CN105597784B - MoS2Iron oxide photocatalysis film, preparation method and its application in Phenol-Containing Wastewater Treatment of doping - Google Patents
MoS2Iron oxide photocatalysis film, preparation method and its application in Phenol-Containing Wastewater Treatment of doping Download PDFInfo
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- CN105597784B CN105597784B CN201511009083.1A CN201511009083A CN105597784B CN 105597784 B CN105597784 B CN 105597784B CN 201511009083 A CN201511009083 A CN 201511009083A CN 105597784 B CN105597784 B CN 105597784B
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- 238000007146 photocatalysis Methods 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 21
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 7
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 87
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 85
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000004070 electrodeposition Methods 0.000 claims abstract description 45
- 238000001354 calcination Methods 0.000 claims abstract description 30
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 238000012545 processing Methods 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 36
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 18
- 239000011261 inert gas Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000001103 potassium chloride Substances 0.000 claims description 12
- 235000011164 potassium chloride Nutrition 0.000 claims description 12
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 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 7
- -1 wherein Chemical compound 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 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
- 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
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 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
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 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
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 19
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 110
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 230000015556 catabolic process Effects 0.000 description 19
- 238000006731 degradation reaction Methods 0.000 description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000005286 illumination Methods 0.000 description 6
- 238000011017 operating method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 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
- 239000000126 substance Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002351 wastewater Substances 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
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001548 drop coating Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 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
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 230000006378 damage Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000003760 hair shine Effects 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004506 ultrasonic cleaning 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 kind of MoS2The preparation method of the iron oxide photocatalysis film of doping, comprises the following steps：(1) by Fe2+Precursor solution be electrodeposited in conductive substrates, obtain Fe through calcination processing2O3Film；(2) in Fe made from step (1)2O3Electro-deposition MoS on film2, calcine obtain Fe under an inert atmosphere2O3‑MoS2Photocatalysis film.Present invention additionally comprises using MoS made from the above method2The iron oxide photocatalysis film of doping and the application by using the film in Phenol-Containing Wastewater Treatment.Preparation method of the invention is simple, cost is low.Using photocatalysis film film forming made from the method for electro-deposition is uniform, stability is good, active component is not easy to peel off；Film size is easy to control.Obtained Fe2O3‑MoS2The light induced electron and hole separative efficiency of film are high, have good photoelectric catalytically active.By measure, the photoelectric current of the composite photocatalysis film of preparation is relative to Fe2O3Film improves about 25 times.
Description
Technical field
The present invention relates to photo-electrocatalytic technology field, more particularly to a kind of MoS2The iron oxide photocatalysis film of doping,
Preparation method and its application in Phenol-Containing Wastewater Treatment.
Background technology
The supply of the regenerative resource of nature such as solar energy and wind energy is not continuously, it is therefore desirable to has been taken
Effect ground storage method mismatches relation to balance between production of energy and consumption.As a kind of preferable energy carrier, hydrogen tool
There is cleaning, renewable, fuel value is high and is readily transported.Photo-electrocatalytic technology is handling various environmental problems and energy at present
Huge potentiality are shown in the crisis of source.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, is irradiated in Uv and visible light
Under have preferable photoresponse.But Fe2O3Material shortcoming is that caused light induced electron and hole are easily compound and perishable.Closely
Come, by Fe2O3Catalyst is doped or composite modified suppresses the compound research of its caused photo-generate electron-hole
It is more and more.At present for Fe2O3Be doped or it is composite modified be mostly the metal ion such as Pt, Ag, Si, Ti, Al, Mo, but its
The efficiency of photodissociation aquatic products hydrogen is also than relatively low.And it is used for preparing Fe at present2O3The method of catalyst is mostly hydro-thermal method, and it prepares step
Rapid cumbersome, cycle length.
Publication No. CN104815668A Chinese patent literature discloses a kind of iron oxide photocatalysis of Ta, Al codope
The preparation method of agent, comprises the following steps：(1) with Al3+And Fe2+Precursor solution as electrolyte, conductive substrates are as work
Make electrode, graphite electrode is to carry out electro-deposition as reference electrode to electrode, Ag/AgCl electrodes；(2) by Ta5+Presoma
Then the multiple drop coating of solution is calcined to the conductive substrates handled through step (1) and obtains Ta/Al-Fe2O3Photocatalysis film.
This method is respectively adopted electro-deposition and drop-coating and Ta/Al is doped on iron oxide photocatalysis film, can improve light to a certain degree
Electric current, photocatalytic activity is lifted, but it is limited to lift effect；And obtained photocatalysis film surface is relatively rough, active component is easy
Peel off；Ta/Al-Fe2O3The more difficult control of effective area of photocatalysis film.
The content of the invention
Further to improve the light induced electron and hole separative efficiency of the iron oxide photocatalysis film of doping, photocatalysis is lifted
Activity, the invention provides a kind of MoS2The preparation method of the iron oxide photocatalysis film of doping.
A kind of MoS2The preparation method of the iron oxide photocatalysis film of doping, comprises the following steps：
Step (1)：Using three-electrode system, with Fe2+Precursor solution as electrolyte, conductive substrates are as work electricity
Pole, graphite electrode are to carry out electro-deposition as reference electrode to electrode, Ag/AgCl electrodes；Fe is made through calcination processing again2O3It is thin
Film；
Step (2)：With MoS2Precursor solution as electrolyte, with Fe made from step (1)2O3Film is work electricity
Pole, titanium sheet is used as carries out electro-deposition to electrode, Ag/AgCl electrodes as reference electrode；Then calcined under atmosphere of inert gases
Fe is made2O3-MoS2Film.
The inventive method is by two step electro-deposition by MoS2It is doped into Fe2O3In film, obtained Fe2O3-MoS2Film table
Face is uniform, film size is easy to control；Active material stability is good, is not easy to peel off；MoS2Band gap marginal position is good, electric conductivity
By force.
Moreover, obtained Fe2O3-MoS2Film (MoS2The iron oxide photocatalysis film of doping) light induced electron
It is high with hole separative efficiency, there is good photoelectric catalytically active.
In the present invention, the conductive substrates of step (1) are FTO glass (e.g., specification can be 10mm × 50 mm × 2mm), are being entered
Before the electro-deposition of row step (1), first conductive substrates need to be cleaned, drying and processing.As with acetone, absolute ethyl alcohol and gone successively
Ionized water is cleaned by ultrasonic to FTO glass, dries rear standby.
The precursor solution used in step (1), during electro-deposition is ferrous ion solution, after electro-deposition, in FTO glass
Upper deposition, oxide (such as ferrous hydroxide) film for forming ferrous ion are thin by the iron oxide that trivalent is obtained after calcining
Film.
In step (1), Fe2+Precursor solution be formulated by soluble ferrite and solvent orange 2 A；Soluble ferrite is excellent
Select water-soluble ferrous salt；Solvent orange 2 A preferred alcohols and/or water, described alcohol is preferably with water infinitely than miscible low molecule amount unit alcohol
Or polyalcohol.
The Fe2+Precursor solution in, Fe2+Molar concentration be 0.01-0.2M；Fe2+From ferrous nitrate, chlorine
Change the one or more of ferrous iron, ferrous sulfate, ferrous acetate and ferrous oxalate, solvent orange 2 A be ethylene glycol, deionized water, methanol and
One or more in ethanol.
Preferably, Fe2+Precursor solution in, the Fe2+From FeCl2, solvent orange 2 A is ethylene glycol and deionized water
Mixed solution, wherein, the volume ratio of ethylene glycol and deionized water is 1:5~12；Fe2+Molar concentration for 0.01~
0.04M。
Fe2+Precursor solution in, the mixed solvent of the ethylene glycol and water is advantageous to hydroxide in electrodeposition process
The formation of iron, wherein, the mixed proportion of ethylene glycol and deionized water can also influence the pattern of prepared film, and then influence film
Photocatalysis performance.
Further preferably, Fe2+Precursor solution in, FeCl2Molar concentration be 0.02M, ethylene glycol and deionized water
Volume ratio be 1:6~10.The volume ratio of ethylene glycol and deionized water is most preferably 1:8.
After the completion of step (1) electro-deposition, high-temperature calcination (further oxidation) need to be carried out to the coating of electro-deposition, electro-deposition
Temperature, time and operating voltage can influence the quality of doping, and calcining heat influences the Fe of generation2O3Crystalline phase；Above-mentioned parameter
The photocatalysis performance of doping can all be influenceed.
In the inventive method, film forming effective area can be controlled by regulating and controlling each step electro-deposition parameter.
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, calcination time is 0.5~3h.Under this condition, the electrodeposition time of step (1) is preferably 1-15min.
Under the calcining heat, Fe2O3The Fe of film2O3Crystalline phase is α-Fe2O3, crystallinity is good, and photocatalytic activity is high.
Further preferably, electrodeposition temperature is 70 DEG C, and electro-deposition voltage is 1.36V；Calcining heat is 500 DEG C, during calcining
Between be 2h.In step (1), electrodeposition time is more preferably 5min.
After the completion of step (1) processing, step (2) is carried out, to the Fe of generation2O3Doping molybdenum in film.
Preferably, in step (2), MoS2Precursor solution by MoS2Precursor and solvent B be formulated, wherein
MoS2Precursor be molybdenum salt, sylvite and ammonium salt；
Wherein, molybdenum salt is four thio ammonium molybdate and/or ammonium molybdate；Sylvite is one kind of potassium chloride, potassium carbonate and potassium nitrate
It is or a variety of；Ammonium salt is the one or more of ammonium chloride, ammonium sulfate, ammonium nitrate and ammonium hydrogen carbonate；Solvent B is formamide, ethylene glycol
With the one or more in methanol；Wherein, the concentration of molybdenum salt is 0.001-0.02M.
Further preferably, MoS2Precursor solution in, the concentration of molybdenum salt is 0.001-0.002M.
The MoS2Precursor solution in, described sylvite molar concentration is 0.01-0.1M；Ammonium salt molar concentration is
0.1-0.5M。
Preferably, the MoS2Precursor solution be four thio ammonium molybdate, potassium chloride, ammonium chloride and formamide it is mixed
Solution is closed, wherein, four thio ammonium molybdate molar concentration is 0.002M；Potassium chloride molar concentration is 0.04M；Ammonium chloride molar concentration
For 0.2M.
Preferably, in step (2), electro-deposition voltage is -0.7~-0.1V；Electrodeposition time is 1~45min.
Further preferably, in step (2), electro-deposition voltage is -0.6V；Electrodeposition time is 15min.
Calcination processing is carried out again after the completion of step (2) electro-deposition.
Calcination processing is carried out under atmosphere of inert gases, is advantageous to the generation of molybdenum disulfide.Inert gas flow velocity is to two sulphur
The production tool for changing molybdenum has a certain impact.Such as, in calcination process, because inert gas flow velocity is too low and caused by molybdenum oxide can drop
Low-doped film (MoS2The iron oxide photocatalysis film of doping) photocatalysis performance.
Preferably, in step (2), the inert gas is N2And/or argon gas；The flow velocity of inert gas be 50~
150mL/min；Calcining heat is 300~600 DEG C；Calcination time is 0.5~3h.
The generation of the suitable molybdenum disulfide of calcining heat, and be advantageous to improve film-forming state, improve obtained doping
The photocatalysis performance of film.If calcining heat is too low (as being less than 300 DEG C), the crystallinity of material is poor, it is possible to prepared by limitation
Doping photocatalytic activity.If calcining heat is too high (as being higher than 600 DEG C), temperature exceedes the heat resisting temperature of conductive substrates,
There is destruction to film.
Further preferably, in step (2), the flow velocity of inert gas is 100mL/min, and calcining heat is 400 DEG C；During calcining
Between be 1h.
The photoelectric catalytically active of photocatalysis film is relevant with thickness, the too thick migration for influenceing photo-generated carrier of film.Thickness
Moderate doping can excite the generation of carrier, moreover it is possible to the migration rate of carrier be improved, so as to improve the photoelectricity of doping
Catalytic activity.
In the present invention, the gross thickness of obtained doping is substantially equal to the thin of the formation of electro-deposition twice under the above parameters
The thickness sum of film, obtained film thickness is moderate, and film forming is uniform.
Present invention also offers one kind using MoS made from above-mentioned preparation method2The iron oxide photocatalysis film of doping, make
To be preferred, the MoS2The thickness of the iron oxide photocatalysis film of doping is 200-600nm.
Further preferably, obtained MoS2The thickness of the iron oxide photocatalysis film of doping is 385nm.
Present invention additionally comprises the MoS obtained by a kind of utilization2The iron oxide photocatalysis film Phenol-Containing Wastewater Treatment of doping
Using.
In the present invention, using photocatalysis film film forming made from the method for electro-deposition is uniform, stability is good, active component is not
Easily peel off；Film size is easy to control.Obtained Fe2O3-MoS2The light induced electron and hole separative efficiency of film are high, have good
Good photoelectric catalytically active.By measure, under visible ray photograph, the photoelectric current of the composite photocatalysis film of preparation is relative to Fe2O3
Film improves about 25 times；Under ultraviolet-visible illumination, photoelectric current is relative to Fe2O3Film improves about 22 times.
Brief description of the drawings
Fig. 1 a are Fe2O3-MoS2Film and Fe2O3Visible ray of the film in 0.2M NaOH solutions is according to linear under alternating
Scan volt-ampere curve；
Fig. 1 b are Fe2O3-MoS2Film and Fe2O3Ultraviolet-visible ray of the film in 0.2M NaOH solutions is according under alternating
Linear sweep voltammetry curve；
Fig. 2 is Fe2O3-MoS2Film and Fe2O3Film is in 0.2M NaOH solutions in the dark state to negative voltage scanning direction
Linear sweep voltammetry curve；
Fig. 3 a are Fe2O3-MoS2Film and Fe2O3AC impedance figure under dark conditions of the film in 0.2M NaOH solutions；
Fig. 3 b are Fe2O3-MoS2Film and Fe2O3AC impedance under visible light conditions of the film in 0.2M NaOH solutions
Figure；
Fig. 4 is Fe2O3-MoS2Film and Fe2O3The degradation rate of film phenol under visible light compares figure；
Fig. 5 is Fe2O3-MoS2The comparison figure of the degradation rate of film photoelectric catalysis, photocatalysis and electrocatalytic oxidation phenol；
Fig. 6 is to recycle Fe2O3-MoS2The degradation rate schematic diagram of phenol in film photoelectric catalytic degradation phenol process.
Embodiment
Below in conjunction with accompanying drawing and instantiation, the present invention will be described in detail.
Embodiment 1
(1) with Fe2+Precursor solution (Fe2+From FeCl2) electrolyte is used as, after over cleaning, drying and processing
Conductive substrates as working electrode, graphite electrode is to electrode, and Ag/AgCl electrodes are used as reference electrode, progress electro-deposition.
Conductive substrates in the present embodiment are FTO glass (specification is 10mm × 50mm × 2mm), are used successively before preparing film
Acetone, absolute ethyl alcohol and deionized water carry out ultrasonic cleaning 10min, then take out and dry.
The thickness of film that electro-deposition obtains is controlled by electro-deposition process parameter, electro-deposition process parameter in the present embodiment
It is as follows：Electrodeposition temperature is 70 DEG C, operating voltage 1.36V, sedimentation time 5min.
(2) conductive substrates and then by step (1) deposited are put into Muffle furnace, and calcining 2h is carried out at 500 DEG C and is obtained
Fe2O3Photocatalysis film (Fe2O3Film).
(3) formamide solution for containing a certain amount of four thio ammonium molybdate, potassium chloride and ammonium chloride is prepared as MoS2's
Precursor solution.Wherein, four thio ammonium molybdate molar concentration is 0.002M；Potassium chloride molar concentration is 0.04M；Ammonium chloride mole
Concentration is 0.2M.
(4) deposition there is into Fe2O3FTO (the Fe made from step (2) of film2O3Film) opposed as working electrode, titanium sheet
Electrode, Ag/AgCl electrodes make reference electrode.The thickness of the film obtained by electro-deposition process parameter control electro-deposition, wherein,
Voltage is -0.6V, time 15min.Dry, then the FTO deposited is put into tube furnace, is passed through N2, N2Flow velocity be
100mL/min, 400 DEG C are warming up to 2 DEG C/min, calcines 1h.Obtain Fe2O3-MoS2Film, it is 385nm to estimate film thickness.
Comparative example 1
For ease of carrying out performance comparison, contrast Fe is prepared by the following method2O3Film, specific preparation method are as follows：
Using three-electrode structure, using FTO as working electrode, graphite is made to make reference electrode to electrode, Ag/AgCl, 70
DEG C, electro-deposition is carried out under the conditions of 1.36V, sedimentation time 5min, deposition liquid is the FeCl prepared2Solution (with embodiment 1).
After electro-deposition, after its naturally dry, it is put into Muffle furnace, 2h is calcined at 500 DEG C and obtains Fe2O3It is thin
Film.
Fig. 1 a are Fe made from embodiment 12O3-MoS2Film and Fe2O3Film (being made by comparative example 1) is in radiation of visible light
Under linear sweep voltammetry curve.
Fig. 1 b are Fe made from embodiment 12O3-MoS2Film and Fe2O3Film (being made by comparative example 1) is in ultraviolet-visible
Linear sweep voltammetry curve under light irradiation.
From Fig. 1 a, under visible ray photograph, compared to Fe2O3Film, MoS2Doping cause photoelectric current (i.e. electric current be close
Degree) accordingly improve 25 times.That is MoS2Incorporation have impact on the catalytic activity of film.From Fig. 1 b, in ultraviolet-visible illumination
Under, compared to Fe2O3Film, MoS2Doping cause photoelectric current (i.e. current density) accordingly to improve 22 times.Understand, do not having
Under the conditions of sacrifice agent is existing, MoS2Be entrained in lifting Fe2O3Highly significant in terms of the photoelectric catalytically active of film.From Fig. 1 a
With in Fig. 1 b it will be evident that for simple Fe2O3Film, in the moment that visible ray or ultraviolet-visible are blocked or shown,
Photoelectric current can be rapidly reached maximum, then just decay to certain value, and this is due to Fe2O3Compound larger, the photoproduction of film in itself
Electronics and hole are soon compound once producing.And adulterate MoS2Be not in then such a phenomenon afterwards, this explanation MoS2In Fe2O3
Film surface can suppress the compound of light induced electron and hole.
Fig. 2 is the Fe that embodiment 1 is prepared2O3-MoS2Film and Fe2O3Film (being made by comparative example 1) is in 0.2M
The linear sweep voltammetry curve that NaOH solution scans since negative direction.It is 5mV/s to sweep speed.From figure 2 it can be seen that Fe2O3-
MoS2Film produces hydrogen take-off potential relative to Fe2O3Film shuffles 0.1V, and Fe2O3-MoS2Film is in -0.18V vs.Ag/AgCl
When photoelectric current be 0.052mA/cm2, and Fe2O3Film needs -0.4V vs.Ag/AgCl up to this Current Voltage.MoS2Doping make
Hydrogen position must be produced to shuffle, illustrate Fe2O3-MoS2Film is compared to Fe2O3Film is more easy to photodissociation aquatic products hydrogen, hence it is evident that it is thin to improve photocatalysis
The photoelectric catalytically active of film.
Fig. 3 a and Fig. 3 b are the Fe that embodiment 1 is prepared2O3-MoS2Film and Fe2O3Film (being made by comparative example 1) exists
In 0.2M NaOH solutions, respectively in the dark with the electrochemical impedance collection of illustrative plates (EIS collection of illustrative plates) under visible light conditions.Electrochemical operation
The frequency range set of standing is 106Hz-0.01Hz.Bar (b, is either still shone in visible ray dark from Fig. 3 a, Fig. 3
Under part, Fe2O3-MoS2The impedance ring radius of film is all significantly less than Fe2O3Film.Understand, Fe2O3-MoS2The electric charge transfer of film
Resistance is smaller, and photo-generate electron-hole can be separated more effectively.
Embodiment 2
Pending waste water is phenolic waste water in the present embodiment, 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, processing procedure are as follows：
The pH of solution before measure reaction, i.e., the pH for not adjusting phenol solution is about 6, carries out photoelectric catalysis degrading.Photoelectricity is urged
Changing the photocatalysis anode used during processing includes conductive substrates and is coated on the MoS on conductive substrates surface2The iron oxide light of doping
Catalytic film (is made) by embodiment 1, and negative electrode is titanium sheet.
When photoelectrocatalysis is handled in the present embodiment, before photochemical catalyst electrode is to applying operating voltage, also processing waste water is entered
The dark adsorption treatment of row, the dark adsorption treatment time is 30min.
The operating voltage being applied to during photoelectrocatalysis processing between photocatalysis anode and negative electrode is 3V, it is seen that the bar of light irradiation
Carried out under part.Reaction time is 4h.
To ensure pending waste water even concentration during the course of the reaction, in photoelectrocatalysis processing procedure, to pending useless
Water carries out magnetic agitation.
Fig. 4 is Fe2O3-MoS2Film and Fe2O3Film (comparative example 1 is made) degradation rate ratio of phenol under visible light conditions
Compared with figure.As shown in Figure 4, under visible light illumination, Fe2O3-MoS2The degradation effect of film is apparently higher than Fe2O3Film, it is respectively
85.3% and 41.6%.The degradation efficiency of laminated film (doping) electrode is improved more than 2 times.This illustrates modified electrode
Photoelectric catalytically active is significantly improved under visible light.
Fig. 5 is Fe2O3-MoS2Film degradation rate of oxidation of phenol during photoelectrocatalysis, photocatalysis and electro-catalysis
Compare figure.After reacting 4h, the degradation rate of the phenol under photoelectrocatalysis effect apparently higher than simple light and the effect of simple electro-catalysis,
Respectively 85.3%, 18.8% and 19.2%.Illustrate that composite film electrode degradation efficiency in the presence of photoelectric-synergetic is optimal.
Fig. 6 is Fe2O3-MoS2Recycling in film photoelectric catalytic degradation phenol process.As seen from the figure, Fe2O3-MoS2
Film circulation degraded 4 times after, the degradation rate of phenol is held essentially constant, this show its have good photoelectrochemical degradation stability and
Higher reusing.
Embodiment 3
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare MoS2The iron oxide photocatalysis film of doping
During, Fe in step (1)2+Precursor solution in Fe2+Source be ferrous acetate.
The Fe prepared under conditions of the present embodiment2O3-MoS2Film photoelectric chemical property is inferior to by the condition system of embodiment 1
The Fe obtained2O3-MoS2Film, under visible ray photograph, compared to Fe2O3Film (with comparative example 1), the Fe of the present embodiment2O3-MoS2
The photoelectric current (i.e. current density) of film accordingly improves 23 times；Under ultraviolet-visible illumination, photoelectric current (i.e. current density) phase
20 times should be improved.The degradation rate of Pyrogentisinic Acid is 83.2% under visible light conditions.
Embodiment 4
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare MoS2The iron oxide photocatalysis film of doping
During, electrodeposition temperature is 50 DEG C in step (1).
The Fe prepared under conditions of the present embodiment2O3-MoS2Film photoelectric chemical property is inferior to by the condition system of embodiment 1
The Fe obtained2O3-MoS2Film, under visible ray photograph, compared to Fe2O3Film (with comparative example 1), the Fe of the present embodiment2O3-MoS2
The photoelectric current (i.e. current density) of film accordingly improves 20 times；Under ultraviolet-visible illumination, photoelectric current (i.e. current density) phase
18 times should be improved.The degradation rate of Pyrogentisinic Acid is 80.2% under visible light conditions.
Embodiment 5
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare MoS2The iron oxide photocatalysis film of doping
During, calcining heat is respectively 300 DEG C and 600 DEG C in step (2).
The Fe prepared under conditions of the present embodiment2O3-MoS2Film photoelectric chemical property is inferior to by the condition of embodiment 1
Obtained Fe2O3-MoS2Film, when calcining heat is 300 DEG C, crystallinity is poor, and uniformity is also poor, when calcining heat is
At 600 DEG C, conductive substrates are by destroying so as to causing membrane structure to be damaged.Under visible ray photograph, compared to Fe2O3Film, this reality
Apply the Fe of example2O3-MoS26 times (300 DEG C) and 10 times (600 DEG C) have been respectively increased in the photoelectric current (i.e. current density) of film；In purple
Under outside-visible ray shines, 5 times (300 DEG C) and 8 times (600 DEG C) have been respectively increased in photoelectric current (i.e. current density).In visible striation
The degradation rate of Pyrogentisinic Acid is 50.2% (300 DEG C) and 61.2% (600 DEG C) under part.
Embodiment 6
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare MoS2The iron oxide photocatalysis film of doping
During, the concentration of adjustment molybdenum salt in step (3), that is, it is 0.001M to adjust molybdenum salt, and sylvite (0.04M) and ammonium salt (0.2M) are dense
Spend constant.
The Fe prepared under conditions of the present embodiment2O3-MoS2Film photoelectric chemical property is inferior to by the condition system of embodiment 1
The Fe obtained2O3-MoS2Film, under visible ray photograph, compared to Fe2O3Film, the Fe of the present embodiment2O3-MoS2The photoelectric current of film
(i.e. current density) accordingly improves 18 times；Under ultraviolet-visible illumination, photoelectric current (i.e. current density) accordingly improves 15
Times.The degradation rate of Pyrogentisinic Acid is 78.2% under visible light conditions.
Embodiment 7
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare MoS2The iron oxide photocatalysis film of doping
During, during electro-deposition it is 10min and 45min in step (4).
The Fe prepared under conditions of the present embodiment2O3-MoS2Film photoelectric chemical property is inferior to by the condition system of embodiment 1
The Fe obtained2O3-MoS2Film, tested by linear scan curve, under 0.6V voltages, when deposited between shorten to 10min (or
It is extended for 45min) when, density of photocurrent is about 54.5% original (or 45.4%).
Embodiment 8
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare MoS2The iron oxide photocatalysis film of doping
During, the flow velocity of inert gas is respectively set as 50 and 150mL/min in step (4).
The Fe prepared under conditions of the present embodiment2O3-MoS2Film and the Fe as made from the condition of embodiment 12O3-MoS2It is thin
Film is compared, and when inert gas flow velocity is 50mL/min, its photoelectrochemical behaviour substantially reduces, accordingly for the degradation rate of phenol
Also declined, when inert gas flow is 150 mL/min, the degradation rate of its photoelectrochemical behaviour and Pyrogentisinic Acid do not have substantially
Change, the flow rate set condition based on the inert gas in cost-effective embodiment 1 is optimal.
The Fe being prepared from above example and comparative example, the present invention2O3-MoS2Photocatalysis film has excellent
Visible light catalysis activity, electrocatalysis characteristic and stability.
Technical scheme and beneficial effect are described in detail above-described embodiment, Ying Li
Solution is to the foregoing is only presently most preferred embodiment of the invention, is not intended to limit the invention, all principle models in the present invention
Interior done any modification, supplement and equivalent substitution etc. are enclosed, should be included in the scope of the protection.
Claims (10)
- A kind of 1. MoS2The preparation method of the iron oxide photocatalysis film of doping, it is characterised in that comprise the following steps：Step (1)：Using three-electrode system, with Fe2+Precursor solution as electrolyte, conductive substrates as working electrode, Graphite electrode is to carry out electro-deposition as reference electrode to electrode, Ag/AgCl electrodes；Fe is made through calcination processing again2O3Film；Step (2)：With MoS2Precursor solution as electrolyte, with Fe made from step (1)2O3Film is working electrode, titanium Piece is used as carries out electro-deposition to electrode, Ag/AgCl electrodes as reference electrode；Then calcine and be made under atmosphere of inert gases Fe2O3-MoS2Film.
- 2. MoS as claimed in claim 12The preparation method of the iron oxide photocatalysis film of doping, it is characterised in that step (1) In, Fe2+Precursor solution be formulated by soluble ferrite and solvent orange 2 A；The Fe2+Precursor solution in, Fe2+'s Molar concentration is 0.01-0.2M；Fe2+From ferrous nitrate, frerrous chloride, ferrous sulfate, ferrous acetate and ferrous oxalate One or more, solvent orange 2 A are the one or more in ethylene glycol, deionized water, methanol and ethanol.
- 3. MoS as claimed in claim 22The preparation method of the iron oxide photocatalysis film of doping, it is characterised in that Fe2+'s In precursor solution, the Fe2+From FeCl2, solvent orange 2 A is the mixed solution of ethylene glycol and deionized water, wherein, ethylene glycol Volume ratio with 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 characterised in that step (1) In, electrodeposition temperature is 50~90 DEG C, and electro-deposition voltage is 1~2V；Calcining heat be 300-600 DEG C, calcination time be 0.5~ 3h。
- 5. the MoS as described in claim any one of 1-42The preparation method of the iron oxide photocatalysis film of doping, its feature exist In, in step (2), MoS2Precursor solution by MoS2Precursor and solvent B be formulated, wherein MoS2Precursor be Molybdenum salt, sylvite and ammonium salt；Wherein, molybdenum salt is four thio ammonium molybdate；Sylvite is the one or more of potassium chloride, potassium carbonate and potassium nitrate；Ammonium salt is chlorine Change the one or more of ammonium, ammonium sulfate, ammonium nitrate and ammonium hydrogen carbonate；Solvent B be formamide, ethylene glycol and methanol in one kind or It is a variety of；Wherein, the concentration of molybdenum salt is 0.001-0.02M.
- 6. MoS as claimed in claim 52The preparation method of the iron oxide photocatalysis film of doping, it is characterised in that step (2) In, 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 characterised in that step (2) In, the inert gas is N2And/or argon gas；The flow velocity of inert gas is 50~150mL/min；Calcining heat is 300~600 ℃；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 characterised in that step (2) In, the flow velocity of inert gas is 100mL/min, and calcining heat is 400 DEG C；Calcination time is 1h.
- 9. using MoS made from the preparation method described in claim any one of 1-82The iron oxide photocatalysis film of doping, it is special Sign is, the MoS2The thickness of the iron oxide photocatalysis film of doping is 200-600nm.
- 10. utilize the MoS described in claim 92Application of the iron oxide photocatalysis film of doping in Phenol-Containing Wastewater Treatment.
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| CN106975501B (en) * | 2017-03-10 | 2020-01-07 | 浙江工商大学 | Visible light response type photocatalytic film and preparation method and application thereof |
| CN107096546B (en) * | 2017-03-15 | 2019-06-25 | 浙江工商大学 | A kind of iron oxide-bismuth oxide-bismuth sulfide visible light catalytic film and its preparation method and application |
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| CN107020103B (en) * | 2017-03-20 | 2019-05-31 | 浙江工商大学 | A kind of iron oxide-molybdenum sulfide-cuprous oxide photocatalysis film and its preparation method and application |
| CN107185519A (en) * | 2017-05-25 | 2017-09-22 | 浙江工业职业技术学院 | A kind of preparation method of high-performance tungsten oxide photcatalyst |
| CN109467958B (en) * | 2017-09-07 | 2021-04-16 | 中国科学院上海硅酸盐研究所 | Iron-doped molybdenum disulfide coating material and preparation method and application thereof |
| 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 |
| CN107930665B (en) * | 2017-10-27 | 2019-10-01 | 浙江工商大学 | A kind of two dimension MoS2Photochemical catalyst of regulation 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 |
| 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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