CN107096546A - 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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- CN107096546A CN107096546A CN201710153919.8A CN201710153919A CN107096546A CN 107096546 A CN107096546 A CN 107096546A CN 201710153919 A CN201710153919 A CN 201710153919A CN 107096546 A CN107096546 A CN 107096546A
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- -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 146
- 238000004070 electrodeposition Methods 0.000 claims abstract description 69
- 238000001354 calcination Methods 0.000 claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000012545 processing Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 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
- 238000001035 drying Methods 0.000 claims abstract description 6
- 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 6
- 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
- 238000005406 washing 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
- 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 47
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 27
- 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
- 239000002131 composite material Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 12
- 238000007146 photocatalysis Methods 0.000 description 12
- 238000011017 operating method 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
- 239000003054 catalyst Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000005286 illumination Methods 0.000 description 7
- 239000011941 photocatalyst Substances 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
- 238000005516 engineering process Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000004065 semiconductor 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
- 238000004140 cleaning Methods 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000003825 pressing Methods 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 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
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000084 colloidal system Substances 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
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 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
- 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
- 239000002904 solvent Substances 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
- 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
- 239000002028 Biomass Substances 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
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002079 cooperative effect 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
- 230000000593 degrading effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 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
- 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
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 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
- 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
- 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
- 238000005259 measurement 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
- 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
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- 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)
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Abstract
The invention discloses a kind of preparation method of iron oxide bismuth oxide bismuth sulfide visible light catalytic film：(1) with Fe2+Precursor solution as electrolyte, conductive substrates are that working electrode carries out calcination processing after electro-deposition using three-electrode system Fe is made2O3Film；(2) with Bi3+Precursor solution be used as electrolyte, Fe2O3Film carries out electro-deposition as working electrode using three-electrode system, is placed in after drying in thiourea solution and carries out hydro-thermal reaction, scrubbed obtained Fe2O3‑Bi2O3‑Bi2S3Visible light catalytic film.Present invention additionally comprises using Fe made from the above method2O3‑Bi2O3‑Bi2S3Visible light catalytic film and the application using the film in Phenol-Containing Wastewater Treatment.Gained visible light catalytic forming thin film is uniform, and stability is good, and active component is difficult to peel off, and light induced electron and hole separative efficiency are high, with good photoelectric catalytically active.
Description
Technical field
The present invention relates to photoelectrocatalysimaterial material technical field, more particularly to a kind of Fe of efficient visible light response2O3-
Bi2O3-Bi2S3Photocatalysis film and its preparation method and application.
Background technology
Problem of environmental pollution is increasingly paid close attention to by all circles, and how high-efficiency cleaning processing pollutant becomes grinding instantly
Study carefully focus.Photo-electrocatalytic technology has the advantages such as efficient, cleaning, non-secondary pollution, and its key is to prepare urging for efficient stable
Agent.
In new photochemical catalyst, Fe2O3It is a kind of semiconductor for having very much an application prospect for transition metal oxide
Material, its energy gap is small (Eg=2.20eV), and stronger optical electro-chemistry response is all shown in Uv and visible light region.But
It is that its light induced electron and hole easily occur to be combined, causes photoelectric activity to reduce.In this regard, many method of modifying arise at the historic moment, it is such as non-
Metal/metal doping, semiconductors coupling etc..Bismuth-containing visible light catalyst also has higher visible light catalysis activity, Bi2O3Energy
Gap band is 2.8eV, and absorbing wavelength is longer, it is seen that the utilization rate of light is higher.
Publication No. CN105344364A Chinese patent literature disclose a kind of iron oxide/bismuth oxybromide composite and
Its preparation method and application.The preparation method includes：Aqueous slkali is added in iron nitrate solution, ferric hydroxide colloid is obtained molten
Liquid；KBr solution is added in bismuth nitrate solution and mixed, mixed solution is obtained；Ferric hydroxide colloid solution is added dropwise to mixed
Close in solution and carry out hydro-thermal reaction, obtain iron oxide/bismuth oxybromide composite.The preparation method have preparation technology it is simple,
Cost is low, have the advantages that good environmental benefit, and the composite of preparation has superior photocatalysis performance, is widely used in
Photocatalytic degradation of dye waste water field, and higher catalytic efficiency can be obtained.
Publication No. CN102824917A Chinese patent literature discloses a kind of iron oxide/bismuth tungstate composite photocatalyst
And preparation method and application.The invention is by dipping-low-temperature bake technology in Bi2WO6Surface deposited 10~30nm's
Fe2O3Nano particle, prepared Fe2O3/Bi2WO6The photocatalytic activity of composite 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 A of Publication No. CN 102500390 Chinese patent literature discloses a kind of iron oxide/bismuth tungstate composite photocatalyst
The preparation method of agent, the composite photo-catalyst is a kind of powder constituted including iron oxide and bismuth tungstate, wherein iron oxide and tungsten
The mol ratio of sour bismuth is 1：2~20, its preparation process includes：By the salpeter solution of five water bismuth nitrates, the sodium hydroxide of ammonium tungstate
After solution and the mixing of soluble iron salting liquid, iron oxide/bismuth tungstate is prepared using the hydro-thermal method of Microwave-assisted firing and is combined
Photochemical catalyst.The invention preparation method is simple, cost is low, and the composite photo-catalyst of preparation has excellent catalytic performance, can
Seeing under light irradiation has the effect that harmful chemical, organic biomass close sterilization of decomposing.
However, traditional composite photo-catalyst is most 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, develop
Efficient and stable film-form catalysis material has considerable application prospect.
The content of the invention
The invention provides a kind of Fe2O3-Bi2O3-Bi2S3Visible light catalytic film and preparation method thereof, is solved existing
Fe in technology2O3Catalysis material catalytic efficiency is not high, stability is bad, reclaim the technical problem of inconvenience.
A kind of preparation method of iron oxide-bismuth oxide-bismuth sulfide visible light catalytic film, comprises the following steps：
(1) with Fe2+Precursor solution as electrolyte, using conductive substrates as working electrode, graphite electrode be to electrode,
Ag/AgCl electrodes carry out electro-deposition as reference electrode；Fe is made through calcination processing in working electrode after electro-deposition2O3Film；
(2) with above-mentioned Fe2O3Film as working electrode, Ti pieces as to electrode, Ag/AgCl electrodes as reference electrode,
With Bi3+Precursor solution be used as electrolyte, carry out electro-deposition；The film obtained after electro-deposition is placed in H after drying2NCSNH2
In the aqueous solution, hydro-thermal reaction is carried out, Fe is made through washing after terminating in reaction2O3-Bi2O3-Bi2S3Visible light catalytic film.
In above-mentioned syntheti c 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-wash, drying conductive substrates are needed before electro-deposition.
The Fe2+Precursor solution be formulated by soluble ferrite and solvent orange 2 A, soluble ferrite can be nitric acid
Ferrous iron, frerrous chloride, ferrous sulfate, ferrous acetate or ferrous oxalate etc., solvent orange 2 A are one in ethylene glycol, methanol, second alcohol and water
Plant or several.Preferably, soluble ferrite is frerrous chloride, solvent orange 2 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 relevant with film thickness, and film thickness is too thin or too thick,
The migration of the photolytic activity and photo-generated carrier of film can be influenceed, and only when film thickness is moderate, light not only excites generation
Carrier, and the migration rate of carrier can be improved, so as to improve the photoelectric catalytically active of film.
The gross thickness of photocatalyst film is substantially equal to the film thickness of electro-deposition formation in the preparation method of the present invention
With the film thickness sum of hydro-thermal method formation.Temperature, time and the operating voltage of electro-deposition are directly connected to the production of electrolytic deposition
The quality (i.e. the thickness of electrodeposited film) of thing and the product formed.After the completion of electro-deposition, the further oxygen of high-temperature calcination need to be passed through
Change, and calcining heat and time also directly affect the Fe of generation2O3Crystalline phase, so as to influence the photocatalysis performance of composite membrane.
Film forming effective area and quality can be controlled by regulating and controlling 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 of the catalytic film obtained by electro-deposition process parameter control electro-deposition, film thickness
It is too thin, it is impossible to fully absorb light, and during as substrate, it is impossible to give full play to its catalytic activity；The too thick then influence photoproduction of film is carried
Flow the migration of son.When film thickness is moderate, light not only excites generation 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, calcine
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, calcine
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 calcining heat, material has good crystallinity, and crystalline phase is α-Fe2O3, photocatalytic activity is higher.When forging
When burning temperature is relatively low, the crystallinity of material is very poor, greatly limits photocatalytic activity；, can be because of conduction when calcining heat is too high
The heat resisting temperature of substrate limits and influences the formation of film.
(2) in step (2)：
The Bi3+Precursor solution preparation method it is as follows：KI is soluble in water, add Bi (NO3)3·5H2O, stirring
Regulation pH value is 1.5~2.0 afterwards, adds 1,4-benzoquinone, is again stirring for obtaining Bi3+Precursor solution.
Preferably, use mass fraction for 68~70% HNO3Adjust pH value；
Preferably, the Bi3+Precursor solution in, KI concentration is 300~500mM, Bi (NO3)3·5H2O concentration
For 20~60mM；Further preferably, KI concentration is 350~450mM, Bi (NO3)3·5H2O concentration is 30~50mM；It is optimal
Selection of land, KI concentration is 400mM, Bi (NO3)3·5H2O concentration is 40mM；
Preferably, pH to 1~2 is adjusted, the concentration of 1,4-benzoquinone is 30~70mM；Further preferably, regulation 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；Enter 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 gravity, conductive more favourable up
In natural subsidence, obtained film surface is uniform；It is conductive down when, composite bed grow on the base layer it is uneven so that
The photoelectric properties of film are influenceed to a certain extent.
Preferably, the H2NCSNH2The concentration of the aqueous solution is 10~30mM, and addition is defined by being totally submerged film, can
Suitably adjusted according to actual conditions, H2NCSNH2The concentration of the aqueous solution determines thickness and form of institute's film forming etc., film forming thickness mistake
The function of other materials on thickness, meeting cover layer.
Preferably, the temperature of the hydro-thermal reaction is 200~240 DEG C, and the time of hydro-thermal reaction is 1~4h.
Present invention also offers a kind of Fe prepared by the above method2O3-Bi2O3-Bi2S3Visible light catalytic film.
The gross thickness of photocatalyst film is substantially equal to the film thickness of electro-deposition formation in the preparation method of the present invention
With the film thickness sum of hydro-thermal method formation.
Gained Fe2O3-Bi2O3-Bi2S3The thickness of visible light catalytic film is 450~600nm.
Obtained Fe is utilized present invention additionally comprises a kind of2O3-Bi2O3-Bi2S3Visible light catalytic film Phenol-Containing Wastewater Treatment
In application.
In the preparation method of the present invention substrate Fe is controlled by adjusting temperature, time and the operating voltage of electro-deposition2O3It is thin
The thickness and Bi of film2O3Thickness, control Bi by adjusting the temperature of hydro-thermal reaction, time, concentration2S3Thickness, so as to obtain
Obtain medium thin Fe2O3-Bi2O3-Bi2S3Visible light catalytic thin-film material, makes it to fully absorb light, produces higher concentration
Photo-generated carrier, the migration rate of carrier can be improved again, higher photoelectric catalytically active is shown.
Compared with prior art, beneficial effects of the present invention：
(1) by determining, under visible ray photograph, with simple Fe2O3Film is compared, the Fe of preparation2O3-Bi2O3-Bi2S3Can
See that the photoelectric current of photocatalysis film improves 8 times.Bi2O3-Bi2S3Layer is in Fe2O3Building altogether on film, especially Bi2S3Layer, makes
Obtain Fe2O3-Bi2O3-Bi2S3The photo-generate electron-hole of film is more effectively separated, and improves the transfer rate and light of photo-generated carrier
Transformation efficiency, not only promotes the lifting of photoelectric properties, and substantially increases the stability of catalyst.
(2) synergy of general electrodeposition process and hydro-thermal method, obtained visible light catalytic forming thin film is uniform, stability
Good, active component is difficult 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.
Brief description of the drawings
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 solutions
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 22O3Linearly sweeping under the film UV, visible light illumination in 0.1M NaOH solutions alternately
Retouch volt-ampere curve；
Fig. 3 is Fe made from embodiment 12O3-Bi2O3-Bi2S3Visible light catalytic film in 0.1M NaOH solutions can
See the illumination alternately lower continuous linear volt-ampere curve for scanning 4 times；
Fig. 4 is Bi made from comparative example 32O3-Bi2S3Visible ray of the film in 0.1M NaOH solutions is according to continuous under 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 collection of illustrative plates of the film in 0.1M NaOH solutions under dark condition
(EIS collection of illustrative plates)；
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 solutions under visible light conditions
Compose (EIS collection of illustrative plates)；
Fig. 7 is obtained Fe in comparative example 22O3Film is in 0.1M NaOH solutions, respectively in 500Hz, 700Hz,
Mott-Schottky curves under the conditions of 1000Hz；
Fig. 8 is obtained Fe in comparative example 12O3-Bi2O3Film is in 0.1M NaOH solutions, respectively in 500Hz, 700Hz,
Mott-Schottky curves under the conditions of 1000Hz；
Fig. 9 is obtained Fe in embodiment 12O3-Bi2O3-Bi2S3Visible light catalytic film divides in 0.1M NaOH solutions
Not in 500Hz, 700Hz, the Mott-Schottky curves under the conditions of 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 Na2SO3Electricity conversion 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 solutions.
Embodiment
Below in conjunction with accompanying drawing and instantiation, 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 used as work
Make electrode, graphite electrode is that, to electrode, Ag/AgCl electrodes carry 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, absolute ethyl alcohol and deionized water, then takes out and dries.
Fe in this embodiment2+Precursor solution be containing FeCl2·4H2O ethylene glycol solution, Fe2+Presoma it is molten
In liquid, Fe2+Molar concentration be 0.025M, solvent is the volume of the mixed liquor of ethylene glycol and distilled water, ethylene glycol and distilled water
Than for 1:8, it is prepared via a method which to obtain：Take a certain amount of FeCl2·4H2O pipettes ethylene glycol in beaker with pipette,
Distilled water is added, dissolving is abundant.
Electro-deposition in the thickness of the film obtained by electro-deposition process parameter control electro-deposition, the present embodiment step (1)
Technological parameter is as follows：Electrodeposition temperature is 70 DEG C, and operating voltage is 1.36V, and sedimentation time is 5min.Then by the work deposited
It is put into as electrode in Muffle furnace, it is to obtain Fe that calcining 2h is carried out at 500 DEG C2O3Film.
(2) 3.32g KI are dissolved in 50mL distilled water, add 0.97g Bi (NO3)3·5H2Ultrasound 5min after O, with not
The pH value of solution is adjusted to 1.75 by diluted concentrated nitric acid, adds 0.27g 1,4-benzoquinone, Bi is obtained after being sufficiently stirred for3+Forerunner
Liquid solution.
Electro-deposition is carried out using three-electrode system using CHI660E types electrochemical workstation, with Fe2O3Film is used as work
Electrode, Ti pieces are as to electrode, and Ag/AgCl electrodes are as reference electrode, in Bi under the conditions of -0.1V3+Precursor solution in
Carry out electro-deposition 5min.After it dries naturally, 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.End is reacted after it naturally cools to room temperature, and Fe is obtained through distilling water washing2O3-
Bi2O3-Bi2S3Visible light catalytic film, measures film thickness for 510nm.
Comparative example 1
For ease of carrying out performance comparison, the operating procedure of embodiment 1 is repeated, be the difference is that only in step (2), hydro-thermal
The solvent of reaction is 15mL distilled water, and other experimental conditions are identical, then prepare Fe2O3-Bi2O3Film.
Comparative example 2
(1) with Fe2+Precursor solution as electrolyte, the conductive substrates after over cleaning, drying and processing are used as work
Make electrode, graphite electrode is that, to electrode, Ag/AgCl electrodes carry 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, absolute ethyl alcohol and deionized water, then takes out and dries.
Fe in this embodiment2+Precursor solution collocation method it is same as Example 1.
Electro-deposition in the thickness of the film obtained by electro-deposition process parameter control electro-deposition, the present embodiment step (1)
Technological parameter is as follows：Electrodeposition temperature is 70 DEG C, and operating voltage is 1.36V, and sedimentation time is 5min.Then by the work deposited
It is put into as electrode in Muffle furnace, it is to obtain Fe that calcining 2h is carried out at 500 DEG C2O3Film.
Comparative example 3
For ease of carrying out performance comparison, Bi is prepared by the following method2O3-Bi2S3Film, specific preparation method is as follows：
3.32g KI are dissolved in 50mL distilled water, 0.97g Bi (NO are added3)3·5H2Ultrasound 5min after O, with without
The pH value of solution is adjusted to 1.75 by the concentrated nitric acid of dilution, adds 0.27g 1,4-benzoquinone, Bi is obtained after being sufficiently stirred for3+Presoma
Solution.
Electro-deposition is carried out using three-electrode system using CHI660E types electrochemical workstation, using FTO as working electrode,
Ti pieces are as to electrode, and Ag/AgCl electrodes are as reference electrode, in Bi under the conditions of -0.1V3+Precursor solution in carry out electricity
Deposit 5min.After it dries naturally, conductive slant setting up is in 15mL H containing 0.35mmol2NCSNH2In solution, warp
220 DEG C of hydro-thermal reaction 2h.End is reacted after it naturally cools to room temperature, and Bi is obtained through distilling water washing2O3-Bi2S3Film.
Comparative example 4
For ease of carrying out performance comparison, the operating procedure of comparative example 3 is repeated, the solution of hydro-thermal reaction is the difference is that only
For 15mL distilled water, other experimental conditions are identical, then prepare Bi2O3Photocatalysis 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 solutions
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 22O3Linearly sweeping under the film UV, visible light illumination in 0.1M NaOH solutions alternately
Retouch volt-ampere curve.
From Fig. 1 and 2, either in visible ray still under UV, visible light illumination, with Fe2O3Constructed on film
Bi2O3Layer, in the range 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 voltages
Under, with simple Fe2O3Film is compared, Fe2O3-Bi2O3-Bi2S3Film is in visible ray and ultraviolet-visible light compared with Fe2O3Film point
About 8 times and 7 times are not improved.This explanation dual catalytic layer (Bi2O3And Bi2S3) in Fe2O3Building altogether on film, especially Bi2S3
Layer, contributes to the enhancing of photoelectric properties, the recombination process of hole and electronics pair is inhibited to a certain extent.Directly by Fe2O3It is thin
Film carries out the Fe that hydro-thermal reaction is obtained in containing thiourea solution2O3(thiourea), photoelectric current does not have significant change, further yet
Illustrate Bi2O3-Bi2S3The necessity that layer is present, i.e. Bi2O3-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 solutions can
See the illumination alternately lower continuous linear volt-ampere curve for scanning 4 times.
Fig. 4 is Bi made from comparative example 32O3-Bi2S3Visible ray of the film in 0.1M NaOH solutions is according to continuous under alternating
The linear volt-ampere curve that scanning is 4 times.
From Fig. 3 and 4, after the scanning of 4 sublinear volt-ampere curves is undergone, Fe2O3-Bi2O3-Bi2S3Film still keep compared with
High PhotoelectrocatalytiPerformance Performance, in addition to second of measurement photoelectric current is declined slightly, follow-up photoelectric current kept stable, and Bi2O3-
Bi2S3Film photoelectric catalytic performance is greatly reduced, and photoelectric current reduces nearly 80%.This explanation Fe2O3-Bi2O3-Bi2S3Visible ray is urged
Changing film not only has higher PhotoelectrocatalytiPerformance Performance, 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 collection of illustrative plates of the film in 0.1M NaOH solutions under dark condition
(EIS collection of illustrative plates).
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 solutions under visible light conditions
Compose (EIS collection of illustrative plates).
From Fig. 5 and Fig. 6, either in dark or under the conditions of visible ray photograph, 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 explanation dual catalytic layer (Bi2O3And Bi2S3) in Fe2O3
Building altogether on film so that Fe2O3-Bi2O3-Bi2S3The photo-generate electron-hole of film is more effectively separated, and improves photoproduction current-carrying
The transfer rate of son.
Fig. 7 is obtained Fe in comparative example 22O3The Mott-Schottky curve maps of film；Fig. 8 is obtained in comparative example 1
Fe2O3-Bi2O3The Mott-Schottky curve maps of film；Fig. 9 is obtained Fe in embodiment 12O3-Bi2O3-Bi2S3It can be seen that
The Mott-Schottky curve maps of photocatalysis film；Mott-Schottky curves can not only embody the type of semi-conducting material,
Also the related data 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 just, it is n-type semiconductor.Work as Bi2O3And Bi2S3After layer is constructed, the slope of curve of film is still just, to show 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 relative
It is more negative, with Bi2O3Layer and Bi2S3Layer is constructed, and moves to that -0.35V is finally negative moves to -0.48V by -0.32V is negative.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 22O3Electricity conversion (IPCE) curve of film.As shown in Figure 10, Fe2O3-
Bi2O3-Bi2S3、Fe2O3-Bi2O3And Fe2O3The trend of the IPCE curves of catalytic film is roughly the same.At 400nm, Fe2O3-
Bi2O3-Bi2S3IPCE values be 31.7%, Fe2O3-Bi2O3IPCE values be 29.4%, Fe2O3IPCE values be 23.2%.
Between 400-560nm wave-length coverage, 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 more preferable phototranstormation 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 solutions.Instantaneous
In photocurrent-time curve figure, for some specific ln D value, if the corresponding t values of surveyed catalysis material are 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 values of photoelectrocatalysithin thin film are maximum all the time, and photo-generated carrier recombination rate is low.When ln D values
For -1 when, Fe2O3-Bi2O3-Bi2S3T values corresponding to photoelectrocatalysithin thin film are 2.5s, and Fe2O3Film and Fe2O3-Bi2O3It is thin
The corresponding t values of film are respectively 1.2s and 1.9s.Therefore, Bi is worked as2O3-Bi2S3Layer is built in Fe altogether2O3After on film, photo-generated carrier
Recombination rate has slowed down, and promotes the lifting of photoelectric properties.
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 obtained Fe in embodiment 12O3-Bi2O3-Bi2S3The wastewater treatment of visible light catalytic film
Method, processing procedure is as follows：
The pH value of pending waste water is about 6, carries out photoelectric catalysis degrading.The photocatalysis anode used during 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
), negative electrode is titanium sheet.
When photoelectrocatalysis is handled in the present embodiment, before photochemical catalyst electrode is to applying operating voltage, also to pending waste water
Dark adsorption treatment is carried out, the dark adsorption treatment time is 30min.
The operating voltage being applied to during photoelectrocatalysis processing between photocatalysis anode and negative electrode is 2.5V, in radiation of visible light
Under conditions of carry out.Reaction time is 6h.
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.
Under conditions of the present embodiment, Fe prepared by embodiment 12O3-Bi2O3-Bi2S3The phenol of visible light catalytic film is gone
Except rate is 76.8%；Fe prepared by comparative example 22O3The phenol clearance of film is 50.3%, Fe prepared by comparative example 12O3-
Bi2O3The phenol clearance of film is 54.6%.This illustrates modified Fe2O3-Bi2O3-Bi2S3Visible light catalytic film is can
See that photoelectric catalytically active is significantly improved under light.
Embodiment 3
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare 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 is with pressing
Fe made from the condition of embodiment 12O3-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 accordingly improves 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, difference is to prepare 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, and calcination time is 1h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property is inferior to
The Fe as made from the condition of embodiment 12O3-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 accordingly improves 7 times, can
The degradation rate for seeing Pyrogentisinic Acid under optical condition is 75.4%.
Embodiment 5
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare 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, and calcination time is 3h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property is with pressing
Fe made from the condition of embodiment 12O3-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 accordingly improves 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, difference is to prepare 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, and calcination time is 1h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property is with pressing
Fe made from the condition of embodiment 12O3-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 accordingly improves 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, difference is to prepare 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, and calcination time is 2h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property is inferior to
The Fe as made from the condition of embodiment 12O3-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 accordingly improves 6 times, can
The degradation rate for seeing Pyrogentisinic Acid under optical condition is 68.1%.
Embodiment 8
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare 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, the reaction time is 4h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property is inferior to
The Fe as made from the condition of embodiment 12O3-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 accordingly improves 5 times, can
The degradation rate for seeing Pyrogentisinic Acid under optical condition is 65.7%.
Embodiment 9
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare 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, the reaction time is 3h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property is with pressing
Fe made from the condition of embodiment 12O3-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 accordingly improves 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, difference is to prepare 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, the reaction time is 1h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property is inferior to
The Fe as made from the condition of embodiment 12O3-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 accordingly improves 7 times, can
The degradation rate for seeing Pyrogentisinic Acid under optical condition is 75.3%.
Embodiment 11
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare 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, the reaction time is 1h.
The Fe prepared under conditions of the present embodiment2O3-Bi2O3-Bi2S3Visible light catalytic film photoelectric chemical property is inferior to
The Fe as made from the condition of embodiment 12O3-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 accordingly improves 4 times, can
The degradation rate for seeing Pyrogentisinic Acid under optical condition is 61.7%.
From above example and comparative example, Bi2O3-Bi2S3Layer is built in Fe altogether2O3On film in terms of photoelectric activity table
Reveal significant cooperative effect.The Fe that the present invention is prepared2O3-Bi2O3-Bi2S3Photocatalysis film has excellent visible ray
Catalytic activity, stability, more preferable photo-generate electron-hole separative efficiency and phototranstormation efficiency.
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, be should be included in the scope of the protection.
Claims (9)
1. the preparation method of a kind of iron oxide-bismuth oxide-bismuth sulfide visible light catalytic film, it is characterised in that including following step
Suddenly：
(1) with Fe2+Precursor solution as electrolyte, using conductive substrates as working electrode, graphite electrode be to electrode, Ag/
AgCl electrodes carry out electro-deposition as reference electrode；Fe is made through calcination processing in working electrode after electro-deposition2O3Film；
(2) with above-mentioned Fe2O3Film as working electrode, Ti pieces as to electrode, Ag/AgCl electrodes as reference electrode, with
Bi3+Precursor solution be used 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, Fe is made through washing after terminating in reaction2O3-Bi2O3-Bi2S3Visible light catalytic film.
2. the preparation method of iron oxide-bismuth oxide according to claim 1-bismuth sulfide visible light catalytic film, its feature
Be, in step (1), the temperature of electro-deposition is 40~90 DEG C, the voltage of electro-deposition is 1~2V, time of electro-deposition for 0.5~
10min。
3. the preparation method of iron oxide-bismuth oxide according to claim 1-bismuth sulfide visible light catalytic film, its feature
It is, in step (1), the temperature of the calcination processing is 400~600 DEG C, and calcination time is 1~5h.
4. the preparation method of iron oxide-bismuth oxide according to claim 1-bismuth sulfide visible light catalytic film, its feature
It is, the Bi3+Precursor solution preparation method it is as follows：KI is soluble in water, add Bi (NO3)3·5H2O, after stirring
It is 1.5~2.0 to adjust pH value, adds 1,4-benzoquinone, is again stirring for obtaining Bi3+Precursor solution.
5. the preparation method of iron oxide-bismuth oxide according to claim 4-bismuth sulfide visible light catalytic film, its feature
It is, the Bi3+Precursor solution in, KI concentration is 300~500mM, Bi (NO3)3·5H2O concentration be 20~
60mM；The concentration of 1,4-benzoquinone is 30~70mM.
6. the preparation method of iron oxide-bismuth oxide according to claim 1-bismuth sulfide visible light catalytic film, its 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. the preparation method of iron oxide-bismuth oxide according to claim 1-bismuth sulfide visible light catalytic film, its 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. the Fe that a kind of method according to any one of claim 1~7 is prepared2O3-Bi2O3-Bi2S3Visible light catalytic
Film, it is characterised in that gained Fe2O3-Bi2O3-Bi2S3The thickness of visible light catalytic film is 450~600nm.
9. utilize the Fe described in claim 82O3-Bi2O3-Bi2S3Application of the visible light catalytic film in Phenol-Containing Wastewater Treatment.
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| CN108505062A (en) * | 2018-05-04 | 2018-09-07 | 厦门大学 | A kind of method that electro-catalysis reduction oxygen generates hydrogen peroxide |
| CN108855231A (en) * | 2018-06-29 | 2018-11-23 | 枣庄学院 | A kind of catalyst for electrochemical applications |
| CN113121124A (en) * | 2021-03-29 | 2021-07-16 | 桂林理工大学 | Preparation method of cerium-doped bismuth sulfide/ferric oxide nano heterojunction |
| CN115216325A (en) * | 2022-07-13 | 2022-10-21 | 中国矿业大学 | High-sulfur petroleum coke efficient desulfurization process |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108505062A (en) * | 2018-05-04 | 2018-09-07 | 厦门大学 | A kind of method that electro-catalysis reduction oxygen generates hydrogen peroxide |
| CN108505062B (en) * | 2018-05-04 | 2019-07-23 | 厦门大学 | A kind of method that electro-catalysis reduction oxygen generates hydrogen peroxide |
| CN108855231A (en) * | 2018-06-29 | 2018-11-23 | 枣庄学院 | A kind of catalyst for electrochemical applications |
| CN113121124A (en) * | 2021-03-29 | 2021-07-16 | 桂林理工大学 | Preparation method of cerium-doped bismuth sulfide/ferric oxide nano heterojunction |
| CN115216325A (en) * | 2022-07-13 | 2022-10-21 | 中国矿业大学 | High-sulfur petroleum coke efficient desulfurization process |
| CN115216325B (en) * | 2022-07-13 | 2023-09-08 | 中国矿业大学 | High-efficiency desulfurization process for high-sulfur petroleum coke |
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