CN107096546B - A kind of iron oxide-bismuth oxide-bismuth sulfide visible light catalytic film and its preparation method and application - Google Patents
A kind of iron oxide-bismuth oxide-bismuth sulfide visible light catalytic film and its preparation method and application Download PDFInfo
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- CN107096546B CN107096546B CN201710153919.8A CN201710153919A CN107096546B CN 107096546 B CN107096546 B CN 107096546B CN 201710153919 A CN201710153919 A CN 201710153919A CN 107096546 B CN107096546 B CN 107096546B
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- -1 iron oxide-bismuth oxide-bismuth sulfide Chemical compound 0.000 title claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 142
- 238000004070 electrodeposition Methods 0.000 claims abstract description 69
- 238000001354 calcination Methods 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 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000012545 processing Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 14
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 16
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 9
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XEYZSEWPHLWVLQ-UHFFFAOYSA-N [O-2].[Fe+2].[Bi+]=O Chemical compound [O-2].[Fe+2].[Bi+]=O XEYZSEWPHLWVLQ-UHFFFAOYSA-N 0.000 claims 6
- 239000010408 film Substances 0.000 abstract description 181
- 239000010409 thin film Substances 0.000 abstract description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000470 constituent Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 54
- 230000000052 comparative effect Effects 0.000 description 49
- 239000000243 solution Substances 0.000 description 48
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000002131 composite material Substances 0.000 description 12
- 238000011017 operating method Methods 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 11
- 238000007146 photocatalysis Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910052797 bismuth Inorganic materials 0.000 description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 4
- 206010011224 Cough Diseases 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 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
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- B01J35/39—
-
- B01J35/59—
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of iron oxide-bismuth oxide-bismuth sulfide visible light catalytic film preparation methods: (1) with Fe2+Precursor solution as electrolyte, conductive substrates are that Fe is made in calcination processing after working electrode carries out electro-deposition using three-electrode system2O3Film；(2) with Bi3+Precursor solution as electrolyte, Fe2O3Film carries out electro-deposition using three-electrode system as working electrode, and dry be placed in thiourea solution carries out hydro-thermal reaction, washed obtained Fe2O3‑Bi2O3‑Bi2S3Visible light catalytic film.The invention also includes using Fe made from the above method2O3‑Bi2O3‑Bi2S3Visible light catalytic film and utilize application of the film in Phenol-Containing Wastewater Treatment.Gained visible light catalytic forming thin film is uniform, and stability is good, and active constituent is not easy to peel off, and light induced electron and hole separative efficiency are high, has good photoelectric catalytically active.
Description
Technical field
The present invention relates to photoelectrocatalysimaterial material technical field, in particular to a kind of Fe of efficient visible light response2O3-
Bi2O3-Bi2S3Photocatalysis film and its preparation method and application.
Background technique
Problem of environmental pollution is increasingly by the concern of all circles, and how high-efficiency cleaning processing pollutant becomes grinding instantly
Study carefully hot spot.There is photo-electrocatalytic technology advantages, the key such as efficient, cleaning, without secondary pollution to be to prepare urging for efficient stable
Agent.
In novel photochemical catalyst, Fe2O3It is a kind of very promising semiconductor for transition metal oxide
Material, forbidden bandwidth is small (Eg=2.20eV), all shows stronger optical electro-chemistry response in Uv and visible light region.But
It is compound to be that its light induced electron and hole easily occur, and photoelectric activity is caused to reduce.In this regard, many method of modifying come into being, it is such as non-
Metal/metal doping, semiconductors coupling etc..Bismuth-containing visible light catalyst also visible light catalysis activity with higher, Bi2O3Energy
Gap band is 2.8eV, and absorbing wavelength is longer, it is seen that the utilization rate of light is higher.
The Chinese patent literature of Publication No. CN105344364A disclose a kind of iron oxide/bismuth oxybromide composite material and
Preparation method and application.The preparation method includes: that aqueous slkali is added in iron nitrate solution, and it is molten to obtain ferric hydroxide colloid
Liquid；KBr solution is added in bismuth nitrate solution and is mixed, mixed solution is obtained；Ferric hydroxide colloid solution is added dropwise to mixed
It closes in solution and carries out hydro-thermal reaction, obtain iron oxide/bismuth oxybromide composite material.The preparation method have preparation process it is simple,
It is at low cost, have many advantages, such as good environmental benefit, the composite material of preparation has superior photocatalysis performance, is widely used in
Photocatalytic degradation of dye waste water field, and higher catalytic efficiency can be obtained.
The Chinese patent literature of Publication No. CN102824917A discloses a kind of iron oxide/bismuth tungstate composite photocatalyst
And the preparation method and application thereof.The invention is by dipping-low-temperature bake technology in Bi2WO6Surface deposited 10~30nm's
Fe2O3Nano particle, prepared Fe2O3/Bi2WO6The photocatalytic activity of composite material is than pure Bi2WO6It is significantly improved, promotes
It is in the practical application potentiality of aspect of curbing environmental pollution, it may also be used for the desulfurization of photocatalysis gasoline and photocatalysis biological sterilization etc..
The Chinese patent literature of 102500390 A of Publication No. CN discloses a kind of iron oxide/bismuth tungstate composite photocatalyst
The preparation method of agent, the composite photo-catalyst are a kind of powder formed including iron oxide and bismuth tungstate, wherein iron oxide and tungsten
The molar ratio of sour bismuth is 1:2~20, and preparation step includes: by the nitric acid solution of five water bismuth nitrates, the sodium hydroxide of ammonium tungstate
After solution and the mixing of soluble iron salting liquid, it is compound that iron oxide/bismuth tungstate is prepared using the hydro-thermal method of Microwave-assisted firing
Photochemical catalyst.The invention preparation method is simple, at low cost, and the composite photo-catalyst of preparation has excellent catalytic performance, can
Have the function of decomposing harmful chemical, organic biomass conjunction sterilization under light-exposed irradiation.
However, traditional composite photo-catalyst is mostly based on powder, after being reacted in liquid-phase system, in powdered
Catalyst be difficult to separate and recycle, so being difficult to apply in the circulatory system of continuous flowing type.Therefore, it develops
Efficient and stable film-form catalysis material has considerable application prospect.
Summary of the invention
The present invention provides a kind of Fe2O3-Bi2O3-Bi2S3Visible light catalytic film and preparation method thereof solves existing
Fe in technology2O3The technical problem that catalysis material catalytic efficiency is not high, stability is bad, recycling is inconvenient.
A kind of preparation method of iron oxide-bismuth oxide-bismuth sulfide visible light catalytic film, includes the following steps:
(1) with Fe2+Precursor solution as electrolyte, using conductive substrates as working electrode, graphite electrode be to electrode,
Ag/AgCl electrode carries out electro-deposition as reference electrode；Fe is made through calcination processing in working electrode after electro-deposition2O3Film；
(2) with above-mentioned Fe2O3As working electrode, Ti piece is used as to electrode film, Ag/AgCl electrode as reference electrode,
With Bi3+Precursor solution as electrolyte, carry out electro-deposition；The film obtained after electro-deposition is placed in H after drying2NCSNH2
In aqueous solution, hydro-thermal reaction is carried out, after reaction washed obtained Fe2O3-Bi2O3-Bi2S3Visible light catalytic film.
In above-mentioned preparation route, the concrete technology condition of each step is as follows:
(1) in step (1):
The conductive substrates are electro-conductive glass (FTO) etc..
Pre-cleaning, drying conductive substrates are needed before electro-deposition.
The Fe2+Precursor solution be formulated by soluble ferrite and solvent A, soluble ferrite can be nitric acid
Ferrous iron, frerrous chloride, ferrous sulfate, ferrous acetate or ferrous oxalate etc., solvent A are ethylene glycol, methanol, one in second alcohol and water
Kind is several.Preferably, soluble ferrite is frerrous chloride, solvent A is the mixed liquor of ethylene glycol and water, ethylene glycol and water
Volume ratio be 1:4~12.
Preferably, the Fe2+Precursor solution in Fe2+Molar concentration is 0.01~0.2M.
The photoelectric catalytically active of photocatalysis film is largely related with film thickness, and film thickness is too thin or too thick,
It will affect the migration of the photolytic activity and photo-generated carrier of film, and only when film thickness is moderate, light not only excites generation
Carrier, and the migration rate of carrier can be improved, to improve the photoelectric catalytically active of film.
The overall thickness of photocatalyst film is substantially equal to the film thickness of electro-deposition formation in preparation method of the invention
The sum of the film thickness formed with hydro-thermal method.Temperature, time and the operating voltage of electro-deposition are directly related to the production of electrolytic deposition
The quality (i.e. the thickness of electrodeposited film) of object and the product of formation.After the completion of electro-deposition, the further oxygen of high-temperature calcination need to be passed through
Change, and calcination temperature and time also directly affect the Fe of generation2O3Crystal phase, so as to influence the photocatalysis performance of composite membrane.
Film forming effective area and quality can be controlled by regulation electro-deposition parameter and calcination parameter.
Preferably, in step (1), the temperature of electro-deposition is 40~90 DEG C, and the voltage of electro-deposition is 1~2V, electro-deposition
Time is 0.5~10min；
Further preferably, in step (1), the temperature of electro-deposition is 60~80 DEG C, and the voltage of electro-deposition is 1~1.5V, electricity
The time of deposition is 4~6min.The thickness for the catalytic film that electro-deposition obtains, film thickness are controlled by electro-deposition process parameter
It is too thin, it cannot be fully absorbed light, and when as substrate, its catalytic activity cannot be given full play to；Film is too thick, influences photoproduction load
Flow the migration of son.When film thickness is moderate, light, which not only excites, generates carrier, and can improve the migration rate of carrier, from
And improve the photoelectric catalytically active of film.
Preferably, the temperature of the calcination processing is 400~600 DEG C, and calcination time is 1~5h；Further preferably, it calcines
The temperature of processing is 450~550 DEG C, and calcination time is 1~3h.
Preferably, the temperature of the calcination processing is 400~600 DEG C, and calcination time is 1~5h；Further preferably, it calcines
The temperature of processing is 450~550 DEG C, and calcination time is 1~3h, and the knot of catalytic film is controlled by calcining at constant temperature temperature and time
Brilliant degree.Under preferred calcination temperature, material has good crystallinity, and crystal phase is α-Fe2O3, photocatalytic activity is higher.When forging
When burning temperature is lower, the crystallinity of material is very poor, greatly limitation photocatalytic activity；It, can be because of conduction when calcination temperature is excessively high
The heat resisting temperature of substrate limits and influences the formation of film.
(2) in step (2):
The Bi3+Precursor solution the preparation method is as follows: KI is soluble in water, Bi (NO is added3)3·5H2O, stirring
Adjusting pH value afterwards is 1.5~2.0, and 1,4-benzoquinone is added, is again stirring for obtaining Bi3+Precursor solution.
Preferably, use mass fraction for 68~70% HNO3Adjust pH value；
Preferably, the Bi3+Precursor solution in, the concentration of KI is 300~500mM, Bi (NO3)3·5H2The concentration of O
For 20~60mM；Further preferably, the concentration of KI is 350~450mM, Bi (NO3)3·5H2The concentration of O is 30~50mM；It is optimal
Selection of land, the concentration of KI are 400mM, Bi (NO3)3·5H2The concentration of O is 40mM；
Preferably, pH to 1~2 is adjusted, the concentration of 1,4-benzoquinone is 30~70mM；Further preferably, adjust pH to 1.5~
2.0, the concentration of 1,4-benzoquinone is 40~60mM；Most preferably, pH to 1.75 is adjusted, the concentration of 1,4-benzoquinone is 50mM.
Preferably, in step (2), the voltage of electro-deposition is -0.3~0.2V, and the time of electro-deposition is 3~8min；Into one
Preferably, electro-deposition voltage is -0.1~0.1V to step in the step, and electrodeposition time is 5~8min.
Preferably, when carrying out hydro-thermal reaction, the conduction of film is up, under the effect of gravity, conductive more advantageous up
In natural subsidence, film surface obtained is uniform；When conductive face-down, composite layer is grown unevenly on the base layer, thus
The photoelectric properties of film are influenced to a certain extent.
Preferably, the H2NCSNH2The concentration of aqueous solution is 10~30mM, and additional amount, which is subject to, is totally submerged film, can
It is appropriate according to the actual situation to adjust, H2NCSNH2The concentration of aqueous solution determines formed a film thickness and form etc., film forming thickness mistake
Thickness understands the function of other materials on cover film.
Preferably, the temperature of the hydro-thermal reaction is 200~240 DEG C, and the time of hydro-thermal reaction is 1~4h.
The present invention also provides a kind of Fe prepared by the above method2O3-Bi2O3-Bi2S3Visible light catalytic film.
The overall thickness of photocatalyst film is substantially equal to the film thickness of electro-deposition formation in preparation method of the invention
The sum of the film thickness formed with hydro-thermal method.
Gained Fe2O3-Bi2O3-Bi2S3Visible light catalytic film with a thickness of 450~600nm.
Obtained Fe is utilized the invention also includes a kind of2O3-Bi2O3-Bi2S3Visible light catalytic film Phenol-Containing Wastewater Treatment
In application.
Substrate Fe is controlled in preparation method of the invention by adjusting the temperature of electro-deposition, time and operating voltage2O3It is thin
The thickness and Bi of film2O3Thickness, control Bi by adjusting the temperature of hydro-thermal reaction, time, concentration2S3Thickness, to obtain
Obtain medium thin Fe2O3-Bi2O3-Bi2S3Visible light catalytic thin-film material makes it that can fully absorb light, generates higher concentration
Photo-generated carrier, and the migration rate of carrier can be improved, show higher photoelectric catalytically active.
Compared with prior art, beneficial effects of the present invention:
(1) by measurement, under visible light photograph, with simple Fe2O3Film is compared, the Fe of preparation2O3-Bi2O3-Bi2S3It can
The photoelectric current of light-exposed catalytic film improves 8 times.Bi2O3-Bi2S3Layer is in Fe2O3Building on film altogether, especially Bi2S3Layer, makes
Obtain Fe2O3-Bi2O3-Bi2S3The photo-generate electron-hole of film more effectively separates, and improves the transfer rate and light of photo-generated carrier
Transformation efficiency, not only promotes the promotion of photoelectric properties, but also substantially increases the stability of catalyst.
(2) synergistic effect of general electrodeposition process and hydro-thermal method, visible light catalytic forming thin film obtained uniformly, stability
Good, active constituent is not easy to peel off, and film size is easy to control.
(3) Fe obtained by2O3-Bi2O3-Bi2S3The light induced electron and hole separative efficiency of visible light catalytic film are high, tool
There is good photoelectric catalytically active.
Detailed description of the invention
Fig. 1 is Fe made from embodiment 12O3-Bi2O3-Bi2S3Visible light catalytic film, Bi made from comparative example 32O3-
Bi2S3Film, Fe made from comparative example 22O3Bi made from film and comparative example 42O3Film is visible in 0.1M NaOH solution
Linear sweep voltammetry curve under illumination alternately；
Fig. 2 is Fe made from embodiment 12O3-Bi2O3-Bi2S3Visible light catalytic film, Fe made from comparative example 12O3-
Bi2O3Fe made from film and comparative example 22O3Film linearly sweeping under the UV, visible light illumination in 0.1M NaOH solution alternately
Retouch volt-ampere curve；
Fig. 3 is Fe made from embodiment 12O3-Bi2O3-Bi2S3Visible light catalytic film in 0.1M NaOH solution can
It is light-exposed to shine alternately lower continuous scanning 4 times linear volt-ampere curves；
Fig. 4 is Bi made from comparative example 32O3-Bi2S3Film is continuous in the case where the visible light in 0.1M NaOH solution is according to alternating
The linear volt-ampere curve that scanning is 4 times；
Fig. 5 is Fe made from embodiment 12O3-Bi2O3-Bi2S3Fe made from visible light catalytic film, comparative example 12O3-
Bi2O3Fe made from film and comparative example 22O3Electrochemical impedance map of the film in 0.1M NaOH solution under dark condition
(EIS map)；
Fig. 6 is Fe made from embodiment 12O3-Bi2O3-Bi2S3Fe made from visible light catalytic film, comparative example 12O3-
Bi2O3Fe made from film and comparative example 22O3Electrochemical impedance figure of the film in 0.1M NaOH solution under visible light conditions
It composes (EIS map)；
Fig. 7 is Fe obtained in comparative example 22O3Film is in 0.1M NaOH solution, respectively in 500Hz, 700Hz,
Mott-Schottky curve under the conditions of 1000Hz；
Fig. 8 is Fe obtained in comparative example 12O3-Bi2O3Film is in 0.1M NaOH solution, respectively in 500Hz, 700Hz,
Mott-Schottky curve under the conditions of 1000Hz；
Fig. 9 is Fe obtained in embodiment 12O3-Bi2O3-Bi2S3Visible light catalytic film divides in 0.1M NaOH solution
Mott-Schottky curve not under the conditions of 500Hz, 700Hz, 1000Hz；
Figure 10 is Fe made from embodiment 12O3-Bi2O3-Bi2S3Fe made from visible light catalytic film, comparative example 12O3-
Bi2O3Fe made from film and comparative example 22O3Film is in 0.1M Na2SO4+0.1M Na2SO3Incident photon-to-electron conversion efficiency in solution
(IPCE) figure；
Figure 11 is Fe made from embodiment 12O3-Bi2O3-Bi2S3Fe made from visible light catalytic film, comparative example 12O3-
Bi2O3Fe made from film and comparative example 22O3Instantaneous photocurrent-time curve of the film in 0.1M NaOH solution.
Specific embodiment
Below in conjunction with attached drawing and specific example, the present invention will be described in detail.
Embodiment 1
(1) with Fe2+Precursor solution as electrolyte, the conductive substrates after over cleaning, drying and processing are as work
Make electrode, graphite electrode is to electrode, and Ag/AgCl electrode carries out electro-deposition as reference electrode.
Conductive substrates in the present embodiment are FTO glass (specification is 10mm × 50mm × 2mm), before electro-deposition successively
Ultrasonic cleaning 10min is carried out with acetone, dehydrated alcohol and deionized water, then takes out and dries.
Fe in this embodiment2+Precursor solution be containing FeCl2·4H2The ethylene glycol solution of O, Fe2+Presoma it is molten
In liquid, Fe2+Molar concentration be 0.025M, solvent be ethylene glycol and distilled water mixed liquor, the volume of ethylene glycol and distilled water
Than being prepared via a method which to obtain: taking a certain amount of FeCl for 1:82·4H2O pipettes ethylene glycol in beaker, with pipette,
Distilled water is added, dissolution is abundant.
The thickness for the film that electro-deposition obtains, electro-deposition in the present embodiment step (1) are controlled by electro-deposition process parameter
Technological parameter is as follows: electrodeposition temperature is 70 DEG C, operating voltage 1.36V, sedimentation time 5min.Then the work that will have been deposited
It is put into Muffle furnace as electrode, calcining 2h is carried out at 500 DEG C and obtains Fe2O3Film.
(2) 3.32g KI is dissolved in 50mL distilled water, the Bi (NO of 0.97g is added3)3·5H2Ultrasound 5min after O, with not
The pH value of solution is adjusted to 1.75 by diluted concentrated nitric acid, and 0.27g 1,4-benzoquinone is added, obtains Bi after being sufficiently stirred3+Forerunner
Liquid solution.
Electro-deposition is carried out using three-electrode system using CHI660E type electrochemical workstation, with Fe2O3Film is as work
Electrode, Ti piece are used as to electrode, and Ag/AgCl electrode is as reference electrode, in Bi under the conditions of -0.1V3+Precursor solution in
Carry out electro-deposition 5min.After natural drying to it, conductive slant setting up is in 15mL H containing 0.35mmol2NCSNH2It is water-soluble
In liquid, through 220 DEG C of hydro-thermal reaction 2h.Reaction terminates after its cooled to room temperature, is distilled water washing and obtains Fe2O3-
Bi2O3-Bi2S3Visible light catalytic film, measuring film thickness is 510nm.
Comparative example 1
To be convenient for performance comparison, the operating procedure of embodiment 1 is repeated, the difference is that only in step (2), hydro-thermal
The solvent of reaction is 15mL distilled water, other experimental conditions are identical, then Fe is prepared2O3-Bi2O3Film.
Comparative example 2
(1) with Fe2+Precursor solution as electrolyte, the conductive substrates after over cleaning, drying and processing are as work
Make electrode, graphite electrode is to electrode, and Ag/AgCl electrode carries out electro-deposition as reference electrode.
Conductive substrates in the present embodiment are FTO glass (specification is 10mm × 50mm × 2mm), before electro-deposition successively
Ultrasonic cleaning 10min is carried out with acetone, dehydrated alcohol and deionized water, then takes out and dries.
Fe in this embodiment2+Precursor solution configuration method it is same as Example 1.
The thickness for the film that electro-deposition obtains, electro-deposition in the present embodiment step (1) are controlled by electro-deposition process parameter
Technological parameter is as follows: electrodeposition temperature is 70 DEG C, operating voltage 1.36V, sedimentation time 5min.Then the work that will have been deposited
It is put into Muffle furnace as electrode, calcining 2h is carried out at 500 DEG C and obtains Fe2O3Film.
Comparative example 3
To be convenient for performance comparison, it is prepared by the following method Bi2O3-Bi2S3Film, it is specific the preparation method is as follows:
3.32g KI is dissolved in 50mL distilled water, the Bi (NO of 0.97g is added3)3·5H2Ultrasound 5min after O, with without
The pH value of solution is adjusted to 1.75 by diluted concentrated nitric acid, and 0.27g 1,4-benzoquinone is added, obtains Bi after being sufficiently stirred3+Presoma
Solution.
Electro-deposition is carried out using three-electrode system using CHI660E type electrochemical workstation, using FTO as working electrode,
Ti piece is used as to electrode, and Ag/AgCl electrode is as reference electrode, in Bi under the conditions of -0.1V3+Precursor solution in carry out electricity
Deposit 5min.After natural drying to it, conductive slant setting up is in 15mL H containing 0.35mmol2NCSNH2In solution, warp
220 DEG C of hydro-thermal reaction 2h.Reaction terminates after its cooled to room temperature, is distilled water washing and obtains Bi2O3-Bi2S3Film.
Comparative example 4
To be convenient for performance comparison, the operating procedure of comparative example 3 is repeated, the difference is that only the solution of hydro-thermal reaction
For 15mL distilled water, other experimental conditions are identical, then Bi is prepared2O3Photocatalysis film.
Fig. 1 is Fe made from embodiment 12O3-Bi2O3-Bi2S3Visible light catalytic film, Bi made from comparative example 32O3-
Bi2S3Film, Fe made from comparative example 22O3Bi made from film and comparative example 42O3Film is visible in 0.1M NaOH solution
Linear sweep voltammetry curve under illumination alternately.
Fig. 2 is Fe made from embodiment 12O3-Bi2O3-Bi2S3Visible light catalytic film, Fe made from comparative example 12O3-
Bi2O3Fe made from film and comparative example 22O3Film linearly sweeping under the UV, visible light illumination in 0.1M NaOH solution alternately
Retouch volt-ampere curve.
By Fig. 1 and 2 it is found that either in visible light still under UV, visible light illumination, in Fe2O3It is constructed on film
Bi2O3Layer, within the scope of surveyed applying bias, Fe2O3-Bi2O3The variation tendency of film light electric current is identical slightly to be improved；But work as
Bi2O3-Bi2S3When layer is built altogether, Fe2O3-Bi2O3-Bi2S3Film photoelectric stream is obviously improved.In 0.45V vs.Ag/AgCl voltage
Under, with simple Fe2O3Film is compared, Fe2O3-Bi2O3-Bi2S3Film is in visible light and ultraviolet-visible light compared with Fe2O3Film point
About 8 times and 7 times are not improved.This illustrates dual catalytic layer (Bi2O3And Bi2S3) in Fe2O3Building on film altogether, especially Bi2S3
Layer, facilitates the enhancing of photoelectric properties, inhibits the recombination process of hole and electronics pair to a certain extent.Directly by Fe2O3It is thin
Film is containing the Fe that progress hydro-thermal reaction obtains in thiourea solution2O3(thiourea), photoelectric current does not have significant change, further yet
Illustrate Bi2O3-Bi2S3Necessity, i.e. Bi existing for layer2O3-Bi2S3Layer and Fe2O3It is compound to be obviously improved photoelectric current.
Fig. 3 is Fe made from embodiment 12O3-Bi2O3-Bi2S3Visible light catalytic film in 0.1M NaOH solution can
It is light-exposed to shine alternately lower continuous scanning 4 times linear volt-ampere curves.
Fig. 4 is Bi made from comparative example 32O3-Bi2S3Film is continuous in the case where the visible light in 0.1M NaOH solution is according to alternating
The linear volt-ampere curve that scanning is 4 times.
By Fig. 3 and 4 it is found that after undergoing the scanning of 4 sublinear volt-ampere curves, Fe2O3-Bi2O3-Bi2S3Film still keep compared with
High PhotoelectrocatalytiPerformance Performance, in addition to second of measurement photoelectric current is declined slightly, subsequent photoelectric current kept stable, and Bi2O3-
Bi2S3Film photoelectric catalytic performance is greatly reduced, and photoelectric current reduces nearly 80%.This illustrates Fe2O3-Bi2O3-Bi2S3Visible light is urged
Change film not only PhotoelectrocatalytiPerformance Performance with higher, is also equipped with preferable stability.
Fig. 5 is Fe made from embodiment 12O3-Bi2O3-Bi2S3Fe made from visible light catalytic film, comparative example 12O3-
Bi2O3Fe made from film and comparative example 22O3Electrochemical impedance map of the film in 0.1M NaOH solution under dark condition
(EIS map).
Fig. 6 is Fe made from embodiment 12O3-Bi2O3-Bi2S3Fe made from visible light catalytic film, comparative example 12O3-
Bi2O3Fe made from film and comparative example 22O3Electrochemical impedance figure of the film in 0.1M NaOH solution under visible light conditions
It composes (EIS map).
By Fig. 5 and Fig. 6 it is found that either in dark or under the conditions of visible light shines, Fe2O3-Bi2O3-Bi2S3Film
Impedance ring radius is all significantly less than Fe2O3-Bi2O3And Fe2O3Film.In electrochemical alternate impedance spectrum, impedance ring radius is smaller,
Illustrate that the resistance of the material is smaller, photogenerated charge transfer ability is stronger.This illustrates dual catalytic layer (Bi2O3And Bi2S3) in Fe2O3
Building on film altogether, so that Fe2O3-Bi2O3-Bi2S3The photo-generate electron-hole of film more effectively separates, and improves photoproduction current-carrying
The transfer rate of son.
Fig. 7 is Fe obtained in comparative example 22O3The Mott-Schottky curve graph of film；Fig. 8 is to be made in comparative example 1
Fe2O3-Bi2O3The Mott-Schottky curve graph of film；Fig. 9 is Fe obtained in embodiment 12O3-Bi2O3-Bi2S3It can be seen that
The Mott-Schottky curve graph of photocatalysis film；Mott-Schottky curve can not only embody the type of semiconductor material,
Also the related datas such as the size of Preventing cough and the interface charge transmission of electrode can be obtained.As shown in Figure 7, Fe2O3The curve of film
Slope is positive, and is n-type semiconductor.Work as Bi2O3And Bi2S3After layer is constructed, the slope of curve of film is still positive, and shows similar
In the curvilinear trend of n-type semiconductor.In addition, three kinds of catalysis materials are compared, Fe2O3-Bi2O3-Bi2S3The Preventing cough of film is opposite
It is more negative, with Bi2O3Layer and Bi2S3Layer is constructed, by -0.32V it is negative move to -0.35V and finally bear move to -0.48V.Preventing cough
Negative shifting, show Fe2O3-Bi2O3-Bi2S3The reducing power of photoelectrocatalysithin thin film increases.
Figure 10 is Fe made from embodiment 12O3-Bi2O3-Bi2S3Fe made from visible light catalytic film, comparative example 12O3-
Bi2O3Fe made from film and comparative example 22O3Incident photon-to-electron conversion efficiency (IPCE) curve of film.As shown in Figure 10, Fe2O3-
Bi2O3-Bi2S3、Fe2O3-Bi2O3And Fe2O3The trend of the IPCE curve of catalytic film is roughly the same.At 400nm, Fe2O3-
Bi2O3-Bi2S3IPCE value be 31.7%, Fe2O3-Bi2O3IPCE value be 29.4%, Fe2O3IPCE value be 23.2%.?
Between the wave-length coverage of 400-560nm, Fe2O3-Bi2O3-Bi2S3Photoresponse value be above other two kinds of materials.This explanation is double
Weight Catalytic Layer (Bi2O3And Bi2S3) construct so that there is better phototransformation efficiency on composite catalyst surface.
Figure 11 is Fe made from embodiment 12O3-Bi2O3-Bi2S3Fe made from visible light catalytic film, comparative example 12O3-
Bi2O3Fe made from film and comparative example 22O3Instantaneous photocurrent-time curve of the film in 0.1M NaOH solution.Instantaneous
In photocurrent-time curve figure, for some specific ln D value, if the corresponding t value of surveyed catalysis material is bigger, the electrode
Middle photo-generated carrier recombination rate is lower.Under surveyed applying bias, compare the curve of three kinds of catalytic films, for any ln D
Value, Fe2O3-Bi2O3-Bi2S3The corresponding t value of photoelectrocatalysithin thin film is maximum always, and photo-generated carrier recombination rate is low.When ln D value
When being -1, Fe2O3-Bi2O3-Bi2S3T value corresponding to photoelectrocatalysithin thin film is 2.5s, and Fe2O3Film and Fe2O3-Bi2O3It is thin
The corresponding t value of film is respectively 1.2s and 1.9s.Therefore, work as Bi2O3-Bi2S3Layer is built altogether in Fe2O3After on film, photo-generated carrier
Recombination rate is slowed down, and the promotion of photoelectric properties is promoted.
Embodiment 2
Waste water to be processed is phenolic waste water in the present embodiment, and wherein the initial concentration of phenol is 10mg/L.
The present embodiment based on Fe obtained in embodiment 12O3-Bi2O3-Bi2S3The wastewater treatment of visible light catalytic film
Method, treatment process are as follows:
The pH value of waste water to be processed is about 6, carries out photoelectric catalysis degrading.The photocatalysis anode used when photoelectrocatalysis processing
Including conductive substrates and the Fe for being coated on conductive substrates surface2O3-Bi2O3-Bi2S3Visible light catalytic film (is made by embodiment 1
), cathode is titanium sheet.
When photoelectrocatalysis is handled in the present embodiment, before photochemical catalyst electrode is to operating voltage is applied, also to waste water to be processed
Dark adsorption treatment is carried out, the dark adsorption treatment time is 30min.
The operating voltage being applied between photocatalysis anode and cathode when photoelectrocatalysis processing is 2.5V, in radiation of visible light
Under conditions of carry out.Reaction time is 6h.
To guarantee waste water to be processed even concentration during the reaction, in photoelectrocatalysis treatment process, to be processed useless
Water carries out magnetic agitation.
Under conditions of the present embodiment, the Fe of the preparation of embodiment 12O3-Bi2O3-Bi2S3The phenol of visible light catalytic film is gone
Except rate is 76.8%；Fe prepared by comparative example 22O3The phenol removal rate of film is 50.3%, Fe prepared by comparative example 12O3-
Bi2O3The phenol removal rate of film is 54.6%.This illustrates modified Fe2O3-Bi2O3-Bi2S3Visible light catalytic film is can
Light-exposed lower photoelectric catalytically active is significantly improved.
Embodiment 3
The operating procedure of Examples 1 and 2 is repeated, the difference is that preparation Fe2O3-Bi2O3-Bi2S3Visible light catalytic is thin
During film, Fe in step (1)2+Precursor solution in Fe2+Source be ferrous sulfate, Fe2+Molar concentration be
0.1M。
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property with press
Fe made from 1 condition of embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film is close, the Fe prepared compared to comparative example 22O3It is thin
Film, the Fe of the present embodiment2O3-Bi2O3-Bi2S3The photoelectric current (i.e. current density) of visible light catalytic film has correspondinglyd increase 8 times,
The degradation rate of Pyrogentisinic Acid is 76.1% under visible light conditions.
Embodiment 4
The operating procedure of Examples 1 and 2 is repeated, the difference is that preparation Fe2O3-Bi2O3-Bi2S3Visible light catalytic is thin
During film, in step (1), the temperature of electro-deposition is 90 DEG C, and the voltage of electro-deposition is 2V, and the time of electro-deposition is 2min；
The temperature of calcination processing is 600 DEG C, calcination time 1h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property is inferior to
By Fe made from 1 condition of embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film, the Fe prepared compared to comparative example 22O3Film,
The Fe of the present embodiment2O3-Bi2O3-Bi2S3The photoelectric current (i.e. current density) of visible light catalytic film has correspondinglyd increase 7 times, can
The degradation rate of Pyrogentisinic Acid is 75.4% under the conditions of light-exposed.
Embodiment 5
The operating procedure of Examples 1 and 2 is repeated, the difference is that preparation Fe2O3-Bi2O3-Bi2S3Visible light catalytic is thin
During film, in step (1), the temperature of electro-deposition is 80 DEG C, and the voltage of electro-deposition is 1.02V, and the time of electro-deposition is
6min；The temperature of calcination processing is 450 DEG C, calcination time 3h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property with press
Fe made from 1 condition of embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film is close, the Fe prepared compared to comparative example 22O3It is thin
Film, the Fe of the present embodiment2O3-Bi2O3-Bi2S3The photoelectric current (i.e. current density) of visible light catalytic film has correspondinglyd increase 8 times,
The degradation rate of Pyrogentisinic Acid is 76.5% under visible light conditions.
Embodiment 6
The operating procedure of Examples 1 and 2 is repeated, the difference is that preparation Fe2O3-Bi2O3-Bi2S3Visible light catalytic is thin
During film, in step (1), the temperature of electro-deposition is 60 DEG C, and the voltage of electro-deposition is 1.5V, and the time of electro-deposition is
5min；The temperature of calcination processing is 550 DEG C, calcination time 1h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property with press
Fe made from 1 condition of embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film is close, the Fe prepared compared to comparative example 22O3It is thin
Film, the Fe of the present embodiment2O3-Bi2O3-Bi2S3The photoelectric current (i.e. current density) of visible light catalytic film has correspondinglyd increase 8 times,
The degradation rate of Pyrogentisinic Acid is 75.9% under visible light conditions.
Embodiment 7
The operating procedure of Examples 1 and 2 is repeated, the difference is that preparation Fe2O3-Bi2O3-Bi2S3Visible light catalytic is thin
During film, in step (1), the temperature of electro-deposition is 40 DEG C, and the voltage of electro-deposition is 1.0V, and the time of electro-deposition is
8min；The temperature of calcination processing is 600 DEG C, calcination time 2h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property is inferior to
By Fe made from 1 condition of embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film, the Fe prepared compared to comparative example 22O3Film,
The Fe of the present embodiment2O3-Bi2O3-Bi2S3The photoelectric current (i.e. current density) of visible light catalytic film has correspondinglyd increase 6 times, can
The degradation rate of Pyrogentisinic Acid is 68.1% under the conditions of light-exposed.
Embodiment 8
The operating procedure of Examples 1 and 2 is repeated, the difference is that preparation Fe2O3-Bi2O3-Bi2S3Visible light catalytic is thin
During film, in step (2), the voltage of electro-deposition is -0.3V, and the time of electro-deposition is 8min；The temperature of hydro-thermal reaction is
200 DEG C, reaction time 4h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property is inferior to
By Fe made from 1 condition of embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film, the Fe prepared compared to comparative example 22O3Film,
The Fe of the present embodiment2O3-Bi2O3-Bi2S3The photoelectric current (i.e. current density) of visible light catalytic film has correspondinglyd increase 5 times, can
The degradation rate of Pyrogentisinic Acid is 65.7% under the conditions of light-exposed.
Embodiment 9
The operating procedure of Examples 1 and 2 is repeated, the difference is that preparation Fe2O3-Bi2O3-Bi2S3Visible light catalytic is thin
During film, in step (2), the voltage of electro-deposition is 0.1V, and the time of electro-deposition is 5min；The temperature of hydro-thermal reaction is
220 DEG C, reaction time 3h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property with press
Fe made from 1 condition of embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film is close, the Fe prepared compared to comparative example 22O3It is thin
Film, the Fe of the present embodiment2O3-Bi2O3-Bi2S3The photoelectric current (i.e. current density) of visible light catalytic film has correspondinglyd increase 8 times,
The degradation rate of Pyrogentisinic Acid is 76.2% under visible light conditions.
Embodiment 10
The operating procedure of Examples 1 and 2 is repeated, the difference is that preparation Fe2O3-Bi2O3-Bi2S3Visible light catalytic is thin
During film, in step (2), the voltage of electro-deposition is 0.2V, and the time of electro-deposition is 3min；The temperature of hydro-thermal reaction is
240 DEG C, reaction time 1h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property is inferior to
By Fe made from 1 condition of embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film, the Fe prepared compared to comparative example 22O3Film,
The Fe of the present embodiment2O3-Bi2O3-Bi2S3The photoelectric current (i.e. current density) of visible light catalytic film has correspondinglyd increase 7 times, can
The degradation rate of Pyrogentisinic Acid is 75.3% under the conditions of light-exposed.
Embodiment 11
The operating procedure of Examples 1 and 2 is repeated, the difference is that preparation Fe2O3-Bi2O3-Bi2S3Visible light catalytic is thin
During film, in step (2), the voltage of electro-deposition is 0.3V, and the time of electro-deposition is 3min；The temperature of hydro-thermal reaction is
250 DEG C, reaction time 1h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property is inferior to
By Fe made from 1 condition of embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film, the Fe prepared compared to comparative example 22O3Film,
The Fe of the present embodiment2O3-Bi2O3-Bi2S3The photoelectric current (i.e. current density) of visible light catalytic film has correspondinglyd increase 4 times, can
The degradation rate of Pyrogentisinic Acid is 61.7% under the conditions of light-exposed.
By above embodiments and comparative example as it can be seen that Bi2O3-Bi2S3Layer is built altogether in Fe2O3On film in terms of photoelectric activity table
Reveal significant synergistic effect.The Fe that the present invention is prepared2O3-Bi2O3-Bi2S3Photocatalysis film has excellent visible light
Catalytic activity, stability, better photo-generate electron-hole separative efficiency and phototransformation efficiency.
Technical solution of the present invention and beneficial effect is described in detail in above-described specific embodiment, Ying Li
Solution is not intended to restrict the invention the foregoing is merely presently most preferred embodiment of the invention, all in principle model of the invention
Interior done any modification, supplementary, and equivalent replacement etc. are enclosed, should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of iron oxide-bismuth oxide-bismuth sulfide visible light catalytic film preparation method, which is characterized in that including walking as follows
It is rapid:
(1) with Fe2+Precursor solution as electrolyte, using conductive substrates as working electrode, graphite electrode be to electrode, Ag/
AgCl electrode carries out electro-deposition as reference electrode；Fe is made through calcination processing in working electrode after electro-deposition2O3Film；
(2) with above-mentioned Fe2O3As working electrode, Ti piece is used as to electrode film, Ag/AgCl electrode as reference electrode, with
Bi3+Precursor solution as electrolyte, carry out electro-deposition；The film obtained after electro-deposition is placed in H after drying2NCSNH2Water
In solution, hydro-thermal reaction is carried out, after reaction washed obtained Fe2O3-Bi2O3-Bi2S3Visible light catalytic film.
2. iron oxide-bismuth oxide according to claim 1-bismuth sulfide visible light catalytic film preparation method, feature
It is, in step (1), the temperature of electro-deposition is 40~90 DEG C, and the voltage of electro-deposition is 1~2V, the time of electro-deposition is 0.5~
10min。
3. iron oxide-bismuth oxide according to claim 1-bismuth sulfide visible light catalytic film preparation method, feature
It is, in step (1), the temperature of the calcination processing is 400~600 DEG C, and calcination time is 1~5h.
4. iron oxide-bismuth oxide according to claim 1-bismuth sulfide visible light catalytic film preparation method, feature
It is, the Bi3+Precursor solution the preparation method is as follows: KI is soluble in water, Bi (NO is added3)3·5H2O, after stirring
Adjusting pH value is 1.5~2.0, and 1,4-benzoquinone is added, is again stirring for obtaining Bi3+Precursor solution.
5. iron oxide-bismuth oxide according to claim 4-bismuth sulfide visible light catalytic film preparation method, feature
It is, the Bi3+Precursor solution in, the concentration of KI is 300~500mM, Bi (NO3)3·5H2The concentration of O be 20~
60mM；The concentration of 1,4-benzoquinone is 30~70mM.
6. iron oxide-bismuth oxide according to claim 1-bismuth sulfide visible light catalytic film preparation method, feature
It is, in step (2), the voltage of electro-deposition is -0.3~0.2V, and the time of electro-deposition is 3~8min.
7. iron oxide-bismuth oxide according to claim 1-bismuth sulfide visible light catalytic film preparation method, feature
It is, in step (2), the temperature of the hydro-thermal reaction is 200~240 DEG C, and the time of hydro-thermal reaction is 1~4h.
8. a kind of Fe that methods described in any item according to claim 1~7 are prepared2O3-Bi2O3-Bi2S3Visible light catalytic
Film, which is characterized in that gained Fe2O3-Bi2O3-Bi2S3Visible light catalytic film with a thickness of 450~600nm.
9. utilizing Fe according to any one of claims 82O3-Bi2O3-Bi2S3Application of the visible light catalytic film in Phenol-Containing Wastewater Treatment.
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| CN105597784A (en) * | 2015-12-29 | 2016-05-25 | 浙江工商大学 | MoS2-doped iron oxide photocatalytic thin film and preparation method as well as application thereof to treatment of phenolic waste water |
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| CN105597784A (en) * | 2015-12-29 | 2016-05-25 | 浙江工商大学 | MoS2-doped iron oxide photocatalytic thin film and preparation method as well as application thereof to treatment of phenolic waste water |
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