CN115608388B - Shell-core Cs 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalyst, preparation method and application thereof - Google Patents
Shell-core Cs 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalyst, preparation method and application thereof Download PDFInfo
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- CN115608388B CN115608388B CN202211386935.9A CN202211386935A CN115608388B CN 115608388 B CN115608388 B CN 115608388B CN 202211386935 A CN202211386935 A CN 202211386935A CN 115608388 B CN115608388 B CN 115608388B
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- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000008367 deionised water Substances 0.000 claims abstract description 44
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 20
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910000024 caesium carbonate Inorganic materials 0.000 claims abstract description 15
- 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 abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 238000006731 degradation reaction Methods 0.000 claims abstract description 10
- 230000015556 catabolic process Effects 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000011978 dissolution method Methods 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 239000011258 core-shell material Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims description 14
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 14
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 14
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 14
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 231100000719 pollutant Toxicity 0.000 claims description 4
- 238000006303 photolysis reaction Methods 0.000 claims description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- -1 cr (VI) Chemical compound 0.000 abstract description 11
- 239000004098 Tetracycline Substances 0.000 abstract description 10
- 229960002180 tetracycline Drugs 0.000 abstract description 10
- 229930101283 tetracycline Natural products 0.000 abstract description 10
- 235000019364 tetracycline Nutrition 0.000 abstract description 10
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 abstract description 7
- 229960000623 carbamazepine Drugs 0.000 abstract description 7
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 abstract description 7
- 229960001180 norfloxacin Drugs 0.000 abstract description 7
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 abstract description 4
- 150000003522 tetracyclines Chemical class 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 15
- 239000007787 solid Substances 0.000 description 9
- 238000011049 filling Methods 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
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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
- 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
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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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
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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
- C02F2101/36—Organic compounds containing halogen
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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
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a shell-core Cs 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalyst, preparation method and application thereof, and sheet MnIn 2 S 4 Assembled to spherical Cs in petal form 3 PMo 12 O 40 The outer surface forms a shell-core structure. The preparation method comprises the following steps: sheet-like MnIn 2 S 4 Sequentially adding phosphomolybdic acid and cesium carbonate into deionized water, stirring uniformly, adopting a precipitation dissolution method, washing and drying. The composite photocatalyst obtained by the invention has simple preparation process, stable property, good dispersibility and strong adsorption capacity, and can be used for lightAnd (3) hydrogen production by water decomposition and photocatalytic degradation. The hydrogen production amount of the composite photocatalyst is improved; the photocatalytic degradation effect can effectively degrade Tetracycline (TC), potassium dichromate (Cr (VI)), norfloxacin (NFX) and Carbamazepine (CBZ), and the degradation rate of TC, cr (VI), NFX and CBZ is up to 80-98% within 1 h.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a shell-core Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst, a preparation method and application thereof.
Background
The photocatalytic semiconductor material can convert solar energy into chemical energy, and is widely used in the aspects of photocatalytic water splitting hydrogen production, photocatalytic degradation and the like at present, and the photocatalytic technology is used for researching how to better utilize the photocatalytic semiconductor material. Polyoxometalates (Cs) 3 PMo 12 O 40 ) Has the advantages of low price, easy synthesis, good stability, large specific surface area, etc. In addition, cs 3 PMo 12 O 40 As a class of semiconductor polyacids, there are many advantages over other inorganic semiconductor materials. But Cs 3 PMo 12 O 40 There are also problems that the photoresponse range is narrow, the visible light cannot be fully absorbed and utilized, the quantum efficiency is too low, the recombination rate of photo-generated electrons and photo-generated holes is high, and the like.
As a semiconductor with a narrow band gap, the S-in-Mn has good visible light response capability. However, due to the narrow forbidden band, the photo-generated electron-hole pair recombination rate is high, so that the photocatalytic performance is limited.
Disclosure of Invention
The invention aims to provide a spherical Cs 3 PMo 12 O 40 And sheet-like MnIn 2 S 4 The composite shell-core photocatalyst and its preparation and application aim at solving the problems in the prior art pointed out in the background art. In order to achieve the above purpose, the invention adopts the following technical scheme:
shell-core Cs 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalyst, sheet MnIn 2 S 4 Assembled to spherical Cs in petal form 3 PMo 12 O 40 The outer surface forms a shell-core structure.
Preferably, the sheet-like MnIn 2 S 4 Spherical Cs with diameter of 5-25nm 3 PMo 12 O 40 The diameter is 200-250nm, and the core-shell Cs 3 PMo 12 O 40 /MnIn 2 S 4 The diameter of the composite photocatalyst is 400-700nm, wherein Cs 3 PMo 12 O 40 With MnIn 2 S 4 The mass ratio of (2) is 7-11:1.
Composite modified shell-core Cs 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst has excellent redox ability, and simultaneously has more positive VB potential and more negative CB potential, which is very advantageous for improving photocatalytic performance. In addition, the shell-core type composite photocatalyst has more active sites in structure, has larger specific surface area than common 0D, 1D and 2D composite catalysts, is more beneficial to the occurrence of degradation reaction and promotes the reaction efficiency.
And, core-shell Cs 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst has good visible light absorptivity, accelerates the separation of photon-generated carriers, increases active sites and improves the photocatalytic activity.
The above-mentioned shell-core Cs 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst comprises the following steps: sheet-like MnIn 2 S 4 Sequentially adding phosphomolybdic acid, cesium carbonate and deionized water, stirring uniformly, adopting a precipitation dissolution method, washing and drying to obtain spherical Cs 3 PMo 12 O 40 And sheet-like MnIn 2 S 4 Composite shell-core photocatalyst.
Preferably, the sheet-like MnIn 2 S 4 The preparation method of (2) comprises the following steps: sequentially adding manganese acetate tetrahydrate, indium chloride and thioacetamide into deionized water, uniformly stirring, and obtaining MnIn by adopting a hydrothermal method 2 S 4 Washing and drying the suspension to obtain sheet MnIn 2 S 4 。
Preferably, the molar ratio of the manganese acetate tetrahydrate, the indium chloride and the thioacetamide is (0.1-2): 1-4): 1-10.
Preferably, the hydrothermal method specifically comprises the following steps: sequentially adding manganese acetate tetrahydrate, indium chloride and thioacetamide into deionized water, uniformly stirring, placing in an oven, controlling the temperature to rise to 180-260 ℃ at the heating rate of 1-5 ℃/min, and carrying out heat preservation and calcination for 18-36h.
Preferably, the MnIn 2 S 4 The suspension is stirred for 4 to 6 hours at room temperature, then washed by deionized water for 6 to 10 times, and dried for 10 to 12 hours in an oven at 60 to 80 ℃.
Preferably, n (Cs) in cesium carbonate and phosphomolybdic acid is n (P) =3:1 to 6:1.
Preferably, the precipitation dissolution method specifically comprises: sheet-like MnIn 2 S 4 Sequentially adding phosphomolybdic acid and cesium carbonate into deionized water, stirring uniformly, centrifuging the obtained solution in a centrifuge tube to obtain a product, washing with deionized water for 6-10 times, and drying in an oven at 60-80 ℃ for 10-12 h.
The above-mentioned shell-core Cs 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst can be used for preparing hydrogen by photocatalytic water splitting or degrading pollutants in water.
The invention has the beneficial effects that:
the invention relates to a shell-core Cs 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst has the characteristics of stable structure, strong dispersibility and strong adsorption capacity, and is beneficial to smooth transmission of electrons; the preparation method is simple and low in cost, and the prepared composite photocatalyst can effectively degrade Tetracycline (TC), potassium dichromate (Cr (VI)), norfloxacin (NFX) and Carbamazepine (CBZ) in sewage, and can degrade TC, cr (VI), NFX and CBZ by 80-98% within 1 h. Meanwhile, under the irradiation of visible light, the device has the property of producing hydrogen by photolysis of water. In addition, the core-shell Cs of the present invention 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst also has the characteristics of low toxicity, simple operation and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 shows Cs obtained in example 1 of the present invention 3 PMo 12 O 40 /MnIn 2 S 4 Is a XRD pattern of (C).
FIG. 2 shows Cs at various ratios 3 PMo 12 O 40 /MnIn 2 S 4 Is a scanning electron microscope image of (1).
FIG. 3 shows Cs produced in comparative example 1 of the present invention 3 PMo 12 O 40 /MnIn 2 S 4 Is a scanning electron microscope image of (1).
FIG. 4 shows Cs at various ratios 3 PMo 12 O 40 /MnIn 2 S 4 Is a photocatalytic hydrogen production amount.
FIG. 5 shows Cs obtained in example 1 of the present invention 3 PMo 12 O 40 /MnIn 2 S 4 Is used for producing hydrogen by circulating photocatalysis.
FIG. 6 shows Cs obtained in example 1 of the present invention 3 PMo 12 O 40 /MnIn 2 S 4 Degradation rate for different contaminants.
FIG. 7 shows Cs obtained in example 1 of the present invention 3 PMo 12 O 40 /MnIn 2 S 4 Is a degradation cycle chart of (2).
FIG. 8 is a graph of Cs at various ratios 3 PMo 12 O 40 /MnIn 2 S 4 TC degradation rate plot of (2).
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Core-shell Cs 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst comprises the following steps:
respectively taking manganese acetate tetrahydrate (1 mmol), indium chloride (1 mmol) and thioacetamide (1 mmol), mixing and stirring uniformly in a beaker (deionized water 50 ml), transferring into a stainless steel autoclave lined with polytetrafluoroethylene, placing into an oven, heating to 240 ℃ at a heating rate of 5 ℃/min, calcining for 24h, washing and drying the suspension to obtain sheet MnIn 2 S 4 A solid. 100mg of sheet MnIn was weighed 2 S 4 Mixing cesium carbonate 1g and phosphomolybdic acid 2g in a beaker (deionized water 50 ml), stirring uniformly, centrifuging the obtained solution in a centrifuge tube to obtain a product, washing with deionized water for 8 times (deionized water filling amount is 50 ml), and drying in an oven at 60 ℃ for 12h to obtain Cs 3 PMo 12 O 40 ：MnIn 2 S 4 Cs with a mass ratio of 9 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst.
Example 2
Core-shell Cs 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst comprises the following steps:
respectively taking manganese acetate tetrahydrate (1 mmol), indium chloride (2 mmol) and thioacetamide (5 mmol), mixing and stirring uniformly in a beaker (deionized water 50 ml), transferring into a stainless steel autoclave lined with polytetrafluoroethylene, placing into an oven, heating to 180 ℃ at a heating rate of 3 ℃/min, calcining for 18h, washing and drying the suspension to obtain sheet MnIn 2 S 4 A solid. 100mg of sheet MnIn was weighed 2 S 4 Mixing cesium carbonate 1g and phosphomolybdic acid 2g in beaker (deionized water 80 ml), stirring, centrifuging the obtained solution in centrifuge tube to obtain product, washing with deionized water 6 times (deionized water filling amount is 60 ml), drying in oven at 60deg.C for 10 hr to obtain Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst.
Example 3
Core-shell Cs 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst comprises the following steps:
respectively taking manganese acetate tetrahydrate (1 mmol), indium chloride (2 mmol) and thioacetamide (5 mmol), mixing and stirring uniformly in a beaker (deionized water 50 ml), transferring into a stainless steel autoclave lined with polytetrafluoroethylene, placing into an oven, heating to 240 ℃ at a heating rate of 1 ℃/min, calcining for 20h, washing and drying the suspension to obtain sheet MnIn 2 S 4 A solid. 100mg of sheet MnIn was weighed 2 S 4 Mixing cesium carbonate 2g and phosphomolybdic acid 1g in beaker (deionized water 50 ml), stirring, centrifuging the obtained solution in centrifuge tube to obtain product, washing with deionized water 6 times (deionized water filling amount is 50 ml), drying in oven at 80deg.C for 10 hr to obtain Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst.
Example 4
Core-shell Cs 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst comprises the following steps: respectively taking manganese acetate tetrahydrate (2 mmol), indium chloride (1 mmol) and thioacetamide (4 mmol), mixing and stirring uniformly in a beaker (deionized water 50 ml), transferring into a stainless steel autoclave lined with polytetrafluoroethylene, placing into an oven, heating to 190 ℃ at a heating rate of 5 ℃/min, calcining for 30h, washing and drying the suspension to obtain sheet MnIn 2 S 4 A solid. 100mg of sheet MnIn was weighed 2 S 4 Mixing cesium carbonate 2g and phosphomolybdic acid 3g in beaker (deionized water 50 ml), centrifuging the obtained solution in centrifuge tube to obtain product, washing with deionized water 7 times (deionized water filling amount is 60 ml), drying in oven at 80deg.C for 12 hr to obtain Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst.
Example 5
Core-shell Cs 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst comprises the following steps: separately taking manganese acetate tetrahydrate (2 mmol) and chloridizingIndium (3 mmol) and thioacetamide (6 mmol) are mixed and stirred uniformly in a beaker (50 ml of deionized water), then transferred into a stainless steel autoclave lined with polytetrafluoroethylene, placed in an oven to be calcined for 28 hours at the temperature rising rate of 4 ℃/min to 240 ℃, and the suspension is washed and dried to obtain sheet MnIn 2 S 4 A solid. 100mg of sheet MnIn was weighed 2 S 4 Mixing cesium carbonate 1g and phosphomolybdic acid 2g in beaker (deionized water 100 ml), centrifuging the obtained solution in centrifuge tube to obtain product, washing with deionized water 6 times (deionized water filling amount 40 ml), and drying in oven at 70deg.C for 10 hr to obtain Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst.
Example 6
Core-shell Cs 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst comprises the following steps: respectively taking manganese acetate tetrahydrate (1 mmol), indium chloride (3 mmol) and thioacetamide (7 mmol), mixing and stirring uniformly in a beaker (deionized water 50 ml), transferring into a stainless steel autoclave lined with polytetrafluoroethylene, placing into an oven, heating to 200 ℃ at a heating rate of 3 ℃/min, calcining for 36h, washing and drying the suspension to obtain sheet MnIn 2 S 4 A solid. 100mg of sheet MnIn was weighed 2 S 4 Mixing cesium carbonate 3g and phosphomolybdic acid 1g in beaker (deionized water 100 ml), centrifuging the obtained solution in centrifuge tube to obtain product, washing with deionized water 6 times (deionized water filling amount is 30 ml), drying in oven at 70deg.C for 11 hr to obtain Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst.
Comparative example 1
Core-shell Cs 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst comprises the following steps:
respectively taking manganese acetate tetrahydrate (2 mmol), indium chloride (1 mmol) and thioacetamide (3 mmol) in a beaker (deionized water 50 ml), mixing and stirring uniformly, transferring into a stainless steel autoclave lined with polytetrafluoroethylene, and placing in an oven to rise at a heating rate of 2 ℃/minCalcining at 200 ℃ for 20 hours, washing and drying the suspension to obtain sheet MnIn 2 S 4 A solid. 100mg of sheet MnIn was weighed 2 S 4 Mixing cesium carbonate 1g and phosphomolybdic acid 2g in beaker (deionized water 50 ml), centrifuging the obtained solution in centrifuge tube to obtain product, washing with deionized water 7 times (deionized water filling amount is 70 ml), drying in oven at 70deg.C for 11h to obtain Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst.
FIG. 3 shows Cs prepared in comparative example 1 3 PMo 12 O 40 /MnIn 2 S 4 Scanning electron microscope image of the composite photocatalyst, from the scanning electron microscope image, it can be seen that the sheet-shaped MnIn prepared in comparative example 1 2 S 4 The solid size is small, petal-shaped morphology is not formed, the active sites are few, and the catalytic performance is poor.
Comparative example 2
Core-shell Cs 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst comprises the following steps:
respectively taking manganese acetate tetrahydrate (1 mmol), indium chloride (2 mmol) and thioacetamide (3 mmol), mixing and stirring uniformly in a beaker (deionized water 50 ml), transferring into a stainless steel autoclave lined with polytetrafluoroethylene, placing into an oven, heating to 220 ℃ at a heating rate of 5 ℃/min, calcining for 22h, washing and drying the suspension to obtain sheet MnIn 2 S 4 A solid. 100mg of sheet MnIn was weighed 2 S 4 Mixing cesium carbonate 1g and phosphomolybdic acid 0.4g in a beaker (deionized water 50 ml), stirring, centrifuging the obtained solution in a centrifuge tube to obtain a product, washing with deionized water for 6 times (deionized water filling amount is 50 ml), and drying in an oven at 70deg.C for 10h to obtain Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst.
Application example 1
Core-shell Cs 3 PMo 12 O 40 /MnIn 2 S 4 Application example of composite photocatalyst:
cs prepared by example 1 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalyst and preparation of Cs 3 PMo 12 O 40 With MnIn 2 S 4 The mass ratio of 7 to 11 is 7, and simultaneously, single Cs is adopted 3 PMo 12 O 40 And MnIn 2 S 4 As a control of photocatalytic performance for each mass ratio, an optimum ratio of 9 was obtained by the control. 20mg of each photocatalyst was weighed and added to 50ml of a 15% triethanolamine solution, and after a reaction time of 1 hour, the amount of hydrogen produced was measured by gas chromatography, with a 420nm filter. The hydrogen production performance is calculated by a formula, and the result is shown in figure 4. Cs with mass ratio of 9 3 PMo 12 O 40 /MnIn 2 S 4 The catalyst was hydrolyzed 5 times in a cycle, and the stability was measured, and the results are shown in FIG. 5.
As can be seen in FIG. 4, the Cs prepared in example 1 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst has excellent photocatalytic water splitting performance under the irradiation of visible light, wherein the hydrogen production performance of the composite photocatalyst with the mass ratio of 9 is as high as 19.26 mu mol.
As can be seen in FIG. 5, the Cs prepared in example 1 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst has good photocatalytic water splitting stability and still has excellent photocatalytic water splitting hydrogen production performance after 5 times of circulation.
Application example 2
Core-shell Cs 3 PMo 12 O 40 /MnIn 2 S 4 Application example of composite photocatalyst:
cs prepared in example 1 was selected 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst is prepared by weighing 20mg of the catalyst, placing the catalyst in 20ml of 40ppm pollutant solution, irradiating the solution for 1h by using a 300W xenon lamp after the desorption equilibrium is reached in the dark treatment, measuring the solution absorption value by ultraviolet, and calculating the degradation rate by a formula, wherein the result is shown in figure 6. The catalyst was cycled for 4 times to determine its stability, and the results are shown in FIG. 7.
FIG. 6 shows the Cs prepared in example 1 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst can degrade 80-98% of pollutants after 1h, and has high degradation rate and quick reaction time, wherein the concentrations of TC, cr (VI), NFX and CBZ solutions are respectively 20ppm, 80ppm, 30ppm and 20ppm.
FIG. 7 shows the Cs prepared in example 1 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst has good photocatalytic degradation stability and still has excellent photocatalytic degradation performance after 4 times of circulation.
Cs prepared according to the above method using examples 2-6 and comparative examples 1-2 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst was used for the degradation of Tetracycline (TC), and the degradation results for 1 hour are shown in Table 1.
TABLE 1
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. Shell-core Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst characterized by a sheet-like MnIn 2 S 4 Assembled to spherical Cs in petal form 3 PMo 12 O 40 The outer surface forms a shell-core structure;
the sheet-shaped MnIn 2 S 4 Spherical Cs with diameter of 5-25nm 3 PMo 12 O 40 The diameter is 200-250nm, and the core-shell Cs 3 PMo 12 O 40 /MnIn 2 S 4 The diameter of the composite photocatalyst is 400-700nm, wherein Cs 3 PMo 12 O 40 With MnIn 2 S 4 The mass ratio of (2) is 7-11:1.
2. A core-shell Cs according to claim 1 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst is characterized by comprising the following steps: sheet-like MnIn 2 S 4 Sequentially adding phosphomolybdic acid, cesium carbonate and deionized water, stirring uniformly, adopting a precipitation dissolution method, washing and drying to obtain spherical Cs 3 PMo 12 O 40 And sheet-like MnIn 2 S 4 Composite shell-core photocatalyst.
3. A core-shell Cs according to claim 2 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that the sheet MnIn 2 S 4 The preparation method of (2) comprises the following steps: sequentially adding manganese acetate tetrahydrate, indium chloride and thioacetamide into deionized water, uniformly stirring, and obtaining MnIn by adopting a hydrothermal method 2 S 4 Washing and drying the suspension to obtain sheet MnIn 2 S 4 。
4. A core-shell Cs according to claim 3 3 PMo 12 O 40 /MnIn 2 S 4 The molar ratio of the manganese acetate tetrahydrate, the indium chloride and the thioacetamide is (0.1-2): 1-4): 1-10.
5. A core-shell Cs according to claim 3 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that the hydrothermal method specifically comprises the following steps: sequentially adding manganese acetate tetrahydrate, indium chloride and thioacetamide into deionized water, stirring uniformly, placing into an oven, controlling the temperature to rise to 180-260 ℃ at the heating rate of 1-5 ℃/min, and carrying out heat preservation and calcination for 18-36h.
6. A core-shell Cs according to claim 3 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that the MnIn 2 S 4 The suspension is stirred for 4 to 6 hours at room temperature, then washed by deionized water for 6 to 10 times, and then placed in an oven for drying for 10 to 12 hours at the temperature of 60 to 80 ℃.
7. A core-shell Cs according to claim 2 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that n (Cs) in cesium carbonate and phosphomolybdic acid is n (P) =3:1-6:1.
8. A core-shell Cs according to claim 2 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that the precipitation dissolution method specifically comprises the following steps: sheet-like MnIn 2 S 4 Sequentially adding phosphomolybdic acid and cesium carbonate into deionized water, stirring uniformly, centrifuging and washing the obtained solution, and drying in an oven at 60-80 ℃ for 10-12 h.
9. A core-shell Cs as claimed in claim 1 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalyst or core-shell Cs prepared by the preparation method of any one of claims 2-8 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalystThe method is applied to hydrogen production by water photolysis or degradation of pollutants in water.
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