CN110152711B - CeO (CeO)2@MoS2/g-C3N4Ternary composite photocatalyst and preparation method thereof - Google Patents
CeO (CeO)2@MoS2/g-C3N4Ternary composite photocatalyst and preparation method thereof Download PDFInfo
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- 229910052961 molybdenite Inorganic materials 0.000 title claims abstract description 108
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 60
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 31
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 30
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002135 nanosheet Substances 0.000 claims abstract description 29
- 238000001354 calcination Methods 0.000 claims abstract description 28
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 23
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 20
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011206 ternary composite Substances 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- -1 cerium oxide hexahydrate Chemical compound 0.000 claims abstract description 14
- 239000002159 nanocrystal Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 12
- 239000002086 nanomaterial Substances 0.000 claims abstract description 11
- 239000004201 L-cysteine Substances 0.000 claims abstract description 10
- 235000013878 L-cysteine Nutrition 0.000 claims abstract description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 10
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000004098 Tetracycline Substances 0.000 claims description 6
- 229960002180 tetracycline Drugs 0.000 claims description 6
- 229930101283 tetracycline Natural products 0.000 claims description 6
- 235000019364 tetracycline Nutrition 0.000 claims description 6
- 150000003522 tetracyclines Chemical class 0.000 claims description 6
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000001027 hydrothermal synthesis Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 230000006798 recombination Effects 0.000 description 7
- 238000005215 recombination Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
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- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000001362 electron spin resonance spectrum Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 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
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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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
- C02F2101/38—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
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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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the field of nano material preparation and discloses CeO2@MoS2/g‑C3N4The composite photocatalytic material is prepared through (1) adding cerium oxide hexahydrate into the mixed solution of butylamine and toluene, hydrothermal treatment of the mixed solution, and calcining the reaction product to obtain CeO2A nanocrystal; (2) mixing sodium molybdate dihydrate with g-C3N4The nano-sheets are ultrasonically dispersed in a mixed solution of L-cysteine and dimethyl sulfoxide, and the obtained mixed solution is subjected to hydrothermal treatment to obtain MoS2/g‑C3N4Nanosheets; (3) adding CeO2Nanocrystalline and MoS2/g‑C3N4Ultrasonically dispersing in methanol solution, volatilizing methanol, and collecting the obtained product as CeO2‑MoS2/g‑C3N4A composite material; (4) adding CeO2‑MoS2/g‑C3N4The composite material is placed in a tube furnace and calcined in the nitrogen atmosphere to obtain CeO2@MoS2/g‑C3N4A ternary composite photocatalyst. The preparation method is simple and has strong controllability, and the obtained composite photocatalyst has excellent photocatalytic degradation performance.
Description
Technical Field
The invention belongs to the technical field of nano material preparation and photocatalytic environmental energy and pollutant treatment, and particularly relates to CeO2@MoS2/g-C3N4A composite photocatalytic material and a preparation method thereof.
Background
With the rapid development of modern industrialization, the problems of environmental pollution and energy crisis become more and more prominent. The photocatalytic technology based on semiconductor and its derivative material as medium is becoming a popular new energy research direction as a solar-driven, pollution-free, economical and effective means. Cerium oxide (CeO)2) The rare earth metal oxide is a rare earth metal oxide which is applied to important industries in China, has rich content, low cost, no pollution and good chemical stability, and has good application prospect in the fields of photocatalysis, hydrogen production and photoelectricity. But CeO2There are two major drawbacks, firstly, the band gap of ceria is 3.2eV, and its wide band gap chemistry results in that it can only be excited by uv light; secondly, the cerium dioxide has a low internal charge transfer rate and a high electron hole pair recombination rate, resulting in CeO2The photon utilization rate is low in the process of photocatalytic chemical reaction.
The construction of the heterojunction can effectively improve the light absorption performance of the composite material and the rapid separation and transfer of the photo-generated electron pair, so that the oxidation and reduction capabilities of the material lost due to charge recombination can be effectively avoided. In recent years, novel organic polymers g-C3N4Are of great interest because of their ease of preparation, high specific surface area and excellent electrical conductivity, their typical two-dimensional sheet structure and their surface functional groups being able to be othersThe semiconductor provides effective support to form the heterostructure. MoS as a good cocatalyst, an effective substitute compound for noble metals2Because a large amount of unsaturated Mo and S elements exist at the exposed edge of the semiconductor, the active site can be effectively activated, so that the visible light utilization rate of the wide band gap semiconductor is enhanced. Thus, a two-dimensional MoS2/g-C3N4The heterojunction structure not only can provide more support carriers, but also can effectively enhance the light absorption capacity and reduce the recombination rate of photo-generated electron-hole pairs. However, to date, there has been no CeO2@MoS2/g-C3N4The preparation of heterojunctions and the application of photocatalysis are reported. Therefore, the invention provides a visible light responding CeO2@MoS2/g-C3N4The preparation method of the heterojunction material aims to prolong the service life of a photon-generated carrier by constructing an excellent heterojunction structure, and further promote the rapid separation of photon-generated electrons and holes so as to enhance the photocatalytic water decomposition hydrogen production and pollutant removal capability of the heterojunction material.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention is directed to providing CeO2@MoS2/g-C3N4A composite photocatalytic material and a preparation method thereof.
The invention realizes the technical purpose through the following technical means:
CeO (CeO)2@MoS2/g-C3N4The preparation method of the ternary composite photocatalyst comprises the following preparation steps:
(1) adding cerium oxide hexahydrate into a mixed solution of butylamine and toluene, uniformly dissolving, carrying out hydrothermal treatment on the obtained mixed solution, and calcining a reaction product to obtain CeO2A nanocrystal;
(2) mixing sodium molybdate dihydrate with g-C3N4The nano-sheets are ultrasonically dispersed in a mixed solution of L-cysteine and dimethyl sulfoxide (DMSO), the obtained mixed solution is subjected to hydrothermal treatment, and a reaction product is washed and dried to obtain MoS2/g-C3N4A composite material;
(3) adding CeO2Nanocrystalline and MoS2/g-C3N4Ultrasonically dispersing the composite material in a methanol solution, reacting at normal temperature until the methanol is completely volatilized, and collecting the obtained product which is CeO2-MoS2/g-C3N4A composite material;
(4) adding CeO2-MoS2/g-C3N4The composite material is placed in a tube furnace and is calcined in the nitrogen atmosphere to strengthen the CeO2Crystals and MoS2/g-C3N4Interface reaction of the nanostructure to obtain CeO2@MoS2/g-C3N4A ternary composite material. CeO prepared by the preparation method2@MoS2/g-C3N4Composite photocatalyst with Ce simultaneously3+、Ce4+In which Ce is3+And Ce4 +Is in the form of a reversible electron pair, which can extend the lifetime of the charge; ce4+Capable of trapping electrons to prevent rapid recombination of electron-hole pairs; ce3+Can have stronger reducing power of a system and can be a reactant H2The O molecules provide a large number of adsorption sites, which in turn reduce their adsorption energy and promote water decomposition.
MoS in the invention2The compound has unique two-dimensional nano structure and g-C of graphite-like structure3N4Can be combined by pi-pi stacking. MoS2The nano sheet has strong absorption effect on visible light on one hand, and can effectively improve the conduction rate of electron-hole pairs when being used as an electron conduction layer on the other hand. And CeO2The introduction of the heterojunction can be in MoS2/g-C3N4A new energy level is introduced into the nanosheet structure, and the photoresponse effect of the composite photocatalyst under visible light is also obviously enhanced.
Preferably, the mass-to-volume ratio of the cerium oxide hexahydrate, the butylamine, the toluene and the distilled water in the step (1) is (0.2-0.6) g: (0.05-0.25) ml: (10-30) ml: (20-30) ml.
Preferably, the hydrothermal treatment temperature in the step (1) is 160-180 ℃, and the hydrothermal treatment time is 24 hours; the calcination temperature is 180 ℃, and the calcination time is 24 h.
Preferably, the sodium molybdate dihydrate in the step (2), the L-cysteine and the g-C3N4The mass-volume ratio of the nanosheet to the DMSO is (0.20-0.40) g: (0.3-0.6) ml: (0.05-0.15) g: (20-40) ml.
Preferably, the hydrothermal treatment temperature in the step (2) is 180-200 ℃, and the hydrothermal treatment time is 36 h.
Preferably, the CeO of step (3)2Nanocrystalline, MoS2/g-C3N4The mass-volume ratio of the composite material to methanol is (0.01-0.03) g: (0.02-0.06) g: 50 ml.
Preferably, the flow rate of the nitrogen gas flow in the calcination treatment process in the nitrogen atmosphere in the step (4) is 0.3-1.5L/min-mm, the calcination temperature is 180 ℃, and the calcination time is 1 h.
Another object of the present invention is to provide a CeO prepared by the present invention2@MoS2/g-C3N4The application of the composite photocatalyst.
CeO prepared by the invention2@MoS2/g-C3N4The composite photocatalyst is used for decomposing water to prepare hydrogen under visible light.
CeO prepared by the invention2@MoS2/g-C3N4The application of the ternary composite photocatalyst in degrading tetracycline under visible light.
In the above technical scheme, the amount of the distilled water is such that the soluble solid can be completely dissolved.
The invention has the beneficial effects that:
(1) MoS in the composite photocatalyst prepared by the invention2The compound has unique two-dimensional nano structure and g-C of graphite-like structure3N4Can be combined by pi-pi stacking. MoS2The nano sheet has strong absorption effect on visible light on one hand, and can effectively improve the conduction rate of electron-hole pairs when being used as an electron conduction layer on the other hand. And can be calcined at high temperature in MoS2/g-C3N4CeO is introduced into nanosheet structure2NovelThe energy level also obviously enhances the photoresponse effect of the composite photocatalyst under visible light.
(2) CeO prepared by the invention2@MoS2/g-C3N4Composite photocatalyst with Ce simultaneously3+、 Ce4+In which Ce is3+And Ce4+Is in the form of a reversible electron pair, which can extend the lifetime of the charge; ce4+Capable of trapping electrons to prevent rapid recombination of electron-hole pairs; ce3+Can have stronger reducing power of a system and can be a reactant H2The O molecules provide a large number of adsorption sites, which in turn reduce their adsorption energy and promote water decomposition.
(3) CeO prepared by the invention2@MoS2/g-C3N4The ternary composite photocatalyst has excellent visible light effect, and realizes effective separation of photo-generated electron-hole pairs.
(4) MoS in the invention2/g-C3N4The nano-sheets are abundant and easily obtained, and the large specific surface area of the nano-sheets is favorable for improving CeO2The dispersion property of (2).
Drawings
FIG. 1 shows CeO prepared by the present invention2@MoS2/g-C3N4A transmission electron microscope image of the composite photocatalyst;
FIG. 2 is an X-ray diffraction pattern and X-ray photoelectron spectrum of a catalyst prepared according to the present invention;
FIG. 3 shows CeO prepared by the present invention2@MoS2/g-C3N4Ultraviolet-visible absorption spectrum, fluorescence spectrum and photo-current spectrum of the composite photocatalyst;
FIG. 4 is a MoS prepared according to the present invention2/g-C3N4With CeO2@MoS2/g-C3N4A contact angle experiment, an infrared absorption spectrum and an electron spin resonance spectrum of the composite photocatalyst;
FIG. 5 shows CeO prepared by the present invention2@MoS2/g-C3N4XPS spectrum of the composite photocatalyst;
FIG. 6 is a diagram of hydrogen production by the photocatalyst prepared by the present invention;
FIG. 7 is a graph showing the effect of photocatalytic degradation of tetracycline under visible light irradiation.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Evaluation of photocatalytic degradation activity of the photocatalyst prepared in the present invention: the method is carried out in a photocatalytic degradation instrument prepared by Shenzhen Lanpu technology Limited, a 200W xenon lamp is used as a light source, and a 420nm filter is arranged in the xenon lamp; 50mg of catalyst is dispersed in 100mL of 20mg/L tetracycline solution; fully ultrasonically energizing N before turning on the lamp2Completely removing air after 30min, maintaining anaerobic condition and uniform light irradiation of catalyst, extracting sample every 5 min, centrifuging, and measuring light absorption intensity.
The activity evaluation of the photocatalytic hydrogen production of the photocatalyst prepared in the invention is as follows: the photocatalysis hydrogen production instrument of Shenzhen Shang Lun science and technology Limited company uses the intensity of 80.0mW cm-2With a 420nm filter, 3W UV-Leds illumination; 50mg of catalyst was dispersed in a solution containing 0.5M Na2SO3And 0.5M Na2S in 80mL solution; fully ultrasonically energizing N before turning on the lamp2And completely removing air in 30min, and keeping anaerobic condition and uniform light irradiation of the catalyst.
Example 1
(1) Putting 5g of urea into a muffle furnace, uniformly heating to 550 ℃ at the heating rate of 2 ℃/min, calcining for 6 hours at the constant temperature, naturally cooling, grinding the obtained solid into fine powder to obtain g-C3N4Nanosheets. As can be seen from FIGS. 1, 2, 3, 4 and 5, pure g-C3N4The morphology of the compound is a two-dimensional sheet structure, no obvious stacking phenomenon exists, and characteristic peaks attributed to C and N elements can be clearly observed in an X-ray diffraction pattern and an X-ray photoelectron spectrum, which shows that the g-C synthesized by the method is applicable3N4The nanosheets have extremely high purity.
(2) 0.2g of cerium oxide hexahydrate can be dissolved in 0.05ml of butylamine, 10ml of toluene and 20ml of distilled waterAnd (3) uniformly stirring the mixed solution until the mixed solution is completely dissolved, transferring the obtained mixed solution into a hydrothermal reaction kettle, sealing the reaction kettle, and then placing the reaction kettle in an oven at 160-180 ℃ for hydrothermal treatment for 24 hours. After the reaction is finished, repeatedly washing the obtained product with ethanol and deionized water, filtering, drying at 60 ℃, and calcining the dried reaction product at 180 ℃ for 24 hours to obtain CeO2And (4) nanocrystals.
(3) Taking 0.20g of sodium molybdate dihydrate and 0.05g of-C3N4The nano-sheets are ultrasonically dispersed in a mixed solution of 0.3ml of L-cysteine and 20ml of dimethyl sulfoxide (DMSO), the obtained mixed solution is transferred into a hydrothermal reaction kettle, and after the reaction kettle is sealed, the hydrothermal treatment is carried out in an oven at 180 ℃ for 36 hours. After the reaction is finished, repeatedly washing the obtained product with ethanol and deionized water, filtering, and drying at 60 ℃ to obtain MoS2/g-C3N4A composite material.
(4) 0.01g of CeO was taken2Nanocrystals and 0.02g MoS2/g-C3N4Ultrasonically dispersing the composite material in 50ml of methanol solution, reacting at normal temperature until the methanol is completely volatilized, and collecting the obtained product which is CeO2-MoS2/g-C3N4And (3) precursor.
(5) 5g of CeO were weighed2-MoS2/g-C3N4Placing the precursor in a tube furnace, heating to 180 ℃ under the nitrogen atmosphere with the nitrogen flow rate of 0.3L/min.mm, calcining for 1h to strengthen CeO2Crystals and MoS2/g-C3N4Interface reaction of the nanostructure to obtain CeO2@MoS2/g-C3N4A ternary composite material.
Example 2
(1) Putting 5g of urea into a muffle furnace, uniformly heating to 550 ℃ at the heating rate of 2 ℃/min, calcining for 6 hours at the constant temperature, naturally cooling, grinding the obtained solid into fine powder to obtain g-C3N4Nanosheets.
(2) Dissolving 0.4g of cerium oxide hexahydrate in a mixed solution of 0.15ml of butylamine, 20ml of toluene and 30ml of distilled water, uniformly stirring until the cerium oxide hexahydrate is completely dissolved, and obtaining a mixtureTransferring the solution into a hydrothermal reaction kettle, sealing the reaction kettle, and placing the reaction kettle in an oven at 170 ℃ for hydrothermal treatment for 24 hours. After the reaction is finished, repeatedly washing the obtained product with ethanol and deionized water, filtering, drying at 60 ℃, and calcining the dried reaction product at 170 ℃ for 24 hours to obtain CeO2And (4) nanocrystals.
(3) 0.30g of sodium molybdate dihydrate and 0.10g g-C are taken3N4The nano-sheets are ultrasonically dispersed in a mixed solution of 0.4ml of L-cysteine and 30ml of dimethyl sulfoxide (DMSO), the obtained mixed solution is transferred into a hydrothermal reaction kettle, and after the reaction kettle is sealed, the hydrothermal treatment is carried out in an oven at 200 ℃ for 36 hours. After the reaction is finished, repeatedly washing the obtained product with ethanol and deionized water, filtering, and drying at 60 ℃ to obtain MoS2/g-C3N4A composite material.
(4) 0.02g of CeO was taken2Nanocrystals and 0.04g MoS2/g-C3N4Ultrasonically dispersing the composite material in 50ml of methanol solution, reacting at normal temperature until the methanol is completely volatilized, and collecting the obtained product which is CeO2-MoS2/g-C3N4And (3) precursor.
(5) 5g of CeO were weighed2-MoS2/g-C3N4Placing the precursor in a tube furnace, heating to 180 ℃ under the nitrogen atmosphere with the nitrogen flow rate of 1.5L/min.mm, calcining for 1h to strengthen CeO2Crystals and MoS2/g-C3N4Interface reaction of the nanostructure to obtain CeO2@MoS2/g-C3N4A ternary composite material. FIG. 1 shows CeO2@MoS2/g-C3N4Transmission electron microscopy of the composite photocatalyst, as shown in the figure, CeO prepared by the preparation method of the embodiment2The crystals are uniformly distributed and have no stacking phenomenon, and the particle size of the crystals is about 19.7nm, MoS2Is in a sheet structure and is uniformly distributed, and CeO can be known by a projection electron microscope2Crystal, MoS2Nanosheets and g-C3N4The three nano sheets are tightly combined to form an obvious heterojunction structure. FIG. 2 shows CeO2@MoS2/g-C3N4CompoundingThe X-ray diffraction pattern and X-ray photoelectron spectrum of the photocatalyst show that CeO is present in the X-ray diffraction pattern2@MoS2/g-C3N4No obvious MoS appears in the composite photocatalyst2And g-C3N4May be due to CeO2Too large peak intensity of (A) to mask the characteristic peaks of (A) and (B), possibly due to MoS2And g-C3N4The amount of supported (A) was small, and the characteristic peak was weak. And the X-ray photoelectron spectroscopy proves that MoS is in the composite photocatalyst2Nanosheets and g-C3N4Presence of nanoplatelets.
FIG. 3 shows CeO prepared in this example2@MoS2/g-C3N4Ultraviolet-visible absorption spectrum, fluorescence and photocurrent of the composite photocatalyst. As can be seen from FIG. 3a, compare g-C3N4、CeO2/g-C3N4Iso-photocatalytic material, MoS2The introduction of the nanosheets greatly improves the absorption of visible light, and as can be seen from fig. 3b and 3c, CeO2@MoS2/g-C3N4The composite photocatalyst has obvious phenomena of fluorescence quenching and photocurrent intensity enhancement, which shows that in each comparative system, CeO is added2@MoS2/g-C3N4The photo-generated electron hole pair separation rate and the recombination rate of the composite photocatalyst are highest and lowest.
Example 3
(1) Putting 5g of urea into a muffle furnace, uniformly heating to 600 ℃ at the heating rate of 5 ℃/min, calcining for 4 hours at the constant temperature, naturally cooling, grinding the obtained solid into fine powder to obtain g-C3N4Nanosheets.
(2) Dissolving 0.6g of cerium oxide hexahydrate in a mixed solution of 0.25ml of butylamine, 30ml of toluene and 25ml of distilled water, uniformly stirring until the cerium oxide hexahydrate is completely dissolved, transferring the obtained mixed solution into a hydrothermal reaction kettle, sealing the reaction kettle, and placing the reaction kettle in an oven at 180 ℃ for hydrothermal treatment for 24 hours. After the reaction is finished, repeatedly washing the obtained product with ethanol and deionized water, filtering, drying at 60 ℃, and calcining the dried reaction product for 24 hours at 180 DEG CTo obtain CeO2And (4) nanocrystals.
(3) Taking 0.40g of sodium molybdate dihydrate and 0.15g g-C3N4The nano-sheets are ultrasonically dispersed in a mixed solution of 0.6ml of L-cysteine and 40ml of dimethyl sulfoxide (DMSO), the obtained mixed solution is transferred into a hydrothermal reaction kettle, and after the reaction kettle is sealed, the hydrothermal treatment is carried out in an oven at 200 ℃ for 36 hours. After the reaction is finished, repeatedly washing the obtained product with ethanol and deionized water, filtering, and drying at 60 ℃ to obtain MoS2/g-C3N4A composite material.
(4) 0.03g of CeO was taken2Nanocrystals and 0.06g MoS2/g-C3N4Ultrasonically dispersing the composite material in 50ml of methanol solution, reacting at normal temperature until the methanol is completely volatilized, and collecting the obtained product which is CeO2-MoS2/g-C3N4A composite material.
(5) 5g of CeO were weighed2-MoS2/g-C3N4Placing the precursor in a tube furnace, heating to 180 ℃ under the nitrogen atmosphere with the nitrogen flow rate of 1.0L/min.mm, and calcining for 1h to strengthen CeO2Crystals and MoS2/g-C3N4Interface reaction of the nanostructure to obtain CeO2@MoS2/g-C3N4A ternary composite material.
FIG. 4 shows MoS prepared by the preparation method of this example2/g-C3N4With CeO2@MoS2/g-C3N4Contact angle experiment of the composite photocatalyst. As can be seen from FIGS. 4a and b, CeO2@MoS2/g-C3N4The contact angle of the ternary composite photocatalyst is less than MoS2/g-C3N4The binary composite photocatalyst shows that the absorption capacity of the photocatalyst on water reactants is greatly improved, and the photocatalyst is beneficial to adsorbing pollutants in water and carrying out photocatalytic hydrolysis hydrogen production reaction. FIG. 4c shows the peak of hydroxyl stretching vibration after water molecules are adsorbed on the infrared absorption spectrum of the catalyst prepared in this example, and it can be seen from the graph that CeO2@MoS2/g-C3N4The three-element composite photocatalyst is widened at the peak of 3000-3600,further proves that the ternary material has stronger water adsorption energy in a contact angle experiment, and is beneficial to physical adsorption in the photocatalytic reaction process, so that the photocatalytic reaction rate is enhanced. FIG. 4d is the electron spin resonance spectrum of this example, from which CeO is known2、CeO2@g-C3N4And CeO2@MoS2/g-C3N4G is 1.96 in the electron spin resonance spectrum of the three-way composite photocatalyst, which shows that CeO2Surface Ce presents trivalent (3)+) And is compared with CeO2、CeO2@g-C3N4，CeO2@MoS2/g-C3N4The EPR peak intensity of the ternary composite photocatalyst is also enhanced, which indicates that more trivalent Ce ions exist in the ternary composite photocatalyst. Importantly, Ce3+And Ce4+Is in the form of a reversible electron pair, which can extend the lifetime of the charge; ce4+Capable of trapping electrons to prevent rapid recombination of electron-hole pairs; ce3+Can have stronger reducing power of a system and can be a reactant H2The O molecules provide a large number of adsorption sites, so that the adsorption energy is reduced, and the water decomposition is promoted, so that the photocatalytic reaction capability is obviously improved.
Example 4
(1) Putting 5g of urea into a muffle furnace, uniformly heating to 550 ℃ at the heating rate of 2 ℃/min, calcining for 6 hours at the constant temperature, naturally cooling, grinding the obtained solid into fine powder to obtain g-C3N4Nanosheets.
(2) Dissolving 0.5g of cerium oxide hexahydrate in a mixed solution of 0.20ml of butylamine, 15ml of toluene and 20ml of distilled water, uniformly stirring until the cerium oxide hexahydrate is completely dissolved, transferring the obtained mixed solution into a hydrothermal reaction kettle, sealing the reaction kettle, and placing the reaction kettle in an oven at 170 ℃ for hydrothermal treatment for 24 hours. After the reaction is finished, repeatedly washing the obtained product with ethanol and deionized water, filtering, drying at 60 ℃, and calcining the dried reaction product at 180 ℃ for 24 hours to obtain CeO2And (4) nanocrystals.
(3) Taking 0.25g of sodium molybdate dihydrate and 0.10g g-C3N4The nano-sheet is ultrasonically dispersed in 0.5ml of L-cysteine and 25ml of dimethyl sulfoxideAnd (DMSO), transferring the obtained mixed solution into a hydrothermal reaction kettle, sealing the reaction kettle, and placing the reaction kettle in a 200 ℃ oven for hydrothermal treatment for 36 hours. After the reaction is finished, repeatedly washing the obtained product with ethanol and deionized water, filtering, and drying at 60 ℃ to obtain MoS2/g-C3N4A composite material.
(4) 0.015g of CeO was taken2Nanocrystals and 0.03g MoS2/g-C3N4Ultrasonically dispersing the composite material in 50ml of methanol solution, reacting at normal temperature until the methanol is completely volatilized, and collecting the obtained product which is CeO2-MoS2/g-C3N4A composite material.
(5) 5g of CeO were weighed2-MoS2/g-C3N4Placing the precursor in a tube furnace, heating to 180 ℃ under the nitrogen atmosphere with the nitrogen flow rate of 0.5L/min.mm, calcining for 1h to strengthen CeO2Crystals and MoS2/g-C3N4Interface reaction of the nanostructure to obtain CeO2@MoS2/g-C3N4A ternary composite material.
FIG. 5 shows MoS prepared by the preparation method of this example2/g-C3N4With CeO2@MoS2/g-C3N4XPS spectrum of the composite photocatalyst can show that CeO2@MoS2/g-C3N4Middle Ce3+And Ce4+When ions coexist, CeO is known from the electron spin resonance spectrum in example 42@MoS2/g-C3N4More Ce is present in3+And then represents CeO2@MoS2/g-C3N4More oxygen vacancies must exist in the composite catalyst, and the existence of the oxygen vacancies is more favorable for the occurrence of photocatalytic redox reaction.
FIG. 6 shows MoS prepared by the preparation method of this example2/g-C3N4With CeO2@MoS2/g-C3N4The photocatalyst hydrogen production experiment of the composite photocatalyst is shown in FIG. 6c, CeO2@MoS2/g-C3N4The composite photocatalyst is maintained for 12 weeks, and the photocatalytic hydrogen production performance of the composite photocatalyst is not obviously different from that of g-C3N4、MoS2/g-C3N4In contrast, CeO2-MoS2/g-C3N4The hydrogen yield of the composite photocatalyst is as high as 65.4 mu mol/L under the condition of no noble metal, the quantum efficiency at 420nm is as high as 10.35 percent, and certain quantum efficiency still exists along with the increase of the wavelength, which shows that CeO2-MoS2/g-C3N4The composite photocatalyst still has good utilization rate of visible light, and is a visible photocatalyst with huge potential.
Example 5
(1) Putting 5g of urea into a muffle furnace, uniformly heating to 600 ℃ at the heating rate of 5 ℃/min, calcining for 4 hours at the constant temperature, naturally cooling, grinding the obtained solid into fine powder to obtain g-C3N4Nanosheets.
(2) Dissolving 0.2g of cerium oxide hexahydrate in a mixed solution of 0.25ml of butylamine, 30ml of toluene and 12ml of distilled water, uniformly stirring until the cerium oxide hexahydrate is completely dissolved, transferring the obtained mixed solution into a hydrothermal reaction kettle, sealing the reaction kettle, and placing the reaction kettle in an oven at 160 ℃ for hydrothermal treatment for 24 hours. After the reaction is finished, repeatedly washing the obtained product with ethanol and deionized water, filtering, drying at 60 ℃, and calcining the dried reaction product at 180 ℃ for 24 hours to obtain CeO2And (4) nanocrystals.
(3) 0.40g of sodium molybdate dihydrate and 0.05g g-C are taken3N4The nano-sheets are ultrasonically dispersed in a mixed solution of 0.3ml of L-cysteine and 40ml of dimethyl sulfoxide (DMSO), the obtained mixed solution is transferred into a hydrothermal reaction kettle, and after the reaction kettle is sealed, the hydrothermal treatment is carried out in an oven at 200 ℃ for 36 hours. After the reaction is finished, repeatedly washing the obtained product with ethanol and deionized water, filtering, and drying at 60 ℃ to obtain MoS2/g-C3N4A composite material.
(4) 0.03g of CeO was taken2Nanocrystals and 0.02g MoS2/g-C3N4Ultrasonically dispersing the composite material in 50ml of methanol solution, and reacting at normal temperature until the composite material is ACompletely volatilizing alcohol, collecting the obtained product as CeO2-MoS2/g-C3N4A composite material.
(5) 5g of CeO were weighed2-MoS2/g-C3N4Placing the precursor in a tube furnace, heating to 180 ℃ in a nitrogen atmosphere with the nitrogen flow rate of 0.8L/min.mm, calcining for 1h to strengthen CeO2Crystals and MoS2/g-C3N4Interface reaction of the nanostructure to obtain CeO2@MoS2/g-C3N4A ternary composite material.
FIG. 7 is a graph showing the effect of photocatalytic degradation of tetracycline under visible light irradiation, as compared to g-C3N4、 MoS2/g-C3N4Isophotocatalytic material, CeO2@MoS2/g-C3N4The three-element composite photocatalyst has a more obvious degradation effect on tetracycline with the concentration of 20mg/L under the irradiation of visible light, the degradation rate is obviously improved, and the photocatalytic degradation efficiency reaches 95% within a 120min time period.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (7)
1. CeO (CeO)2@MoS2/g-C3N4The preparation method of the ternary composite photocatalyst is characterized by comprising the following preparation steps:
(1) adding cerium oxide hexahydrate into a mixed solution of butylamine, toluene and distilled water, uniformly dissolving, carrying out hydrothermal treatment on the obtained mixed solution, and calcining a reaction product to obtain CeO2A nanocrystal; the hydrothermal treatment temperature is 160-180 ℃, and the hydrothermal treatment time is 24 hours; the calcination temperature is 180 ℃, and the calcination time is 24 hours;
(2) mixing sodium molybdate dihydrate with g-C3N4The nano-sheet is ultrasonically dispersed in L-cysteine and IIIn the methyl sulfoxide mixed solution, washing and drying the obtained mixed solution after hydrothermal treatment to obtain MoS2/g-C3N4Nanosheets; the sodium molybdate dihydrate, the L-cysteine and the g-C3N4The mass-volume ratio of the nanosheet to the dimethyl sulfoxide is (0.20-0.40) g: (0.3-0.6) ml: (0.05-0.15) g: (20-40) ml;
(3) adding CeO2Nanocrystalline and MoS2/g-C3N4The nano-sheet is ultrasonically dispersed in a methanol solution, the reaction is carried out at normal temperature until the methanol is completely volatilized, and the product obtained by collecting is CeO2-MoS2/g-C3N4A composite material;
(4) adding CeO2-MoS2/g-C3N4The composite material is placed in a tube furnace and is calcined in the nitrogen atmosphere to strengthen the CeO2Crystals and MoS2/g-C3N4Interface reaction of the nanostructure to obtain CeO2@MoS2/g-C3N4A ternary composite photocatalyst; the calcination temperature is 180 ℃, and the calcination time is 1 h.
2. CeO according to claim 12@MoS2/g-C3N4The preparation method of the ternary composite photocatalyst is characterized by comprising the following steps: in the step (1), the mass-to-volume ratio of the cerium oxide hexahydrate, the butylamine, the toluene and the distilled water is (0.2-0.6) g: (0.05-0.25) ml: (10-30) ml: (20-30) ml.
3. CeO according to claim 12@MoS2/g-C3N4The preparation method of the ternary composite photocatalyst is characterized by comprising the following steps: and (3) performing hydrothermal treatment at 180-200 ℃ for 36h in the step (2).
4. CeO according to claim 12@MoS2/g-C3N4The preparation method of the ternary composite photocatalyst is characterized by comprising the following steps: ce of step (3)O2Nanocrystalline, MoS2/g-C3N4The mass-volume ratio of the composite material to methanol is (0.01-0.03) g: (0.02-0.06) g: 50 ml.
5. CeO according to claim 12@MoS2/g-C3N4The preparation method of the ternary composite photocatalyst is characterized by comprising the following steps: and (4) in the calcining treatment process under the nitrogen atmosphere, the flow rate of nitrogen gas flow is 0.3-1.5L/min.
6. CeO prepared by the preparation method according to any one of claims 1 to 52@MoS2/g-C3N4The application of the three-way composite photocatalyst is characterized in that: adding CeO2@MoS2/g-C3N4The composite photocatalyst is used for decomposing water to prepare hydrogen under visible light.
7. CeO prepared by the preparation method according to any one of claims 1 to 52@MoS2/g-C3N4The application of the three-way composite photocatalyst is characterized in that: adding CeO2@MoS2/g-C3N4The composite photocatalysis is used for degrading tetracycline under visible light.
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