CN115608388A - Shell-core type Cs 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalyst and preparation method and application thereof - Google Patents
Shell-core type Cs 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN115608388A CN115608388A CN202211386935.9A CN202211386935A CN115608388A CN 115608388 A CN115608388 A CN 115608388A CN 202211386935 A CN202211386935 A CN 202211386935A CN 115608388 A CN115608388 A CN 115608388A
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- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000008367 deionised water Substances 0.000 claims abstract description 44
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 44
- 239000011258 core-shell material Substances 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 9
- 238000006303 photolysis reaction Methods 0.000 claims abstract description 8
- 230000015843 photosynthesis, light reaction Effects 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 15
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 14
- 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
- 238000005406 washing Methods 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 238000011978 dissolution method Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000003344 environmental pollutant Substances 0.000 claims description 3
- 231100000719 pollutant Toxicity 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 239000004098 Tetracycline Substances 0.000 abstract description 10
- -1 cr (VI) Chemical compound 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
- 238000000034 method Methods 0.000 abstract description 5
- 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
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 229910001220 stainless steel Inorganic materials 0.000 description 14
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- 230000000052 comparative effect Effects 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 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 5
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000007146 photocatalysis Methods 0.000 description 2
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- 238000005215 recombination Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph 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
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 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
- 238000001000 micrograph Methods 0.000 description 1
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- 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
-
- B01J35/39—
-
- B01J35/397—
-
- 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
-
- 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
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a shell-core type Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst and a preparation method and application thereof,flake MnIn 2 S 4 Petal-shaped assembly to spherical Cs 3 PMo 12 O 40 The outer surface forms a core-shell structure. The preparation method comprises the following steps: subjecting the flaky MnIn 2 S 4 And phosphomolybdic acid and cesium carbonate are sequentially added into deionized water and uniformly stirred, and a precipitation dissolving method is adopted, and the mixture is washed and dried. The composite photocatalyst prepared by the invention has the advantages of simple preparation process, stable property, good dispersibility and strong adsorption capacity, and can be used for hydrogen production by photolysis and photocatalytic degradation. The hydrogen yield 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 of TC, cr (VI), NFX and CBZ can reach 80-98% within 1 h.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a shell-core type Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst and a preparation method and application thereof.
Background
The photocatalytic semiconductor material can convert solar energy into chemical energy, and is widely applied to the aspects of hydrogen production by photolysis, photocatalytic degradation and the like at present, and the photocatalytic technology is a better photocatalytic semiconductor material. Polyoxometallate (Cs) 3 PMo 12 O 40 ) Has the advantages of low price, easy synthesis, good stability, large specific surface area and the like. In addition, cs 3 PMo 12 O 40 As a class of semiconductor polyacids, exhibit more advantages than other inorganic semiconductor materials. But Cs 3 PMo 12 O 40 The problems that the photoresponse range is narrow, visible light cannot be fully absorbed and utilized, the quantum efficiency utilization is too low, the recombination rate of photo-generated electrons and photo-generated holes is high and the like exist.
The S-in-Mn semiconductor has good visible light response capability as a narrow band gap semiconductor. However, the narrow forbidden band results in fast recombination rate of photogenerated electron-hole pairs, thereby limiting the photocatalytic performance.
Disclosure of Invention
The invention aims to provide a spherical Cs 3 PMo 12 O 40 With flaky MnIn 2 S 4 A composite shell-core photocatalyst, its preparation and use are disclosed, which are aimed at solving the problems of existing technique pointed out in the background art. In order to achieve the purpose, the invention adopts the following technical scheme:
shell-core type Cs 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalyst, sheet-like MnIn 2 S 4 Petal-shaped assembly to spherical Cs 3 PMo 12 O 40 The outer surface forms a core-shell structure.
Preferably, the flaky MnIn 2 S 4 Diameter of 5-25nm, spherical Cs 3 PMo 12 O 40 200-250nm in diameter and core-shell type Cs 3 PMo 12 O 40 /MnIn 2 S 4 The diameter of the composite photocatalyst is 400-700nm, wherein Cs is 3 PMo 12 O 40 With MnIn 2 S 4 The mass ratio of (A) to (B) is 7-11.
Composite modified shell-core type Cs 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst has excellent oxidation-reduction capability and simultaneously has more positive VB potential and more negative CB potential, which is very favorable for improving the photocatalytic performance. In addition, the shell-core type composite photocatalyst has more active point 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 type 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 point positions and improves the photocatalytic activity.
Above core-shell type Cs 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst comprises the following steps: flake MnIn 2 S 4 Sequentially adding phosphomolybdic acid and cesium carbonate into deionized water, uniformly stirring, washing and drying by adopting a precipitation dissolution method to obtain spherical Cs 3 PMo 12 O 40 With flaky MnIn 2 S 4 Composite shell-core photocatalysts.
Preferably, the flaky MnIn 2 S 4 The preparation method 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 Suspending liquid, washing and drying the suspending liquid to obtain flaky MnIn 2 S 4 。
Preferably, the molar ratio of manganese acetate tetrahydrate, indium chloride and thioacetamide is (0.1-2) to (1-4) to (1-10).
Preferably, the hydrothermal method specifically comprises: sequentially adding manganese acetate tetrahydrate, indium chloride and thioacetamide into deionized water, uniformly stirring, placing in an oven, controlling the temperature rise speed to be 180-260 ℃ at the speed 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 for 6 to 10 times by deionized water and dried for 10 to 12 hours in a drying oven at the temperature of between 60 and 80 ℃.
Preferably, in the cesium carbonate and phosphomolybdic acid, n (Cs) = 3.
Preferably, the precipitation dissolution method specifically comprises: subjecting the flaky MnIn 2 S 4 And phosphomolybdic acid and cesium carbonate are sequentially added into deionized water and uniformly stirred, the obtained solution is placed in a centrifuge tube for centrifugation to obtain a product, then the product is washed by the deionized water for 6-10 times and is placed in an oven for drying for 10-12 hours at the temperature of 60-80 ℃.
Above core-shell type Cs 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst can be used for preparing hydrogen by photolysis of water or degrading pollutants in water.
The invention has the beneficial effects that:
core-Shell type Cs of the invention 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 respectively degrade the TC, the Cr (VI), the NFX and the CBZ by 80-98% within 1 h. Meanwhile, the device has the performance of hydrogen production by photolysis of water under the irradiation of visible light. In addition, the core-shell type 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 used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows Cs obtained in example 1 of the present invention 3 PMo 12 O 40 /MnIn 2 S 4 XRD pattern of (a).
FIG. 2 shows the different ratios Cs 3 PMo 12 O 40 /MnIn 2 S 4 Scanning electron micrograph (c).
FIG. 3 shows Cs obtained in comparative example 1 of the present invention 3 PMo 12 O 40 /MnIn 2 S 4 Scanning electron micrograph (c).
FIG. 4 shows different ratios Cs 3 PMo 12 O 40 /MnIn 2 S 4 The photocatalytic hydrogen production amount of (1).
FIG. 5 shows Cs produced in example 1 of the present invention 3 PMo 12 O 40 /MnIn 2 S 4 The amount of hydrogen produced by the cyclic photocatalysis.
FIG. 6 shows Cs produced 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 produced in example 1 of the present invention 3 PMo 12 O 40 /MnIn 2 S 4 Degradation cycle map of (c).
FIG. 8 shows different ratios Cs 3 PMo 12 O 40 /MnIn 2 S 4 TC degradation rate graph of (a).
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
Core-shell type 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) to mix and stir evenly in a beaker (50 ml of deionized water), then transferring the mixture into a stainless steel autoclave lined with polytetrafluoroethylene, putting the stainless steel autoclave in a baking oven to be calcined for 24 hours at the temperature rising rate of 5 ℃/min to 240 ℃, washing and drying the suspension to obtain flaky MnIn 2 S 4 And (3) a solid. Weighing 100mg of flaky MnIn 2 S 4 1g of cesium carbonate and 2g of phosphomolybdic acid are mixed and stirred uniformly in a beaker (50 ml of deionized water), the obtained solution is placed in a centrifuge tube for centrifugation to obtain a product, then the product is washed for 8 times by the deionized water (the adding amount of the deionized water is 50 ml), and the product is placed in an oven for drying for 12 hours at 60 ℃ to obtain Cs 3 PMo 12 O 40 ：MnIn 2 S 4 Cs in a mass ratio of 9 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst.
Example 2
Core-shell type 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) to mix and stir evenly in a beaker (50 ml of deionized water), then transferring to a stainless steel autoclave lined with polytetrafluoroethylene, putting the stainless steel autoclave in an oven, heating to 180 ℃ at the heating rate of 3 ℃/min, calcining for 18h, washing and drying the suspension to obtain flaky MnIn 2 S 4 And (3) solid. Weighing 100mg of flaky MnIn 2 S 4 1g of cesium carbonate and 2g of phosphomolybdic acid are mixed and stirred uniformly in a beaker (80 ml of deionized water), the obtained solution is placed in a centrifuge tube for centrifugation to obtain a product, then the product is washed for 6 times by the deionized water (the adding amount of the deionized water is 60 ml), and the product is placed in an oven for drying at 60 ℃ for 10 hours to obtain Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst is provided.
Example 3
Core-shell type 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) to mix and stir evenly in a beaker (50 ml of deionized water), then transferring to a stainless steel autoclave lined with polytetrafluoroethylene, putting the stainless steel autoclave in an oven, heating to 240 ℃ at the heating rate of 1 ℃/min, calcining for 20h, washing and drying the suspension to obtain flaky MnIn 2 S 4 And (3) solid. Weighing 100mg of flaky MnIn 2 S 4 Mixing and stirring 2g of cesium carbonate and 1g of phosphomolybdic acid uniformly in a beaker (50 ml of deionized water), placing the obtained solution in a centrifuge tube for centrifugation to obtain a product, washing the product for 6 times by using the deionized water (the filling amount of the deionized water is 50 ml), and placing the product in an oven for drying at 80 ℃ for 10 hours to obtain Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst is provided.
Example 4
Core-shell type 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) to mix and stir evenly in a beaker (50 ml of deionized water), then transferring to a stainless steel autoclave lined with polytetrafluoroethylene, putting the stainless steel autoclave in an oven, heating to 190 ℃ at the heating rate of 5 ℃/min, calcining for 30h, washing and drying the suspension to obtain flaky MnIn 2 S 4 And (3) a solid. Weighing 100mg of flaky MnIn 2 S 4 2g of cesium carbonate and 3g of phosphomolybdic acid are mixed and stirred uniformly in a beaker (50 ml of deionized water), the obtained solution is placed in a centrifuge tube for centrifugation to obtain a product, then the product is washed 7 times by the deionized water (the adding amount of the deionized water is 60 ml), and the product is placed in an oven for drying for 12 hours at 80 ℃ to obtain Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst.
Example 5
Core-shell type 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 (3 mmol) and thioacetamide (6 mmol) to mix and stir evenly in a beaker (50 ml of deionized water), then transferring the beaker to a stainless steel autoclave lined with polytetrafluoroethylene, putting the autoclave in a baking oven to be calcined for 28h at the temperature rising rate of 4 ℃/min to 240 ℃, washing and drying the suspension to obtain flaky MnIn 2 S 4 And (3) a solid. Weighing 100mg of flaky MnIn 2 S 4 1g of cesium carbonate and 2g of phosphomolybdic acid are mixed and stirred uniformly in a beaker (100 ml of deionized water), the obtained solution is placed in a centrifuge tube for centrifugation to obtain a product, then the product is washed for 6 times by the deionized water (the adding amount of the deionized water is 40 ml), and the product is placed in an oven for drying at 70 ℃ for 10 hours to obtain Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst is provided.
Example 6
Core-shell type 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) to mix and stir evenly in a beaker (50 ml of deionized water), then transferring to a stainless steel autoclave lined with polytetrafluoroethylene, putting the stainless steel autoclave in an oven, raising the temperature to 200 ℃ at the rate of 3 ℃/min, calcining for 36h, washing and drying the suspension to obtain flaky MnIn 2 S 4 And (3) a solid. Weighing 100mg of flaky MnIn 2 S 4 3g of cesium carbonate and 1g of phosphomolybdic acid are mixed and stirred uniformly in a beaker (100 ml of deionized water), the obtained solution is placed in a centrifuge tube for centrifugation to obtain a product, then the product is washed for 6 times by the deionized water (the adding amount of the deionized water is 30 ml), and the product is placed in an oven for drying at 70 ℃ for 11 hours to obtain Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst is provided.
Comparative example 1
Core-shell type 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(50 ml of deionized water), uniformly mixing and stirring, transferring to a stainless steel autoclave lined with polytetrafluoroethylene, putting in an oven, heating to 200 ℃ at the heating rate of 2 ℃/min, calcining for 20h, washing and drying the suspension to obtain flaky MnIn 2 S 4 And (3) a solid. Weighing 100mg of flaky MnIn 2 S 4 1g of cesium carbonate and 2g of phosphomolybdic acid are mixed and stirred uniformly in a beaker (50 ml of deionized water), the obtained solution is placed in a centrifuge tube for centrifugation to obtain a product, then the product is washed for 7 times by the deionized water (the adding amount of the deionized water is 70 ml), and the product is placed in an oven for drying at 70 ℃ for 11 hours to obtain Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst is provided.
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 shows that the flaky MnIn prepared in the comparative example 1 2 S 4 The solid has small size, no petaloid appearance, few active point positions and poor catalytic performance.
Comparative example 2
Core-shell type 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) to mix and stir evenly in a beaker (50 ml of deionized water), then transferring to a stainless steel autoclave lined with polytetrafluoroethylene, putting the stainless steel autoclave in an oven, heating to 220 ℃ at the heating rate of 5 ℃/min, calcining for 22h, washing and drying the suspension to obtain flaky MnIn 2 S 4 And (3) a solid. Weighing 100mg of flaky MnIn 2 S 4 1g of cesium carbonate and 0.4g of phosphomolybdic acid are mixed and stirred uniformly in a beaker (50 ml of deionized water), the obtained solution is placed in a centrifuge tube for centrifugation to obtain a product, then the product is washed for 6 times by the deionized water (the adding amount of the deionized water is 50 ml), and the product is placed in an oven for drying at 70 ℃ for 10 hours to obtain Cs 3 PMo 12 O 40 /MnIn 2 S 4 A composite photocatalyst is provided.
Application example 1
Core-shell type Cs 3 PMo 12 O 40 /MnIn 2 S 4 Application examples of the composite photocatalyst are as follows:
cs prepared in example 1 was used 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 composite photocatalyst has the mass ratio of 7 to 11, and single Cs is adopted 3 PMo 12 O 40 And MnIn 2 S 4 As a comparison of photocatalytic performance for each mass ratio, the optimum ratio was 9 by comparison. 20mg of each photocatalyst was weighed out and added to 50ml of 15% triethanolamine solution, followed by reaction with a 420nm filter for 1 hour, and then the amount of hydrogen generation was measured by gas chromatography. The hydrogen production performance is calculated by a formula, and the result is shown in figure 4. Mixing Cs with mass ratio of 9 3 PMo 12 O 40 /MnIn 2 S 4 The catalyst was hydrolyzed 5 times in cycles and the stability was determined as shown in FIG. 5.
As can be seen in FIG. 4, cs prepared in example 1 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst has excellent water photolysis 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, cs prepared in example 1 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst has good stability of water photolysis, and still has excellent performance of hydrogen production by water photolysis after 5 cycles.
Application example 2
Core-shell type Cs 3 PMo 12 O 40 /MnIn 2 S 4 Application example of the composite photocatalyst:
cs prepared in example 1 was selected 3 PMo 12 O 40 /MnIn 2 S 4 Weighing 20mg of the composite photocatalyst, placing the catalyst in 20ml of contaminant solution with 40ppm, irradiating for 1h by using a 300W xenon lamp after dark treatment to achieve desorption balance, measuring the absorption value of the solution by using ultraviolet, and calculating the degradation rate by using a formula, wherein the result is shown in figure 6. Mixing the catalystThe degradation was performed 4 times in cycles and the stability was determined as shown in FIG. 7.
FIG. 6 shows that Cs prepared in example 1 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst can degrade pollutants by 80-98% after 1h, has high degradation rate and quick reaction time, wherein the concentrations of TC, cr (VI), NFX and CBZ solutions are 20ppm, 80ppm, 30ppm and 20ppm respectively.
FIG. 7 shows that 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 cycles.
Cs prepared according to the above-described method using examples 2 to 6 and comparative examples 1 to 2 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst is used for degrading Tetracycline (TC), and the degradation result after 1 hour is shown in table 1.
TABLE 1
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
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 (10)
1. Shell-core type Cs 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst is characterized in that the flaky MnIn 2 S 4 Assembled into spherical Cs in petal shape 3 PMo 12 O 40 The outer surface forms a core-shell structure.
2. The shell-and-core type Cs of claim 1 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst is characterized in that the flaky MnIn 2 S 4 Diameter of 5-25nm, spherical Cs 3 PMo 12 O 40 200-250nm in diameter and core-shell type 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 (1) to (7) is.
3. The shell-core type Cs according to claim 1 or 2 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst is characterized by comprising the following steps: flake MnIn 2 S 4 Sequentially adding phosphomolybdic acid and cesium carbonate into deionized water, uniformly stirring, washing and drying by adopting a precipitation dissolution method to obtain spherical Cs 3 PMo 12 O 40 With flaky MnIn 2 S 4 Composite shell-core photocatalysts.
4. The shell-and-core type Cs of claim 3 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that the flaky MnIn 2 S 4 The preparation method 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 Suspending liquid, washing and drying the suspending liquid to obtain flaky MnIn 2 S 4 。
5. The shell-and-core type Cs of claim 4 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst comprises the steps of mixing manganese acetate tetrahydrate, indium chloride and thioacetamide in a molar ratio of (0.1-2) to (1-4) to (1-10).
6. The shell-and-core type Cs of claim 4 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, uniformly stirring, placing in an oven, controlling the temperature rise speed to be 180-260 ℃ at the speed of 1-5 ℃/min, and carrying out heat preservation and calcination for 18-36h.
7. The shell-and-core type Cs of claim 4 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that the MnIn is 2 S 4 The suspension is stirred for 4-6 h at room temperature, then washed for 6-10 times by deionized water and then placed in a drying oven for drying for 10-12 h at 60-80 ℃.
8. The shell-and-core type Cs of claim 3 3 PMo 12 O 40 /MnIn 2 S 4 A method for producing a composite photocatalyst, characterized in that n (Cs) =3 in cesium carbonate and phosphomolybdic acid.
9. The shell-and-core type Cs of claim 3 3 PMo 12 O 40 /MnIn 2 S 4 The preparation method of the composite photocatalyst is characterized in that the precipitation and dissolution method specifically comprises the following steps: subjecting the flaky MnIn 2 S 4 And phosphomolybdic acid and cesium carbonate are sequentially added into deionized water and uniformly stirred, and the obtained solution is centrifuged and washed and then is dried in an oven at the temperature of 60-80 ℃ for 10-12 hours.
10. A shell-core type Cs according to claim 1 or 2 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalyst or shell-core type Cs prepared by preparation method of any one of claims 3-9 3 PMo 12 O 40 /MnIn 2 S 4 The composite photocatalyst is applied to hydrogen production by photolysis of water or degradation of pollutants in water.
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