sulfide-tin sulfide-molybdenum disulfide multielement composite semiconductor material and preparation method and application thereof |
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