CN105597784A - MoS2-doped iron oxide photocatalytic thin film and preparation method as well as application thereof to treatment of phenolic waste water - Google Patents
MoS2-doped iron oxide photocatalytic thin film and preparation method as well as application thereof to treatment of phenolic waste water Download PDFInfo
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- CN105597784A CN105597784A CN201511009083.1A CN201511009083A CN105597784A CN 105597784 A CN105597784 A CN 105597784A CN 201511009083 A CN201511009083 A CN 201511009083A CN 105597784 A CN105597784 A CN 105597784A
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000002351 wastewater Substances 0.000 title claims abstract description 9
- 239000010409 thin film Substances 0.000 title abstract description 15
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 87
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 87
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000004070 electrodeposition Methods 0.000 claims abstract description 39
- 238000001354 calcination Methods 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 26
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000007146 photocatalysis Methods 0.000 claims description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 32
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000001103 potassium chloride Substances 0.000 claims description 10
- 235000011164 potassium chloride Nutrition 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 150000002751 molybdenum Chemical class 0.000 claims description 9
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 8
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 8
- 239000011609 ammonium molybdate Substances 0.000 claims description 8
- 229940010552 ammonium molybdate Drugs 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 7
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- -1 thio ammonium molybdate Chemical compound 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910000859 α-Fe Inorganic materials 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 94
- 239000000758 substrate Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000005259 measurement Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 12
- 238000005286 illumination Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000011017 operating method Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000003760 hair shine Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000004502 linear sweep voltammetry Methods 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- B01J35/59—
-
- 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
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- Y02W10/33—Wastewater or sewage treatment systems using renewable energies using wind energy
-
- 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 MoS2-doped iron oxide photocatalytic thin film. The preparation method of the MoS2-doped iron oxide photocatalytic thin film comprises the following steps of (1), electrodepositing a precursor solution of Fe<2+> on a conducting substrate, and obtaining a Fe2O3 thin film through calcination treatment; (2), electrodepositing MoS2 on the Fe2O3 thin film prepared in the step (1), calcining the Fe2O3 thin film in an inert atmosphere to obtain a Fe2O3-MoS2 photocatalytic thin film. The invention also discloses the MoS2-doped iron oxide photocatalytic thin film prepared by adopting the above method and application to the treatment of phenolic waste water by utilizing the film. The preparation method provided by the invention is simple and low-cost. The photocatalytic thin film prepared by adopting an electrodeposition method is uniform in film formation and good in stability; an active component is difficult to peel off; the area of the thin film is easy to control. The separation efficiency of photoelectrons and holes of the prepared Fe2O3-MoS2 thin film is high; the prepared Fe2O3-MoS2 thin film has favorable photoelectrocatalytic activity. Through measurement, the photoelectric current of a prepared composite photocatalytic thin film is increased by approximately 25 times relative to that of the Fe2O3 thin film.
Description
Technical field
The present invention relates to photoelectrocatalysis technical field, particularly relate to a kind of MoS2The iron oxide of dopingPhotocatalysis film, preparation method and the application in Phenol-Containing Wastewater Treatment thereof.
Background technology
Natural regenerative resource as the supply of solar energy and wind energy be not continuously, thereforeNeed to take effectively storage means to carry out between balance production of energy and consumption not matching relationship. As oneKind desirable energy carrier, that hydrogen has is clean, renewable, fuel value is high and be convenient to the advantages such as transport.Photoelectrocatalysis technology demonstrates huge potentiality in processing various environmental problems and energy crisis at present.Its key problem in technology is to prepare efficient, stable photocatalysis film.
Fe2O3As a kind of visible-light response type semi-conducting material, its band-gap energy is 2.1eV, at purpleAll there is good photoresponse outward and under radiation of visible light. But, Fe2O3Material shortcoming is the light producingRaw electronics and hole are easily compound and perishable. Recently, by Fe2O3Catalyst adulterate orThe compound research in the composite modified light induced electron-hole that suppresses its generation is more and more. Right at presentIn Fe2O3Adulterate or the composite modified Pt of mostly being, Ag, Si, Ti, the metal ion such as Al, Mo,But the efficiency of its photodissociation aquatic products hydrogen is also lower. And be used at present preparing Fe2O3The side of catalystFado is hydro-thermal method, and its preparation process is loaded down with trivial details, the cycle is long.
Publication number is that the Chinese patent literature of CN104815668A discloses a kind of Ta, Al codopeThe preparation method of iron oxide photochemical catalyst, comprise the steps: that (1) is with Al3+And Fe2+PresomaSolution is as electrolyte, and conductive substrates is as working electrode, and graphite electrode is to electrode, Ag/AgClElectrode, as reference electrode, carries out electro-deposition; (2) by Ta5+Precursor solution repeatedly drip and be coated onto through stepSuddenly the conductive substrates that process (1), then calcines and obtains Ta/Al-Fe2O3Photocatalysis film. ShouldMethod adopts respectively electro-deposition and drop-coating that Ta/Al is doped on iron oxide photocatalysis film, energy oneDetermine degree and improve photoelectric current, promote photocatalytic activity, but it is limited to promote effect; And the photocatalysis makingFilm surface is more coarse, active component easily peels off; Ta/Al-Fe2O3The effective area of photocatalysis filmMore difficult control.
Summary of the invention
For further improving light induced electron and the hole separative efficiency of the iron oxide photocatalysis film of doping,Promote photocatalytic activity, the invention provides a kind of MoS2The system of the iron oxide photocatalysis film of dopingPreparation Method.
A kind of MoS2The preparation method of the iron oxide photocatalysis film of doping, comprises the steps:
Step (1): adopt three-electrode system, with Fe2+Precursor solution as electrolyte, conductionSubstrate is as working electrode, and graphite electrode is to electrode, and Ag/AgCl electrode, as reference electrode, entersRow electro-deposition; Make Fe through calcination processing again2O3Film;
Step (2): with MoS2Precursor solution as electrolyte, make with step (1)Fe2O3Film is working electrode, and titanium sheet is as to electrode, and Ag/AgCl electrode is as reference electrode,Carry out electro-deposition; Then under atmosphere of inert gases, calcining makes Fe2O3-MoS2Film.
The inventive method is passed through two step electro-deposition by MoS2Be doped into Fe2O3In film, makeFe2O3-MoS2Film surface is even, film size is easy to control; Active material good stability, is difficult for strippingFall; MoS2Band gap marginal position is good, electric conductivity is strong.
Moreover, prepared Fe2O3-MoS2Film (MoS2The iron oxide photocatalysis of doping is thinFilm) light induced electron and hole separative efficiency high, there is good photoelectric catalytically active.
In the present invention, the conductive substrates of step (1) be FTO glass (as, specification can be 10mm × 50Mm × 2mm), carrying out before the electro-deposition of step (1), need first to conductive substrates clean,Drying and processing. As FTO glass carried out ultrasonic clear by acetone, absolute ethyl alcohol and deionized water successivelyWash, dry rear for subsequent use.
In step (1), the precursor solution adopting when electro-deposition is ferrous ion solution, and electricity is heavyAfter long-pending, at the oxide (as ferrous hydroxide) of FTO deposition on glass, formation ferrous ionFilm, by obtaining the sull of trivalent after calcining.
In step (1), Fe2+Precursor solution formulated by soluble ferrite and solvent orange 2 A;Soluble ferrite preferred water dissolubility ferrous salt; Solvent orange 2 A preferred alcohols and/or water, described alcohol is preferredWith water infinitely than miscible low-molecular-weight unit alcohol or polyalcohol.
Described Fe2+Precursor solution in, Fe2+Molar concentration be 0.01-0.2M; Fe2+Derive fromOne or more of ferrous nitrate, frerrous chloride, ferrous sulfate, ferrous acetate and ferrous oxalate, moltenAgent A is one or more in ethylene glycol, deionized water, methyl alcohol and ethanol.
As preferably, Fe2+Precursor solution in, described Fe2+Derive from FeCl2, solvent orange 2 A isThe mixed solution of ethylene glycol and deionized water, wherein, the volume ratio of ethylene glycol and deionized water is1:5～12；Fe2+Molar concentration be 0.01～0.04M.
Fe2+Precursor solution in, the mixed solvent of described ethylene glycol and water is conducive to electrodeposition processThe formation of middle ferrous hydroxide, wherein, the mixed proportion of ethylene glycol and deionized water also can affect madeThe pattern of standby film, and then affect the photocatalysis performance of film.
Further preferably, Fe2+Precursor solution in, FeCl2Molar concentration be 0.02M, second twoThe volume ratio of alcohol and deionized water is 1:6～10. The volume ratio of ethylene glycol and deionized water most preferably is1:8。
After step (1) electro-deposition completes, need carry out high-temperature calcination (further to the coating of electro-depositionOxidation), temperature, time and the operating voltage of electro-deposition all can affect the quality of doping, calcining temperatureThe Fe that degree impact generates2O3Crystalline phase; Above-mentioned parameter all can affect the photocatalysis performance of doping.
In the inventive method, can control film forming effective area by regulating and controlling each step electro-deposition parameter.
As preferably, in step (1), electrodeposition temperature is 50～90 DEG C, and electro-deposition voltage is 1～2V;Calcining heat is 300-600 DEG C, and calcination time is 0.5～3h. Under this condition, the electricity of step (1)Sedimentation time is preferably 1-15min.
Under described calcining heat, Fe2O3The Fe of film2O3Crystalline phase is α-Fe2O3, degree of crystallinity is good,Photocatalytic activity is high.
Further preferably, electrodeposition temperature is 70 DEG C, and electro-deposition voltage is 1.36V; Calcining heat is500 DEG C, calcination time is 2h. In step (1), electrodeposition time is 5min more preferably.
After step (1) is finished dealing with, carry out step (2), to the Fe generating2O3Molybdenum adulterates in film.
As preferably, in step (2), MoS2Precursor solution by MoS2Precursor and moltenAgent B is formulated, wherein MoS2Precursor be molybdenum salt, sylvite and ammonium salt;
Wherein, molybdenum salt is four thio ammonium molybdate and/or ammonium molybdate; Sylvite is potassium chloride, potash and nitreOne or more of acid potassium; Ammonium salt be a kind of of ammonium chloride, ammonium sulfate, ammonium nitrate and carbonic hydroammonium orMultiple; Solvent B is one or more in formamide, ethylene glycol and methyl alcohol; Wherein, molybdenum salt is denseDegree is 0.001-0.02M.
Further preferably, MoS2Precursor solution in, the concentration of molybdenum salt is 0.001-0.002M.
Described MoS2Precursor solution in, described sylvite molar concentration is 0.01-0.1M; Ammonium saltMolar concentration is 0.1-0.5M.
As preferably, described MoS2Precursor solution be four thio ammonium molybdate, potassium chloride, chlorinationThe mixed solution of ammonium and formamide, wherein, four thio ammonium molybdate molar concentration is 0.002M; ChlorinationPotassium molar concentration is 0.04M; Ammonium chloride molar concentration is 0.2M.
As preferably, in step (2), electro-deposition voltage is-0.7～-0.1V; Electrodeposition time is1～45min。
Further preferably, in step (2), electro-deposition voltage is-0.6V; Electrodeposition time is 15min.
After completing, step (2) electro-deposition carries out again calcination processing.
Under atmosphere of inert gases, carry out calcination processing, be conducive to the generation of molybdenum bisuphide. Inert gasFlow velocity has a certain impact to the production tool of molybdenum bisuphide. As, in calcination process, because of inert gasFlow velocity molybdenum oxide too low and that produce can reduce doping (MoS2The iron oxide photocatalysis film of doping)Photocatalysis performance.
As preferably, in step (2), described inert gas is N2And/or argon gas; Inert gasFlow velocity is 50～150mL/min; Calcining heat is 300～600 DEG C; Calcination time is 0.5～3h.
The generation of the suitable molybdenum bisuphide of described calcining heat, and be conducive to improve into membrane stage, improve instituteThe photocatalysis performance of the doping making. If calcining heat too low (as lower than 300 DEG C), the knot of materialCrystallinity is poor, likely limits the photocatalytic activity of prepared doping. If calcining heat too high (asHigher than 600 DEG C), temperature exceedes the heat resisting temperature of conductive substrates, and film is had to destruction.
Further preferably, in step (2), the flow velocity of inert gas is 100mL/min, calcining temperatureDegree is 400 DEG C; Calcination time is 1h.
The photoelectric catalytically active of photocatalysis film is relevant with thickness, and film is too thick affects photo-generated carrierMigration. The moderate doping of thickness can excite the generation of carrier, can also improve the migration speed of carrierRate, thereby the photoelectric catalytically active of raising doping.
In the present invention, it is heavy that the gross thickness of the doping making under above-mentioned parameter is substantially equal to twice electricityThe thickness sum of the long-pending film forming, the film thickness making is moderate, and film forming is even.
The present invention also provides a kind of MoS that adopts above-mentioned preparation method to make2The iron oxide light of dopingCatalytic film, as preferably, described MoS2The thickness of the iron oxide photocatalysis film of doping is200-600nm。
Further preferably, prepared MoS2The thickness of the iron oxide photocatalysis film of doping is385nm。
The present invention also comprises that one utilizes prepared MoS2The iron oxide photocatalysis film processing of dopingThe application of phenol wastewater.
In the present invention, adopt photocatalysis film film forming that the method for electro-deposition makes evenly, good stability,Active component is incrust; Film size is easy to control. Prepared Fe2O3-MoS2The photoproduction of filmElectronics and hole separative efficiency are high, have good photoelectric catalytically active. By measuring, at visible rayAccording under, the photoelectric current of the composite photocatalysis film of preparation is with respect to Fe2O3Film has improved approximately 25 times;Under ultraviolet-visible illumination, photoelectric current is with respect to Fe2O3Film has improved approximately 22 times.
Brief description of the drawings
Fig. 1 a is Fe2O3-MoS2Film and Fe2O3Visible in 0.2MNaOH solution of filmLinear sweep voltammetry curve under illumination alternately;
Fig. 1 b is Fe2O3-MoS2Film and Fe2O3The ultraviolet of film in 0.2MNaOH solution-Visible ray is according to the linear sweep voltammetry curve under replacing;
Fig. 2 is Fe2O3-MoS2Film and Fe2O3Film in 0.2MNaOH solution under dark stateTo the linear sweep voltammetry curve of negative voltage scanning direction;
Fig. 3 a is Fe2O3-MoS2Film and Fe2O3The dark place of film in 0.2MNaOH solutionAC impedance figure under condition;
Fig. 3 b is Fe2O3-MoS2Film and Fe2O3Visible in 0.2MNaOH solution of filmAC impedance figure under optical condition;
Fig. 4 is Fe2O3-MoS2Film and Fe2O3The degradation rate comparison of film phenol under visible rayFigure;
Fig. 5 is Fe2O3-MoS2Falling of film photoelectric catalysis, photocatalysis and catalytic oxidation phenolThe comparison diagram of solution rate;
Fig. 6 is for recycling Fe2O3-MoS2In film photoelectric catalytic degradation phenol process, phenol fallsSolution rate schematic diagram.
Detailed description of the invention
Below in conjunction with accompanying drawing and instantiation, the present invention will be described in detail.
Embodiment 1
(1) with Fe2+Precursor solution (Fe2+Derive from FeCl2) as electrolyte, through clearWash, conductive substrates after drying and processing is as working electrode, graphite electrode is to electrode, Ag/AgClElectrode, as reference electrode, carries out electro-deposition.
Conductive substrates in the present embodiment is FTO glass (specification is 10mm × 50mm × 2mm),Before preparing film, carry out ultrasonic cleaning 10min by acetone, absolute ethyl alcohol and deionized water successively, thenTaking-up is dried.
The thickness of the film obtaining by electro-deposition process parameter control electro-deposition, in the present embodiment, electricity is heavyLong-pending technological parameter is as follows: electrodeposition temperature is 70 DEG C, and operating voltage is 1.36V, and sedimentation time is5min。
(2) conductive substrates then step (1) having been deposited is put into Muffle furnace, enters at 500 DEG CRow calcining 2h obtains Fe2O3Photocatalysis film (Fe2O3Film).
(3) formamide that preparation contains a certain amount of four thio ammonium molybdate, potassium chloride and ammonium chloride is moltenLiquid is as MoS2Precursor solution. Wherein, four thio ammonium molybdate molar concentration is 0.002M; ChlorineChanging potassium molar concentration is 0.04M; Ammonium chloride molar concentration is 0.2M.
(4) will deposit Fe2O3FTO (the Fe that step (2) makes of film2O3Film) conductWorking electrode, titanium sheet do electrode, Ag/AgCl electrode to make reference electrode. Join by electrodeposition technologyThe thickness of the film that numerical control electro-deposition processed obtains, wherein, voltage is-0.6V that the time is 15min.Dry, then the FTO having deposited is put into tube furnace, pass into N2，N2Flow velocity be100mL/min, is warming up to 400 DEG C with 2 DEG C/min, calcining 1h. Obtain Fe2O3-MoS2Film,Estimating film thickness is 385nm.
Comparative example 1
For ease of carrying out performance comparison, preparation contrast Fe by the following method2O3Film, specifically preparationMethod is as follows:
Adopt three-electrode structure, using FTO as working electrode, graphite is done electrode, Ag/AgClMake reference electrode, under 70 DEG C, 1.36V condition, carry out electro-deposition, sedimentation time is 5min, heavyHydrops is the FeCl preparing2Solution (with embodiment 1).
After electro-deposition, after it dries naturally, put into Muffle furnace, at 500 DEG C, calcine 2hObtain Fe2O3Film.
Fig. 1 a is the Fe that embodiment 1 makes2O3-MoS2Film and Fe2O3Film (is made by comparative example 1) linear sweep voltammetry curve under radiation of visible light.
Fig. 1 b is the Fe that embodiment 1 makes2O3-MoS2Film and Fe2O3Film (is made by comparative example 1) linear sweep voltammetry curve under ultraviolet-visible irradiation.
From Fig. 1 a, under visible ray shines, compared to Fe2O3Film, MoS2Doping makePhotoelectric current (being current density) is corresponding has improved 25 times. Be MoS2Mix and affected urging of filmChange active. From Fig. 1 b, under ultraviolet-visible illumination, compared to Fe2O3Film, MoS2Doping make that photoelectric current (being current density) is corresponding has improved 22 times. Known, do not sacrificingUnder the condition that agent exists, MoS2Be entrained in promote Fe2O3The photoelectric catalytically active aspect of film verySignificantly. From Fig. 1 a and Fig. 1 b, can obviously find out, for simple Fe2O3Film, at visible rayOr ultraviolet-visible moment of being blocked or manifesting, photoelectric current can reach rapidly maximum, just declines subsequentlyReduce to certain value, this is due to Fe2O3Film itself compound larger, light induced electron and hole onceProduce just compound immediately. And doping MoS2After there will not be this kind of phenomenon, this illustrates MoS2?Fe2O3Film surface can suppress the compound of light induced electron and hole.
Fig. 2 is the Fe that embodiment 1 prepares2O3-MoS2Film and Fe2O3Film is (by comparative example 1Make) 0.2MNaOH solution from negative direction start scanning linear sweep voltammetry curve. Sweeping speed is5mV/s. As can be seen from Figure 2, Fe2O3-MoS2Film produces hydrogen take-off potential with respect to Fe2O3Film shuffle 0.1V and Fe2O3-MoS2Film photoelectric current in the time of-0.18Vvs.Ag/AgCl is 0.052mA/cm2, and Fe2O3Film reaches this current/voltage need-0.4Vvs.Ag/AgCl. MoS2'sDoping makes to produce hydrogen position and shuffles, and Fe is described2O3-MoS2Film is compared to Fe2O3The easier photodissociation water of filmProduce hydrogen, obviously improved the photoelectric catalytically active of photocatalysis film.
Fig. 3 a and Fig. 3 b are the Fe that embodiment 1 prepares2O3-MoS2Film and Fe2O3Film (byComparative example 1 makes) in 0.2MNaOH solution, respectively in the dark with visible ray condition under electrificationLearn impedance spectrum (EIS collection of illustrative plates). The frequency range of electrochemical workstation setting is 106Hz-0.01Hz。From Fig. 3 a, Fig. 3, (no matter b, be in dark or under visible illumination condition, Fe2O3-MoS2The impedance ring radius of film is all significantly less than Fe2O3Film. Known, Fe2O3-MoS2The electric charge of filmTransfer resistance is less, the more effective separation of light induced electron-cavity energy.
Embodiment 2
In the present embodiment, pending waste water is phenolic waste water, and wherein the initial concentration of phenol is 10mg/L.
The present embodiment based on MoS2The method of wastewater treatment of the iron oxide photocatalysis film of doping, locatesReason process is as follows:
Before assaying reaction, the pH of solution, does not regulate the pH of phenol solution to be about 6, carries out photoelectricity and urgesChange degraded. The photocatalysis anode adopting when photoelectrocatalysis is processed comprises conductive substrates and is coated on conductive baseThe MoS of basal surface2The iron oxide photocatalysis film (being made by embodiment 1) of doping, negative electrode is titanium sheet.
When in the present embodiment, photoelectrocatalysis is processed, to applying before operating voltage, also right at photochemical catalyst electrodeProcess waste water and carry out dark adsorption treatment, the dark adsorption treatment time is 30min.
The operating voltage that photoelectrocatalysis is applied between photocatalysis anode and negative electrode while processing is 3V, canSee under light-struck condition and carry out. Reaction time is 4h.
Even for ensureing pending waste water concentration in course of reaction, in photoelectrocatalysis processing procedure,Pending waste water is carried out to magnetic agitation.
Fig. 4 is Fe2O3-MoS2Film and Fe2O3Film (comparative example 1 makes) is under visible ray conditionThe degradation rate comparison diagram of phenol. As shown in Figure 4, under radiation of visible light, Fe2O3-MoS2FilmDegradation effect is apparently higher than Fe2O3Film, is respectively 85.3% and 41.6%. Laminated film (doping)The degradation efficiency of electrode has improved more than 2 times. Electrode photoelectrocatalysis under visible ray after this explanation modificationActivity is significantly improved.
Fig. 5 is Fe2O3-MoS2Film is oxidized in photoelectrocatalysis, photocatalysis and electro-catalysis processThe comparison diagram of the degradation rate of phenol. After reaction 4h, the degradation rate of the phenol under photoelectrocatalysis effect is brightThe aobvious effect higher than simple light and simple electro-catalysis, is respectively 85.3%, 18.8% and 19.2%. ExplanationComposite film electrode is degradation efficiency the best under the effect of photoelectric-synergetic.
Fig. 6 is Fe2O3-MoS2Recycling in film photoelectric catalytic degradation phenol process. By schemingKnown, Fe2O3-MoS2After film circulation degraded 4 times, the degradation rate of phenol remains unchanged substantially, thisShow that it has good photoelectrochemical degradation stability and higher reusing.
Embodiment 3
The operating procedure that repeats embodiment 1 and 2, difference is to prepare MoS2The oxidation of dopingIn the process of iron photocatalysis film, Fe in step (1)2+Precursor solution in Fe2+Source beFerrous acetate.
The Fe preparing under the condition of the present embodiment2O3-MoS2Film photoelectric chemical property is inferior to by realityExecute the Fe that example 1 condition makes2O3-MoS2Film, under visible ray shines, compared to Fe2O3Film (withComparative example 1), the Fe of the present embodiment2O3-MoS2Corresponding the carrying of photoelectric current (being current density) of filmHigh 23 times; Under ultraviolet-visible illumination, photoelectric current (being current density) is corresponding has improved 20Doubly. Under visible ray condition, Pyrogentisinic Acid's degradation rate is 83.2%.
Embodiment 4
The operating procedure that repeats embodiment 1 and 2, difference is to prepare MoS2The oxidation of dopingIn the process of iron photocatalysis film, in step (1), electrodeposition temperature is 50 DEG C.
The Fe preparing under the condition of the present embodiment2O3-MoS2Film photoelectric chemical property is inferior to by realityExecute the Fe that example 1 condition makes2O3-MoS2Film, under visible ray shines, compared to Fe2O3Film (withComparative example 1), the Fe of the present embodiment2O3-MoS2Corresponding the carrying of photoelectric current (being current density) of filmHigh 20 times; Under ultraviolet-visible illumination, photoelectric current (being current density) is corresponding has improved 18Doubly. Under visible ray condition, Pyrogentisinic Acid's degradation rate is 80.2%.
Embodiment 5
The operating procedure that repeats embodiment 1 and 2, difference is to prepare MoS2The oxidation of dopingIn the process of iron photocatalysis film, in step (2), calcining heat is respectively 300 DEG C and 600 DEG C.
The Fe preparing under the condition of the present embodiment2O3-MoS2Film photoelectric chemical property be all inferior to byThe Fe that embodiment 1 condition makes2O3-MoS2Film, in the time that calcining heat is 300 DEG C, crystallinityPoor, uniformity is also poor, and in the time that calcining heat is 600 DEG C, thereby conductive substrates is damaged and causesThe damage of membrane structure. Under visible ray shines, compared to Fe2O3Film, the Fe of the present embodiment2O3-MoS2The photoelectric current (being current density) of film has improved respectively 6 times (300 DEG C) and 10 times (600 DEG C);Under ultraviolet-visible illumination, photoelectric current (being current density) improved respectively 5 times (300 DEG C) and8 times (600 DEG C). Under visible ray condition, Pyrogentisinic Acid's degradation rate is 50.2% (300 DEG C) and 61.2%(600℃)。
Embodiment 6
The operating procedure that repeats embodiment 1 and 2, difference is to prepare MoS2The oxidation of dopingIn the process of iron photocatalysis film, adjust the concentration of molybdenum salt in step (3), adjust molybdenum salt and be0.001M, sylvite (0.04M) and ammonium salt (0.2M) concentration are constant.
The Fe preparing under the condition of the present embodiment2O3-MoS2Film photoelectric chemical property is inferior to by realityExecute the Fe that example 1 condition makes2O3-MoS2Film, under visible ray shines, compared to Fe2O3Film,The Fe of the present embodiment2O3-MoS2The photoelectric current (being current density) of film is corresponding has improved 18 times;Under ultraviolet-visible illumination, photoelectric current (being current density) is corresponding has improved 15 times. At visible rayUnder condition, Pyrogentisinic Acid's degradation rate is 78.2%.
Embodiment 7
The operating procedure that repeats embodiment 1 and 2, difference is to prepare MoS2The oxidation of dopingIn the process of iron photocatalysis film, when the middle electro-deposition of step (4), be 10min and 45min.
The Fe preparing under the condition of the present embodiment2O3-MoS2Film photoelectric chemical property is inferior to by realityExecute the Fe that example 1 condition makes2O3-MoS2Film, tests by linear scan curve, at 0.6V electricityDepress, in the time that sedimentation time shortens to 10min (or being extended for 45min), density of photocurrent is about54.5% (or 45.4%) originally.
Embodiment 8
The operating procedure that repeats embodiment 1 and 2, difference is to prepare MoS2The oxidation of dopingIn the process of iron photocatalysis film, in step (4), the flow velocity of inert gas is set as respectively 50 Hes150mL/min。
The Fe preparing under the condition of the present embodiment2O3-MoS2Film with make by embodiment 1 conditionFe2O3-MoS2Film is compared, when inert gas flow velocity is 50mL/min, and its photoelectrochemical behaviourObviously reduce, also decline to some extent for the degradation rate of phenol accordingly, when inert gas flow is 150ML/min, its photoelectrochemical behaviour and Pyrogentisinic Acid's degradation rate does not change substantially, based on savingBecome the flow velocity of the inert gas in the present embodiment 1 optimum that imposes a condition.
From above embodiment and comparative example, the Fe that the present invention prepares2O3-MoS2PhotocatalysisFilm has excellent visible light catalysis activity, electrocatalysis characteristic and stability.
Above-described detailed description of the invention has been carried out technical scheme of the present invention and beneficial effect in detailDescribe in detail brightly, be understood that and the foregoing is only most preferred embodiment of the present invention, be not limited toThe present invention, all any amendments of making within the scope of principle of the present invention, supplements and is equal to replacement etc.,Within all should being included in protection scope of the present invention.
Claims (10)
1. a MoS2The preparation method of the iron oxide photocatalysis film of doping, is characterized in that, bagDraw together following steps:
Step (1): adopt three-electrode system, with Fe2+Precursor solution as electrolyte, conductionSubstrate is as working electrode, and graphite electrode is to electrode, and Ag/AgCl electrode, as reference electrode, entersRow electro-deposition; Make Fe through calcination processing again2O3Film;
Step (2): with MoS2Precursor solution as electrolyte, make with step (1)Fe2O3Film is working electrode, and titanium sheet is as to electrode, and Ag/AgCl electrode is as reference electrode,Carry out electro-deposition; Then under atmosphere of inert gases, calcining makes Fe2O3-MoS2Film.
2. MoS as claimed in claim 12The preparation method of the iron oxide photocatalysis film of doping,It is characterized in that, in step (1), Fe2+Precursor solution by soluble ferrite and solvent orange 2 AFormulated; Described Fe2+Precursor solution in, Fe2+Molar concentration be 0.01-0.2M; Fe2+Derive from a kind of or many of ferrous nitrate, frerrous chloride, ferrous sulfate, ferrous acetate and ferrous oxalateKind, solvent orange 2 A is one or more in ethylene glycol, deionized water, methyl alcohol and ethanol.
3. MoS as claimed in claim 22The preparation method of the iron oxide photocatalysis film of doping,It is characterized in that Fe2+Precursor solution in, described Fe2+Derive from FeCl2, solvent orange 2 A is secondThe mixed solution of glycol and deionized water, wherein, the volume ratio of ethylene glycol and deionized water is 1:5～12;Fe2+Molar concentration be 0.01～0.04M.
4. MoS as claimed in claim 12The preparation method of the iron oxide photocatalysis film of doping,It is characterized in that, in step (1), electrodeposition temperature is 50～90 DEG C, and electro-deposition voltage is 1～2V;Calcining heat is 300-600 DEG C, and calcination time is 0.5～3h.
5. the MoS as described in claim 1-4 any one2The system of the iron oxide photocatalysis film of dopingPreparation Method, is characterized in that, in step (2), and MoS2Precursor solution by MoS2Front bodyBody and solvent B are formulated, wherein MoS2Precursor be molybdenum salt, sylvite and ammonium salt;
Wherein, molybdenum salt is four thio ammonium molybdate and/or ammonium molybdate; Sylvite is potassium chloride, potash and nitreOne or more of acid potassium; Ammonium salt be a kind of of ammonium chloride, ammonium sulfate, ammonium nitrate and carbonic hydroammonium orMultiple; Solvent B is one or more in formamide, ethylene glycol and methyl alcohol; Wherein, molybdenum salt is denseDegree is 0.001-0.02M.
6. MoS as claimed in claim 52The preparation method of the iron oxide photocatalysis film of doping,It is characterized in that, in step (2), electro-deposition voltage is-0.7～-0.1V; Electrodeposition time is 1～45min.
7. MoS as claimed in claim 62The preparation method of the iron oxide photocatalysis film of doping,It is characterized in that, in step (2), described inert gas is N2And/or argon gas; The stream of inert gasSpeed is 50～150mL/min; Calcining heat is 300～600 DEG C; Calcination time is 0.5～3h.
8. MoS as claimed in claim 72The preparation method of the iron oxide photocatalysis film of doping,It is characterized in that, in step (2), the flow velocity of inert gas is 100mL/min, and calcining heat is400 DEG C; Calcination time is 1h.
9. the MoS that the preparation method described in employing claim 1-8 any one makes2The oxidation of dopingIron photocatalysis film, is characterized in that, described MoS2The thickness of the iron oxide photocatalysis film of dopingFor 200-600nm.
10. utilize the MoS described in claim 92The iron oxide photocatalysis film of doping contains in processingApplication in phenol waste water.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106676565A (en) * | 2016-12-09 | 2017-05-17 | 吉林大学 | Fe2-xTixO3/FTO photo-anode preparing technology and treatment method capable of improving photocurrent density of photo-anode |
| CN106975501A (en) * | 2017-03-10 | 2017-07-25 | 浙江工商大学 | A kind of visible light responsive photocatalytic film and its preparation method and application |
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| CN108031477A (en) * | 2017-10-16 | 2018-05-15 | 浙江工商大学 | A kind of photocatalysis film of electrochemical treatments phosphorus-molybdenum sulfide codope iron oxide and its preparation method and application |
| CN109467958A (en) * | 2017-09-07 | 2019-03-15 | 中国科学院上海硅酸盐研究所 | A kind of Fe2O3 doping molybdenum disulfide coating material and its preparation method and application |
| CN110563095A (en) * | 2019-09-24 | 2019-12-13 | 上海师范大学 | Microwave liquid phase synthesis of MoS2/Fe(1-x)Preparation method and application of S/stainless steel mesh composite electrode |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006110470A (en) * | 2004-10-14 | 2006-04-27 | Ueda Shikimono Kojo:Kk | Water cleaning agent |
| CN104815668A (en) * | 2015-04-27 | 2015-08-05 | 浙江工商大学 | Method for preparing Ta and Al co-doped iron oxide photochemical catalysts |
-
2015
- 2015-12-29 CN CN201511009083.1A patent/CN105597784B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006110470A (en) * | 2004-10-14 | 2006-04-27 | Ueda Shikimono Kojo:Kk | Water cleaning agent |
| CN104815668A (en) * | 2015-04-27 | 2015-08-05 | 浙江工商大学 | Method for preparing Ta and Al co-doped iron oxide photochemical catalysts |
Non-Patent Citations (1)
| Title |
|---|
| HONGGUI WANG ET AL: ""Flower-like Fe2O3@MoS2 nanocomposite decorated glassy carbonelectrode for the determination of nitrite"", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
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| CN108031477B (en) * | 2017-10-16 | 2019-08-27 | 浙江工商大学 | A kind of photocatalysis film and its preparation method and application of electrochemical treatments phosphorus-molybdenum sulfide codope iron oxide |
| CN107930665A (en) * | 2017-10-27 | 2018-04-20 | 浙江工商大学 | A kind of two dimension MoS2Photochemical catalyst of regulation and control and its preparation method and application |
| CN110563095A (en) * | 2019-09-24 | 2019-12-13 | 上海师范大学 | Microwave liquid phase synthesis of MoS2/Fe(1-x)Preparation method and application of S/stainless steel mesh composite electrode |
| CN114457348A (en) * | 2022-01-28 | 2022-05-10 | 厦门稀土材料研究所 | Ordered porous titanium-based iron oxide film photoelectrocatalysis material and preparation method and application thereof |
| CN114457348B (en) * | 2022-01-28 | 2023-08-29 | 厦门稀土材料研究所 | Ordered porous titanium-based ferric oxide film photoelectrocatalysis material and preparation method and application thereof |
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