CN114931936B - Preparation and application of MoS2/TiO2/rGO composite photocatalytic material - Google Patents
Preparation and application of MoS2/TiO2/rGO composite photocatalytic material Download PDFInfo
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- CN114931936B CN114931936B CN202210544754.8A CN202210544754A CN114931936B CN 114931936 B CN114931936 B CN 114931936B CN 202210544754 A CN202210544754 A CN 202210544754A CN 114931936 B CN114931936 B CN 114931936B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 265
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 102
- 229910052961 molybdenite Inorganic materials 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 68
- 239000000243 solution Substances 0.000 claims abstract description 62
- 239000007864 aqueous solution Substances 0.000 claims abstract description 53
- 239000011259 mixed solution Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 41
- 239000000017 hydrogel Substances 0.000 claims abstract description 40
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002135 nanosheet Substances 0.000 claims abstract description 31
- 238000004108 freeze drying Methods 0.000 claims abstract description 21
- 238000007146 photocatalysis Methods 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 239000011218 binary composite Substances 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims description 45
- 238000001035 drying Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 238000000502 dialysis Methods 0.000 claims description 23
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 22
- 239000000419 plant extract Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 229910052724 xenon Inorganic materials 0.000 claims description 12
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 12
- 235000006679 Mentha X verticillata Nutrition 0.000 claims description 11
- 235000002899 Mentha suaveolens Nutrition 0.000 claims description 11
- 235000001636 Mentha x rotundifolia Nutrition 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 11
- 239000011609 ammonium molybdate Substances 0.000 claims description 11
- 229940010552 ammonium molybdate Drugs 0.000 claims description 11
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 11
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052770 Uranium Inorganic materials 0.000 claims description 8
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002354 radioactive wastewater Substances 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 230000008961 swelling Effects 0.000 claims description 5
- 230000002195 synergetic effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 238000013032 photocatalytic reaction Methods 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 2
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims 7
- 239000002699 waste material Substances 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 8
- 238000003756 stirring Methods 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 239000002244 precipitate Substances 0.000 description 19
- 238000002156 mixing Methods 0.000 description 18
- -1 polytetrafluoroethylene Polymers 0.000 description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 description 18
- 239000004964 aerogel Substances 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 11
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 3
- 239000001263 FEMA 3042 Substances 0.000 description 3
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 3
- 229940033123 tannic acid Drugs 0.000 description 3
- 235000015523 tannic acid Nutrition 0.000 description 3
- 229920002258 tannic acid Polymers 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 230000001443 photoexcitation Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 235000016257 Mentha pulegium Nutrition 0.000 description 1
- 244000246386 Mentha pulegium Species 0.000 description 1
- 235000004357 Mentha x piperita Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 235000001050 hortel pimenta Nutrition 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 238000005215 recombination Methods 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
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Classifications
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B01J35/39—
-
- B01J35/60—
-
- 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
-
- 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
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
-
- 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
- C02F2101/006—Radioactive 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a preparation method of a macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material for photocatalysis, which comprises the following steps: dispersing a titanium source in hydrofluoric acid solution, and synthesizing titanium dioxide nano-sheets with thin layer characteristics by adopting a hydrothermal method; adding the titanium dioxide nanosheets into a mixed solution containing a molybdenum source and a sulfur source, uniformly dispersing, and then growing metal phase molybdenum disulfide on the surfaces of the titanium dioxide nanosheets in situ by a hydrothermal method, wherein the washed and dried solid is binary composite material MoS2/TiO2; uniformly dispersing the binary composite material MoS2/TiO2 in graphene oxide aqueous solution, and transferring the graphene oxide aqueous solution into a high-pressure reaction kettle for hydrothermal treatment to obtain macroscopic three-dimensional MoS2/TiO2/rGO hydrogel; and (3) circularly dialyzing the macroscopic three-dimensional MoS2/TiO2/rGO hydrogel, and then freeze-drying to obtain the macroscopic three-dimensional MoS2/TiO2/rGO composite material. The MoS2/TiO2/rGO material has higher removal rate and good cycle stability for simulating organic matters and U (VI) in nuclear waste liquid.
Description
Technical Field
The invention relates to preparation and application of a macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material for photocatalysis.
Background
Titanium dioxide has been widely used in photocatalytic technology for various applications as the most widely studied photocatalytic material. The band gap width of anatase phase titanium dioxide at normal temperature is 3.2eV, the light wavelength range of the response is limited to the ultraviolet light area, but the ultraviolet light area only accounts for 3% -5% of the whole solar spectrum range. Increasing the photoexcitation charge transfer path and separation efficiency of the photocatalytic material by constructing a heterojunction is an effective means of improving photocatalytic efficiency. From this point, by a certain construction method, titanium dioxide and other materials (conductors such as metallic molybdenum disulfide, reduced graphene oxide, noble metal platinum and the like, semiconductors such as carbon nitride, cadmium sulfide, graphene oxide and the like) can be involved in constructing heterojunction photocatalytic materials, and the photocatalytic efficiency of the heterojunction photocatalytic materials can be improved.
Molybdenum disulfide is commonly used in a stable state (2H-MoS) 2 ) And a metal having conductive propertiesPhase molybdenum disulfide (1T-MoS) 2 ). Compared with the 2H phase, the 1T phase molybdenum disulfide has more abundant edge active sites, and the heterojunction photocatalytic material formed by combining the molybdenum disulfide and the titanium dioxide is beneficial to the transfer of the photogenerated electrons of the titanium dioxide, which are transferred to the guide belt by photoexcitation of the titanium dioxide, to 1T-MoS due to the balance of fermi energy levels 2 On the energy level of (2) so as to realize the space separation of electrons and holes generated by light excitation and effectively reduce the recombination probability of carriers on the surface of the catalyst. The heterojunction composite material expands the response range of the catalytic material to visible light, and the active sites with rich surfaces of molybdenum disulfide are beneficial to the adsorption performance of the material to the substrate, and the oxidation-reduction reaction between the material and the contacted substrate on more active sites, so that the purpose of catalytic removal is achieved.
Based on the above-mentioned teaching, the present stage of photocatalysis technology has developed rapidly, and the powder photocatalytic material still has a serious test that is difficult to recycle. The invention utilizes graphene oxide to form a cross-linked structure with rich pore channels as a supporting structure and a heterojunction composite material formed by conductor materials, titanium dioxide and molybdenum disulfide to construct a macroscopic three-dimensional heterojunction composite photocatalytic material. The invention lays a foundation for constructing a macroscopic and efficient multielement composite material combining adsorption, catalysis and environmental pollution restoration.
Disclosure of Invention
The invention aims to overcome the defects of a powder photocatalytic material, and the preparation method of the invention uses graphene aerogel as a carrier, titanium dioxide as a main catalyst and molybdenum disulfide as a cocatalyst to prepare the macroscopic efficient three-dimensional MoS2/TiO2/rGO composite photocatalytic material by a hydrothermal method. Can be used in the fields of uranium reduction removal, organic matter degradation and the like in strong acid, high salt and polynuclear element environments.
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a method for preparing a macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material for photocatalysis, comprising the steps of:
dispersing a titanium source in hydrofluoric acid solution, and synthesizing titanium dioxide nanosheets with thin layer characteristics by adopting a hydrothermal method;
adding the titanium dioxide nanosheets into a mixed solution containing a molybdenum source and a sulfur source, uniformly dispersing, and then growing metal phase molybdenum disulfide on the surfaces of the titanium dioxide nanosheets in situ by a hydrothermal method, wherein the washed and dried solid is binary composite material MoS2/TiO2;
uniformly dispersing the binary composite material MoS2/TiO2 in a graphene oxide aqueous solution, and transferring the graphene oxide aqueous solution into a high-pressure reaction kettle for hydrothermal treatment to obtain macroscopic three-dimensional MoS2/TiO2/rGO hydrogel;
and fourthly, circularly dialyzing the macroscopic three-dimensional MoS2/TiO2/rGO hydrogel, and then freeze-drying to obtain the macroscopic three-dimensional MoS2/TiO2/rGO composite material.
Preferably, in the first step, the titanium source is any one of titanium tetrachloride, tetrabutyl titanate and titanium dioxide P25, the titanium source is added in a titanium source solution mode, the concentration of the titanium source solution is 98wt%, the concentration of the hydrofluoric acid solution is more than or equal to 40wt%, and the volume ratio of the titanium source solution to the hydrofluoric acid solution is 15-30:2-4; the temperature of the hydrothermal method is 160-220 ℃ and the duration time is 10-24 hours; in the first step, washing and drying are carried out after a hydrothermal method, wherein the washing method is any one of suction filtration washing, centrifugal washing and ultrasonic sedimentation washing, and the drying method is any one of freeze drying, natural drying, constant temperature drying and program variable temperature drying.
Preferably, in the second step, the molybdenum source is any one of molybdenum trioxide, ammonium molybdate and ammonium molybdate tetrahydrate, and the sulfur source is one or a combination of two of thioacetamide and thiourea; the temperature of the hydrothermal method is 160-220 ℃ and the duration time is 3-12 h; the mass ratio of the titanium dioxide nanosheets to the molybdenum source is 4-6:1; the mass ratio of the titanium dioxide nanosheets to the sulfur source is 4-6:1-3; in the second step, the washing method is any one of suction filtration washing, centrifugal washing and ultrasonic sedimentation washing, and the drying method is any one of freeze drying, natural drying, constant temperature drying and program variable temperature drying.
Preferably, in the third step, the graphene oxide aqueous solution is any one of a self-made graphene aqueous solution, a directly purchased graphene aqueous solution, a single-layer graphene powder aqueous solution and a single-layer graphene oxide powder aqueous solution by adopting a Hummers method.
Preferably, in the third step, a cross-linking agent is added into the graphene oxide aqueous solution to form hydrogel, wherein the cross-linking agent is one or a combination of a plurality of borax aqueous solution, peppermint plant extract and left-handed fragrant plant extract; the concentration of the graphene oxide aqueous solution is 5-15 mg/mL; the concentration of the cross-linking agent is 5-15 mg/mL; the volume ratio of the graphene oxide aqueous solution to the cross-linking agent is 4-6:1; the mass volume ratio of the binary composite material MoS2/TiO2 to the graphene oxide aqueous solution is 0.1-0.2 g:4-6 mL; the temperature of the hydrothermal treatment is 120-180 ℃ and the duration time is 3-12 h.
Preferably, the process of the third step is as follows: adding a binary composite material MoS2/TiO2, graphene oxide aqueous solution and a cross-linking agent into a microwave and ultrasonic integrated reactor, starting microwaves and ultrasonic waves simultaneously, performing synergistic treatment for 60-90 min, and transferring into a high-pressure reaction kettle for hydrothermal treatment to obtain macroscopic three-dimensional MoS2/TiO2/rGO hydrogel; wherein the temperature of the cooperative treatment is 65-75 ℃, the microwave power is 800-1000W, the ultrasonic power is 600-800W, and the ultrasonic frequency is 35-45 KHz; the concentration of the graphene oxide aqueous solution is 5-15 mg/mL; the concentration of the cross-linking agent is 5-15 mg/mL; the cross-linking agent is one or a combination of a plurality of borax aqueous solution, mint plant extract and left-handed fragrant plant extract; the volume ratio of the graphene oxide aqueous solution to the cross-linking agent is 4-6:1; the mass volume ratio of the binary composite material MoS2/TiO2 to the graphene oxide aqueous solution is 0.1-0.2 g:4-6 mL; the temperature of the hydrothermal treatment is 120-180 ℃ and the duration time is 3-12 h.
Preferably, in the third step, the obtained macroscopic three-dimensional MoS2/TiO2/rGO hydrogel is added into supercritical CO 2 CO of 10MPa was injected into the reaction apparatus 2 Heating to 60-65 deg.C, and continuously injecting CO 2 Soaking and swelling macroscopic three-dimensional MoS2/TiO2/rGO hydrogel for 1-2 h until the pressure is 15-25 MPa, and releasing pressure to obtain pretreated macroscopic three-dimensional MoS2/TiO2/rGO waterAnd (5) gel.
Preferably, in the fourth step, deionized water or 0.5-5 wt% ethanol water solution is adopted for circulating dialysis, and the circulating dialysis is carried out for 5-10 times; in the fourth step, the freeze drying process is as follows: precooling for 12h at-18 to-15 ℃, taking out, and freeze-drying at-60 to-40 ℃ for at least 48h. The hydrogel is pre-frozen under the low-temperature condition, so that the water in the reduced graphene oxide hydrogel can form ice crystals; under the condition of freeze drying, the water in the hydrogel volatilizes to finally form aerogel.
The invention also provides application of the macroscopic three-dimensional MoS2/TiO2/rGO composite material prepared by the preparation method in radioactive wastewater treatment, wherein the macroscopic three-dimensional MoS2/TiO2/rGO composite material is added into uranium-containing radioactive wastewater, and a photocatalytic reaction is carried out under the condition that a xenon lamp simulates sunlight, so that the photocatalytic reduction of hexavalent uranium in the uranium-containing radioactive wastewater is realized.
The invention also provides application of the macroscopic three-dimensional MoS2/TiO2/rGO composite material prepared by the preparation method in organic wastewater treatment, wherein the macroscopic three-dimensional MoS2/TiO2/rGO composite material is added into the organic wastewater, and photocatalytic reaction is carried out under the condition that a xenon lamp simulates sunlight, so that degradation of organic matters in the organic wastewater is realized.
The invention at least comprises the following beneficial effects:
(1) According to the preparation method, graphene oxide and plant extract are used as cross-linking agents, and the reduced graphene oxide aerogel with a macroscopic three-dimensional porous cross-linking structure is prepared by a hydrothermal method;
(2) The preparation method has the advantages of simple and efficient steps, low energy consumption and no environmental pollution, and the prepared multi-element composite photocatalytic material has excellent organic matter degradation performance and nuclide reduction performance;
(3) The prepared macroscopic three-dimensional multi-element composite photocatalytic material can be used in the fields of organic matter treatment in common industrial sewage, reduction and removal of U (VI) in simple nuclear waste liquid, nuclide adsorption reduction and removal in complex environment and the like.
(4) The preparation method has simple and convenient operation process and convenient operation, and can realize the recycling of the catalytic material.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is a physical diagram of a macroscopic three-dimensional MoS2/TiO2/rGO composite material prepared in example 1 of the invention;
FIG. 2 is an SEM image of a macroscopic three-dimensional MoS2/TiO2/rGO composite material prepared in example 1 of the present invention;
FIG. 3 shows the removal rate of U (VI) in the simulated nuclear waste liquid by photocatalytic reduction under dark conditions and 300W xenon lamp illumination conditions of the macroscopic three-dimensional MoS2/TiO2/rGO composite material prepared in the embodiments 1-6;
FIG. 4 shows the removal rate of U (VI) in the simulated nuclear waste liquid by photocatalytic reduction under dark conditions and 300W xenon lamp illumination conditions of the macroscopic three-dimensional MoS2/TiO2/rGO composite material prepared in the embodiments 1 and 7-9;
FIG. 5 shows a macroscopic three-dimensional MoS2/TiO2/rGO composite material, tiO, prepared in example 1 of the present invention 2 And 1T-MoS 2 The photocatalytic reduction under dark conditions and 300W xenon light source simulates the kinetic profile of U (VI) in nuclear waste.
The specific embodiment is as follows:
the present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a preparation method of a macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material for photocatalysis comprises the following steps:
step one, 20mL of n-butyl titanate solution (98 wt%) and 3.2mL of hydrofluoric acid solution (40 wt%) were taken and added to a high pressure of 50mL of polytetrafluoroethylene linerContinuously stirring and uniformly mixing the materials in the inner lining of the reaction kettle to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at 200 ℃ to obtain white precipitate, centrifugally washing with deionized water and absolute ethyl alcohol for 3-5 times, fully mixing and washing with 1% sodium hydroxide solution for the last time, and drying at 80 ℃ to obtain anatase-phase titanium dioxide nanosheets (TiO) 2 )；
Adding 0.5g of the obtained titanium dioxide nanosheets into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain a black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain the MoS2/TiO2 composite material;
step three, taking 3.75mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract, stirring, and performing ultrasonic treatment to obtain a mixed graphene oxide aqueous solution, wherein the ultrasonic power is 800W, and the ultrasonic frequency is 35KHz; adding 0.15g of the obtained MoS2/TiO2 composite material into a mixed graphene oxide aqueous solution, continuously stirring to obtain a fully and uniformly mixed solution, transferring the mixed solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, and reacting for 6 hours at 180 ℃ to obtain reduced graphene oxide hydrogel;
dialyzing the hydrogel by adopting an ethanol water solution with the concentration of 2wt%, wherein the dialysis time is 4 hours, and repeating for 3 times; precooling for 12 hours at the temperature of minus 17 ℃ after dialysis, taking out, and freeze-drying for 48 hours at the temperature of minus 50 ℃ to obtain the macroscopic three-dimensional MoS2/TiO2/rGO aerogel.
FIG. 1 is a physical diagram of a macroscopic three-dimensional MoS2/TiO2/rGO composite material prepared in example 1 of the invention;
FIG. 2 shows an SEM image of MoS2/TiO2/rGO aerogel prepared in example 1; from the figure, it can be seen that the graphene aerogel has a 3D layered porous skeleton which is uniformly distributed, which can greatly increase the adsorption performance and the macrostructure support performance of the material.
FIG. 3 shows the removal rate of U (VI) in the simulated nuclear waste liquid by photocatalytic reduction under dark conditions and 300W xenon lamp illumination conditions of the macroscopic three-dimensional MoS2/TiO2/rGO composite material prepared in the embodiments 1-6;
FIG. 5 shows a macroscopic three-dimensional MoS2/TiO2/rGO composite material, tiO, prepared in example 1 of the present invention 2 、1T-MoS 2 And simulating the dynamic curve of U (VI) in the nuclear waste liquid by the photocatalytic reduction of MoS2/TiO2/rGO under dark conditions and 300W xenon lamp light source.
Example 2:
a preparation method of a macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material for photocatalysis comprises the following steps:
step one, adding 20mL of n-butyl titanate solution and 3.2mL of hydrofluoric acid solution into a high-pressure reaction kettle liner with a 50mL polytetrafluoroethylene liner, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing with deionized water and absolute ethyl alcohol for 3-5 times, fully mixing and washing with 1% sodium hydroxide solution for the last time, and drying at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
adding 0.5g of the obtained titanium dioxide nanosheets into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain a black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain the MoS2/TiO2 composite material;
step three, taking 4.5mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract, stirring, and performing ultrasonic treatment to obtain a mixed graphene oxide aqueous solution, wherein the ultrasonic power is 800W, and the ultrasonic frequency is 35KHz; adding 0.15g of the obtained MoS2/TiO2 composite material into a mixed graphene oxide aqueous solution, continuously stirring to obtain a fully and uniformly mixed solution, transferring the mixed solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, and reacting for 6 hours at 180 ℃ to obtain reduced graphene oxide hydrogel;
dialyzing the hydrogel by adopting an ethanol water solution with the concentration of 2%, wherein the dialysis time is 4 hours, and repeating for 3 times; precooling for 12 hours at the temperature of minus 17 ℃ after dialysis, taking out, and freeze-drying for 48 hours at the temperature of minus 50 ℃ to obtain the macroscopic three-dimensional MoS2/TiO2/rGO aerogel.
Example 3:
a preparation method of a macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material for photocatalysis comprises the following steps:
step one, adding 20mL of n-butyl titanate solution and 3.2mL of hydrofluoric acid solution into a high-pressure reaction kettle liner with a 50mL polytetrafluoroethylene liner, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing with deionized water and absolute ethyl alcohol for 3-5 times, fully mixing and washing with 1% sodium hydroxide solution for the last time, and drying at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
adding 0.5g of the obtained titanium dioxide nanosheets into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain a black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain the MoS2/TiO2 composite material;
step three, taking 3mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract, stirring, and performing ultrasonic treatment to obtain a mixed graphene oxide aqueous solution, wherein the ultrasonic power is 800W, and the ultrasonic frequency is 35KHz; adding 0.15g of the obtained MoS2/TiO2 composite material into a mixed graphene oxide aqueous solution, continuously stirring to obtain a fully and uniformly mixed solution, transferring the mixed solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, and reacting for 6 hours at 180 ℃ to obtain reduced graphene oxide hydrogel;
dialyzing the hydrogel by adopting an ethanol water solution with the concentration of 2%, wherein the dialysis time is 4 hours, and repeating for 3 times; precooling for 12 hours at the temperature of minus 17 ℃ after dialysis, taking out, and freeze-drying for 48 hours at the temperature of minus 50 ℃ to obtain the macroscopic three-dimensional MoS2/TiO2/rGO aerogel.
Example 4:
a preparation method of a macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material for photocatalysis comprises the following steps:
step one, adding 20mL of n-butyl titanate solution and 3.2mL of hydrofluoric acid solution into a high-pressure reaction kettle liner with a 50mL polytetrafluoroethylene liner, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing with deionized water and absolute ethyl alcohol for 3-5 times, fully mixing and washing with 1% sodium hydroxide solution for the last time, and drying at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
adding 0.5g of the obtained titanium dioxide nanosheets into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain a black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain the MoS2/TiO2 composite material;
step three, 2.25mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract are taken, stirred, and mixed graphene oxide aqueous solution is obtained by ultrasonic treatment, wherein the ultrasonic power is 800W, and the ultrasonic frequency is 35KHz; adding 0.15g of the obtained MoS2/TiO2 composite material into a mixed graphene oxide aqueous solution, continuously stirring to obtain a fully and uniformly mixed solution, transferring the mixed solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, and reacting for 6 hours at 180 ℃ to obtain reduced graphene oxide hydrogel;
dialyzing the hydrogel by adopting an ethanol water solution with the concentration of 2%, wherein the dialysis time is 4 hours, and repeating for 3 times; precooling for 12 hours at the temperature of minus 17 ℃ after dialysis, taking out, and freeze-drying for 48 hours at the temperature of minus 50 ℃ to obtain the macroscopic three-dimensional MoS2/TiO2/rGO aerogel.
Example 5:
a preparation method of a macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material for photocatalysis comprises the following steps:
step one, adding 20mL of n-butyl titanate solution and 3.2mL of hydrofluoric acid solution into a high-pressure reaction kettle liner with a 50mL polytetrafluoroethylene liner, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing with deionized water and absolute ethyl alcohol for 3-5 times, fully mixing and washing with 1% sodium hydroxide solution for the last time, and drying at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
adding 0.5g of the obtained titanium dioxide nanosheets into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain a black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain the MoS2/TiO2 composite material;
step three, taking 1.5mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract, stirring, and performing ultrasonic treatment to obtain a mixed graphene oxide aqueous solution, wherein the ultrasonic power is 800W, and the ultrasonic frequency is 35KHz; adding 0.15g of the obtained MoS2/TiO2 composite material into a mixed graphene oxide aqueous solution, continuously stirring to obtain a fully and uniformly mixed solution, transferring the mixed solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, and reacting for 6 hours at 180 ℃ to obtain reduced graphene oxide hydrogel;
dialyzing the hydrogel by adopting an ethanol water solution with the concentration of 2%, wherein the dialysis time is 4 hours, and repeating for 3 times; precooling for 12 hours at the temperature of minus 17 ℃ after dialysis, taking out, and freeze-drying for 48 hours at the temperature of minus 50 ℃ to obtain the macroscopic three-dimensional MoS2/TiO2/rGO aerogel.
Example 6:
a preparation method of a macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material for photocatalysis comprises the following steps:
step one, adding 20mL of n-butyl titanate solution and 3.2mL of hydrofluoric acid solution into a high-pressure reaction kettle liner with a 50mL polytetrafluoroethylene liner, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing with deionized water and absolute ethyl alcohol for 3-5 times, fully mixing and washing with 1% sodium hydroxide solution for the last time, and drying at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
adding 0.5g of the obtained titanium dioxide nanosheets into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain a black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain the MoS2/TiO2 composite material;
step three, taking 0.75mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract, stirring, and performing ultrasonic treatment to obtain a mixed graphene oxide aqueous solution, wherein the ultrasonic power is 800W, and the ultrasonic frequency is 35KHz; adding 0.15g of the obtained MoS2/TiO2 composite material into a mixed graphene oxide aqueous solution, continuously stirring to obtain a fully and uniformly mixed solution, transferring the mixed solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, and reacting for 6 hours at 180 ℃ to obtain reduced graphene oxide hydrogel;
dialyzing the hydrogel by adopting an ethanol water solution with the concentration of 2%, wherein the dialysis time is 4 hours, and repeating for 3 times; precooling for 12 hours at the temperature of minus 17 ℃ after dialysis, taking out, and freeze-drying for 48 hours at the temperature of minus 50 ℃ to obtain the macroscopic three-dimensional MoS2/TiO2/rGO aerogel.
Example 7:
a preparation method of a macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material for photocatalysis comprises the following steps:
step one, adding 20mL of n-butyl titanate solution (98 wt%) and 3.2mL of hydrofluoric acid solution (40 wt%) into a high-pressure reaction kettle liner with 50mL of polytetrafluoroethylene liner, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing with deionized water and absolute ethyl alcohol for 3-5 times, fully mixing and washing with 1% sodium hydroxide solution for the last time, and drying at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
adding 0.5g of the obtained titanium dioxide nanosheets into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain a black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain the MoS2/TiO2 composite material;
step three, adding 0.15g of the obtained MoS2/TiO2 composite material, 3.75mL of 10mg/mL of graphene oxide aqueous solution and 1mL of 10mg/mL of mint plant extract into a microwave and ultrasonic integrated reactor, simultaneously starting microwaves and ultrasonic waves for carrying out synergistic treatment for 60min, transferring the materials into a high-pressure reaction kettle, and reacting for 6 hours at 180 ℃ to obtain reduced graphene oxide hydrogel; wherein, the temperature of the cooperative treatment is 70 ℃, the microwave power is 1000W, the ultrasonic power is 800W, and the ultrasonic frequency is 35KHz;
dialyzing the hydrogel by adopting an ethanol water solution with the concentration of 2wt%, wherein the dialysis time is 4 hours, and repeating for 3 times; precooling for 12 hours at the temperature of minus 17 ℃ after dialysis, taking out, and freeze-drying for 48 hours at the temperature of minus 50 ℃ to obtain the macroscopic three-dimensional MoS2/TiO2/rGO aerogel.
Example 8:
a preparation method of a macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material for photocatalysis comprises the following steps:
step one, adding 20mL of n-butyl titanate solution (98 wt%) and 3.2mL of hydrofluoric acid solution (40 wt%) into a high-pressure reaction kettle liner with 50mL of polytetrafluoroethylene liner, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing with deionized water and absolute ethyl alcohol for 3-5 times, fully mixing and washing with 1% sodium hydroxide solution for the last time, and drying at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
adding 0.5g of the obtained titanium dioxide nanosheets into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain a black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain the MoS2/TiO2 composite material;
step three, taking 3.75mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract, stirring, and performing ultrasonic treatment to obtain a mixed graphene oxide aqueous solution, wherein the ultrasonic power is 800W, and the ultrasonic frequency is 35KHz; adding 0.15g of the obtained MoS2/TiO2 composite material into a mixed graphene oxide aqueous solution, continuously stirring to obtain a fully and uniformly mixed solution, transferring the mixed solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, and reacting for 6 hours at 180 ℃ to obtain reduced graphene oxide hydrogel; adding the obtained reduced graphene oxide hydrogel into supercritical CO 2 CO of 10MPa was injected into the reaction apparatus 2 Heating to 60 ℃, and then continuously injecting CO 2 Soaking and swelling macroscopic three-dimensional MoS2/TiO2/rGO hydrogel for 1h until the pressure is 20MPa, and decompressing to obtain pretreated reduced graphene oxide hydrogel;
dialyzing the pretreated reduced graphene oxide hydrogel by adopting an ethanol aqueous solution with the concentration of 2wt%, wherein the dialysis time is 4 hours, and repeating for 3 times; precooling for 12 hours at the temperature of minus 17 ℃ after dialysis, taking out, and freeze-drying for 48 hours at the temperature of minus 50 ℃ to obtain the macroscopic three-dimensional MoS2/TiO2/rGO aerogel.
Example 9:
a preparation method of a macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material for photocatalysis comprises the following steps:
step one, adding 20mL of n-butyl titanate solution (98 wt%) and 3.2mL of hydrofluoric acid solution (40 wt%) into a high-pressure reaction kettle liner with 50mL of polytetrafluoroethylene liner, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing with deionized water and absolute ethyl alcohol for 3-5 times, fully mixing and washing with 1% sodium hydroxide solution for the last time, and drying at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
adding 0.5g of the obtained titanium dioxide nanosheets into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain a black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain the MoS2/TiO2 composite material;
step three, adding 0.15g of the obtained MoS2/TiO2 composite material, 3.75mL of 10mg/mL of graphene oxide aqueous solution and 1mL of 10mg/mL of mint plant extract into a microwave and ultrasonic integrated reactor, simultaneously starting microwaves and ultrasonic waves for carrying out synergistic treatment for 60min, transferring the materials into a high-pressure reaction kettle, and reacting for 6 hours at 180 ℃ to obtain reduced graphene oxide hydrogel; adding the obtained reduced graphene oxide hydrogel into supercritical CO 2 CO of 10MPa was injected into the reaction apparatus 2 Heating to 60 ℃, and then continuously injecting CO 2 Soaking and swelling macroscopic three-dimensional MoS2/TiO2/rGO hydrogel for 1h until the pressure is 20MPa, and decompressing to obtain pretreated reduced graphene oxide hydrogel; wherein the temperature of the synergistic treatment is 70 ℃ and the microwave power1000W, the ultrasonic power is 800W, and the ultrasonic frequency is 35KHz;
dialyzing the hydrogel by adopting an ethanol water solution with the concentration of 2wt%, wherein the dialysis time is 4 hours, and repeating for 3 times; precooling for 12 hours at the temperature of minus 17 ℃ after dialysis, taking out, and freeze-drying for 48 hours at the temperature of minus 50 ℃ to obtain the macroscopic three-dimensional MoS2/TiO2/rGO aerogel.
FIG. 5 shows the removal rate of U (VI) in the simulated nuclear waste liquid by photocatalytic reduction under dark conditions and 300W xenon lamp illumination conditions of the macroscopic three-dimensional MoS2/TiO2/rGO composite material prepared in the embodiments 1 and 7-9 of the invention; by CO-processing with microwaves and ultrasound and by supercritical CO 2 The removal rate of U (VI) in the simulated nuclear waste liquid is obviously improved by soaking and swelling the prepared macroscopic three-dimensional MoS2/TiO2/rGO composite material.
The photocatalytic activity of the macroscopic three-dimensional MoS2/TiO2/rGO aerogel composite material prepared in the example was studied by reducing and removing U (VI) -containing wastewater; the dark reaction stage is the ability of the material to adsorb the target removal, expressed as a negative time value. The specific process of the catalytic experiment is as follows: 10mg of MoS2/TiO2/rGO composite material is added into 50mL of 10mg/L U (VI) solution; transferring the solution into a photocatalytic reactor, and irradiating the solution with a xenon lamp (300W, lambda >365 nm) for 60min; at 20, 40, 60, 80, 100 and 120min, taking 5mL of reaction solution in a centrifuge tube, filtering the sediment by a filter head to obtain a clear solution, and measuring the uranium concentration of the solution by ICP-OES; the specific process for the tannic acid degradation rate experiment is as follows: 10mg of MoS2/TiO2/rGO composite material is added into 50mL of 40mg/L tannic acid solution; transferring the solution into a photocatalytic reactor, and irradiating the solution with a xenon lamp (300W, lambda >365 nm) for 120min; at 20, 40, 60, 80, 100, 120min, 5mL of the reaction solution was placed in a centrifuge tube, the precipitate was filtered with a filter head to obtain a clear solution, and the concentration of remaining tannic acid in the solution was measured with an ultraviolet spectrophotometer.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (6)
1. Macroscopic three-dimensional MoS for photocatalysis 2 /TiO 2 The preparation method of the rGO composite photocatalytic material is characterized by comprising the following steps:
dispersing a titanium source in hydrofluoric acid solution, and synthesizing titanium dioxide nanosheets with thin layer characteristics by adopting a hydrothermal method;
adding the titanium dioxide nanosheets into a mixed solution containing a molybdenum source and a sulfur source, uniformly dispersing, and then growing metal phase molybdenum disulfide on the surfaces of the titanium dioxide nanosheets in situ by a hydrothermal method, wherein the washed and dried solid is binary composite material MoS 2 /TiO 2 ；
Step three, moS of binary composite material 2 /TiO 2 Adding graphene oxide aqueous solution and cross-linking agent into a microwave-ultrasonic integrated reactor, simultaneously starting microwaves and ultrasonic waves, performing synergistic treatment for 60-90 min, and transferring into a high-pressure reaction kettle for hydrothermal treatment to obtain macroscopic three-dimensional MoS 2 /TiO 2 a/rGO hydrogel; wherein the temperature of the cooperative treatment is 65-75 ℃, the microwave power is 800-1000W, the ultrasonic power is 600-800W, and the ultrasonic frequency is 35-45 KHz; the concentration of the graphene oxide aqueous solution is 5-15 mg/mL; the concentration of the cross-linking agent is 5-15 mg/mL; the cross-linking agent is one or a combination of a plurality of borax aqueous solution, mint plant extract and left-handed fragrant plant extract; the volume ratio of the graphene oxide aqueous solution to the cross-linking agent is 4-6:1; binary composite MoS 2 /TiO 2 The mass volume ratio of the graphene oxide to the graphene oxide aqueous solution is 0.1-0.2 g:4-6 mL; the temperature of the hydrothermal treatment is 120-180 ℃ and the duration time is 3-12 h;
step four, macroscopic three-dimensional MoS 2 /TiO 2 Freeze-drying after rGO hydrogel circulatory dialysis to obtain macroscopic three-dimensional MoS 2 /TiO 2 rGO composite;
the step threeAdding the obtained macroscopic three-dimensional MoS2/TiO2/rGO hydrogel into supercritical CO 2 CO of 10MPa was injected into the reaction apparatus 2 Heating to 60-65 deg.C, and continuously injecting CO 2 Soaking and swelling macroscopic three-dimensional MoS2/TiO2/rGO hydrogel for 1-2 h until the pressure is 15-25 MPa, and decompressing to obtain pretreated macroscopic three-dimensional MoS2/TiO2/rGO hydrogel;
in the fourth step, deionized water or 0.5-5 wt% ethanol water solution is adopted for circulating dialysis, and the circulating dialysis is carried out for 5-10 times; in the fourth step, the freeze drying process is as follows: precooling for 12h at-18 to-15 ℃, taking out, and freeze-drying at-60 to-40 ℃ for at least 48h.
2. The preparation method of the macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material for photocatalysis according to claim 1, which is characterized in that in the first step, a titanium source is any one of titanium tetrachloride, tetrabutyl titanate and titanium dioxide P25, the titanium source is added in a titanium source solution mode, the concentration of the titanium source solution is 98wt%, the concentration of hydrofluoric acid solution is more than or equal to 40wt%, and the volume ratio of the titanium source solution to the hydrofluoric acid solution is 15-30:2-4; the temperature of the hydrothermal method is 160-220 ℃ and the duration time is 10-24 hours; in the first step, washing and drying are carried out after a hydrothermal method, wherein the washing method is any one of suction filtration washing, centrifugal washing and ultrasonic sedimentation washing, and the drying method is any one of freeze drying, natural drying, constant temperature drying and program variable temperature drying.
3. The method for preparing a macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material for photocatalysis according to claim 1, characterized in that in the second step, the molybdenum source is any one of molybdenum trioxide, ammonium molybdate and ammonium molybdate tetrahydrate, and the sulfur source is one or a combination of two of thioacetamide and thiourea; the temperature of the hydrothermal method is 160-220 ℃ and the duration time is 3-12 h; the mass ratio of the titanium dioxide nanosheets to the molybdenum source is 4-6:1; the mass ratio of the titanium dioxide nanosheets to the sulfur source is 4-6:1-3; in the second step, the washing method is any one of suction filtration washing, centrifugal washing and ultrasonic sedimentation washing, and the drying method is any one of freeze drying, natural drying, constant temperature drying and program variable temperature drying.
4. The method for preparing a macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material for photocatalysis according to claim 1, wherein in the third step, the graphene oxide aqueous solution is any one of a self-made graphene aqueous solution, a directly purchased graphene aqueous solution, a single-layer graphene powder aqueous solution, and a single-layer graphene oxide powder aqueous solution by adopting a Hummers method.
5. The application of the macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material prepared by the preparation method according to claim 1 in radioactive wastewater treatment, wherein the macroscopic three-dimensional MoS2/TiO2/rGO composite material is added into uranium-containing radioactive wastewater, and the photocatalytic reaction is carried out under the condition that a xenon lamp simulates sunlight, so that the photocatalytic reduction of hexavalent uranium in the uranium-containing radioactive wastewater is realized.
6. The application of the macroscopic three-dimensional MoS2/TiO2/rGO composite photocatalytic material prepared by the preparation method according to claim 1 in the treatment of organic wastewater, which is characterized in that the macroscopic three-dimensional MoS2/TiO2/rGO composite material is added into the organic wastewater, and the photocatalytic reaction is carried out under the condition that a xenon lamp simulates sunlight, so that the degradation of organic matters in the organic wastewater is realized.
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