CN107020140A - A kind of iron oxide molybdenum sulfide cadmium sulfide visible light catalytic film and its preparation method and application - Google Patents
A kind of iron oxide molybdenum sulfide cadmium sulfide visible light catalytic film and its preparation method and application Download PDFInfo
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- CN107020140A CN107020140A CN201710157433.1A CN201710157433A CN107020140A CN 107020140 A CN107020140 A CN 107020140A CN 201710157433 A CN201710157433 A CN 201710157433A CN 107020140 A CN107020140 A CN 107020140A
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- light catalytic
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 101
- SVIWJDFOHBAJGW-UHFFFAOYSA-N [S-2].[Cd+2].[Mo+2]=S.[O-2].[Fe+2] Chemical compound [S-2].[Cd+2].[Mo+2]=S.[O-2].[Fe+2] SVIWJDFOHBAJGW-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 159
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 135
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 101
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 101
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 238000004070 electrodeposition Methods 0.000 claims abstract description 29
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000012545 processing Methods 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 6
- 239000012528 membrane Substances 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 259
- 238000006243 chemical reaction Methods 0.000 claims description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 6
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- LRSBUFPXQZFANS-UHFFFAOYSA-N [Mo+2]=S.[O-2].[Fe+2].[O-2] Chemical compound [Mo+2]=S.[O-2].[Fe+2].[O-2] LRSBUFPXQZFANS-UHFFFAOYSA-N 0.000 claims 5
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 238000007146 photocatalysis Methods 0.000 abstract description 17
- 238000005516 engineering process Methods 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 54
- 239000000243 solution Substances 0.000 description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 239000002351 wastewater Substances 0.000 description 30
- 230000000694 effects Effects 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 238000006731 degradation reaction Methods 0.000 description 21
- 230000015556 catabolic process Effects 0.000 description 19
- 239000000463 material Substances 0.000 description 16
- 238000006555 catalytic reaction Methods 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000013508 migration Methods 0.000 description 9
- 230000005012 migration Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000011017 operating method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000875 corresponding effect Effects 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 6
- 238000004502 linear sweep voltammetry Methods 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 150000002751 molybdenum Chemical class 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000008236 heating water Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- -1 wherein Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 description 3
- 230000005622 photoelectricity Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method 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
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- 101100476210 Caenorhabditis elegans rnt-1 gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [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
- 239000011149 active material Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 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
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- KSSNXJHPEFVKHY-UHFFFAOYSA-N phenol;hydrate Chemical compound O.OC1=CC=CC=C1 KSSNXJHPEFVKHY-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
-
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- 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
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- 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
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a kind of preparation method of iron oxide molybdenum sulfide cadmium sulfide visible light catalytic film：(1) with Fe2+Precursor solution make electrolyte, in conductive substrates carry out electro-deposition after calcination processing obtain Fe2O3Film；(2) by above-mentioned Fe2O3Membranes submerged is in MoS2Precursor solution in, with hydro-thermal method be made Fe2O3‑MoS2Film；(3) by above-mentioned Fe2O3‑MoS2Film is placed in Cd2+Precursor solution in, Fe is made in heating response2O3‑MoS2CdS visible light catalytic films.Present invention additionally comprises using iron oxide molybdenum sulfide cadmium sulfide visible light catalytic film made from the above method and the application using the film in Phenol-Containing Wastewater Treatment.Preparation technology of the present invention is simple, and repeatability is high, and financial cost is relatively low.By the combination of three kinds of photochemical catalysts with different band structures, synergy is formed, photocatalysis performance is substantially increased.
Description
Technical field
The present invention relates to photoelectrocatalysimaterial material technical field, more particularly to a kind of iron oxide-molybdenum sulfide-cadmium sulfide is visible
Photocatalysis film and its preparation method and application.
Background technology
Now, as the energy and environmental problem are increasingly aggravated, the environment-friendly pollutant abatement technology of effective, harmless is sought
Mankind's problem urgently to be resolved hurrily is turned into.Photo-electrocatalytic technology with its efficient, harmless, energy consumption it is low, it is environment-friendly the features such as and it is standby
Attract attention, there are huge potentiality in terms of the depollution of environment and new energy development, and present its superior application prospect.This
The key of technology is to prepare photocatalysis film efficiently, stable.However, developing the efficient and strong photocatalysis material of practical application
Material is still a huge challenge.
Fe2O3As a kind of visible-light response type semi-conducting material, its band-gap energy is 2.2eV, and maximum absorption wave is a length of
560nm, has preferable photoresponse under Uv and visible light irradiation.In addition, it also has concurrently, physics and chemical stability are good, pass through
Help cost it is low, to the low advantage of environmental hazard.But, Fe2O3Material shortcoming is light induced electron and hole easily compound and light absorbs
Coefficient is small, causes photocatalytic activity relatively low.In recent years, by Fe2O3Catalyst is doped or composite modified improved
Fe2O3The research of photocatalytic activity is arisen at the historic moment.
MoS2It is good two-dimensional sheet nano material, due to its excellent electrical and optical properties in photocatalysis, lithium
The field such as ion battery and opto-electronic device is received significant attention, and its specific surface area is big, can fix a variety of as base material
Material.In addition, CdS is a kind of very potential semiconductor (band gap width is 2.4eV), its band gap width and Fe2O3It is close.
In order to improve visible light catalyst activity, suppress the compound of photo-generate electron-hole, at present, generally can band by two kinds
The semiconductors coupling of structure matching, forms the composite photo-catalyst of heterojunction structure.It can typically take modified doping and semiconductor multiple
The methods such as conjunction.Wherein, semiconductors coupling is that the different photochemical catalysts for being mutually matched two or more band gap are combined, and is formed
The composite photo-catalyst of heterojunction structure, and its catalytic activity is also far above the catalytic performance of single semi-conducting material.But different half
Energy band and structure etc. have larger difference, two or more for being only mutually matched valence band and conduction band positions between conductor
Catalysis material is combined, and could farthest reduce electronics and compound, the lifting photocatalysis effect in hole.Therefore, seek
It is crucial to look for the semiconductor that can be mutually matched to carry out the compound photochemical catalyst so as to form efficient stable.
For how to lift photocatalysis performance, the electric conductivity of different materials itself, band-gap energy, valence band (or conduction band) position
It can all be influenceed Deng many factors, the compound of two kinds of semiconductors is paid attention in most researchs at present, and its photocatalysis effect is not
It is fully up to expectations, and the research that a variety of semiconductors are combined altogether is less.However, a variety of semiconductors are codoping modified can to obtain collaboration work
With effect, catalyst performance is set to obtain the lifting of matter.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of Fe2O3-MoS2- CdS visible light catalytics are thin
Film and preparation method thereof, composite photocatalyst material shows higher photocatalytic activity and stability, and preparation method is simply passed through
Ji.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：
A kind of iron oxide-molybdenum sulfide-cadmium sulfide visible light catalytic film, comprises the following steps：
(1) three-electrode system is used, with Fe2+Precursor solution as electrolyte, conductive substrates are used as working electrode, stone
Electrode ink is that, to electrode, Ag/AgCl electrodes carry out electro-deposition as reference electrode；Fe is made through calcination processing again2O3Film；
(2) by Fe made from step (1)2O3Membranes submerged is in MoS2Precursor solution in carry out hydro-thermal reaction, reaction knot
Shu Houjing washings obtain Fe2O3-MoS2Film；
(3) by Fe made from step (2)2O3-MoS2Film is placed in Cd2+Precursor solution in, enter under conditions of heating
Row reaction, is made Fe2O3-MoS2- CdS visible light catalytic films.
Using photocatalysis film film forming made from electro-deposition, hydro-thermal reaction, the method for heating response is uniform, stability is good,
Active component is difficult to peel off；Film size is easy to control.Obtained Fe2O3-MoS2The light induced electron of-CdS film and hole separation
Efficiency high, with good photoelectric catalytically active.
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.Fe2+Precursor solution in, the mixed liquor of the ethylene glycol and water is conducive in electrodeposition process
The formation of ferrous hydroxide, wherein, the mixed proportion of ethylene glycol and water can also influence the pattern of prepared film, and then influence thin
The photocatalysis performance of film.
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 present invention preparation method in photocatalyst film gross thickness be substantially equal to electro-deposition formation film thickness,
Hydro-thermal method and the film thickness sum of heating response formation.Temperature, time and the operating voltage of electro-deposition are directly connected to electrolysis
The quality (i.e. the thickness of electrodeposited film) of the product of deposition and the product formed.After the completion of electro-deposition, high-temperature calcination need to be passed through
Further oxidation, and calcining heat and time also directly affect the Fe of generation2O3Crystalline phase, so as to influence the light of composite membrane to urge
Change performance.
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 0.5~15min；
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 300~600 DEG C, and calcination time is 0.5~5h；Further preferably, forge
The temperature for burning processing is 450~550 DEG C, and calcination time is 1~3h, and catalytic film is controlled by calcining at constant temperature temperature and time
Crystallinity.Under preferred calcining heat, material has good crystallinity, and crystalline phase is α-Fe2O3, crystallinity is good, photocatalysis
Activity is higher.When calcining heat is relatively low, the crystallinity of material is very poor, greatly limits photocatalytic activity；When calcining heat mistake
Gao Shi, can influence the formation of film because the heat resisting temperature of conductive substrates is limited.
(2) in step (2)：
Preferably, the MoS2Precursor solution be formulated by molybdenum salt, thiocarbamide and water, wherein, molybdenum salt be tetrathio
Ammonium molybdate and/or ammonium molybdate.
Preferably, the MoS2Precursor solution in, the concentration of molybdenum salt is 0.001~0.006M, and the concentration of thiocarbamide is
0.01~0.08M；Further preferably, the concentration of molybdenum salt is 0.001~0.003M, and the concentration of thiocarbamide is 0.02~0.03M.
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；When conductive face-down, MoS2Layer grow on the base layer it is uneven so that
The photoelectric properties of film are influenceed to a certain extent.
In the present invention, Fe is made using hydro-thermal method2O3-MoS2Film, and MoS2The thickness of film is mainly by controlling hydro-thermal
Time of reaction and temperature are controlled, it is preferable that the temperature of hydro-thermal reaction is 100~400 DEG C, and the reaction time is 1~5h；Enter one
Step is preferred, and the temperature of hydro-thermal reaction is 100~250 DEG C, and the reaction time is 1~3h；Most preferably, hydrothermal temperature is 220
DEG C, the reaction time is 2h；
(3) in step (3)：
Preferably, the Cd2+Precursor solution by cadmium sulfate (CdH16O12S), thiocarbamide (CH4N2S), ammoniacal liquor and water are prepared
Form.
Preferably, the Cd2+Precursor solution in, the concentration of cadmium sulfate is 0.1~2mM, and the mass fraction of ammoniacal liquor is
25~28%, the concentration of thiocarbamide is 1~10mM；Further preferably, the concentration of cadmium sulfate is 0.3~1mM, the mass fraction of ammoniacal liquor
For 5~8%, the concentration of thiocarbamide is 2~7mM.
Preferably, in step (3), the temperature of the reaction is 50~80 DEG C, and the time of reaction is 5~20min；Further
It is preferred that, the temperature of the reaction is 50~70 DEG C, and the time of reaction is 5~15min.
The photoelectric catalytically active of photocatalysis film is relevant with thickness, the migration of the too thick influence photo-generated carrier of film.Thickness
Moderate doping can excite the generation of carrier, moreover it is possible to improve the migration rate of carrier, so as to improve the photoelectricity of doping
Catalytic activity.
Present invention also offers a kind of Fe prepared by the above method2O3-MoS2- CdS visible light catalytic films, institute
Obtain Fe2O3-MoS2- CdS visible light catalytics film includes the Fe being located in conductive substrates successively from the bottom to top2O3Film and it is located at
Fe2O3MoS on film2Film and CdS film.
The photoelectric catalytically active of photocatalysis film is relevant with thickness, the migration of the too thick influence photo-generated carrier of film.Thickness
Moderate doping can excite the generation of carrier, moreover it is possible to improve the migration rate of carrier, so as to improve the photoelectricity of doping
Catalytic activity.
The present invention preparation method in photocatalyst film gross thickness be substantially equal to electro-deposition formation film thickness,
Hydro-thermal method and the film thickness sum of heating response formation.
The Fe2O3-MoS2The thickness of-CdS visible light catalytic films is 500~600nm.Under the thickness, Fe2O3-MoS2-
CdS visible light catalytics film can excite the generation of carrier, moreover it is possible to improve the migration rate of carrier, so as to improve doping
Photoelectric catalytically active.
Obtained Fe is utilized present invention additionally comprises a kind of2O3-MoS2- CdS visible light catalytic films are in Phenol-Containing Wastewater Treatment
In application.
Compared with prior art, the invention has the advantages that：
(1) Fe produced by the present invention2O3-MoS2- CdS film surface is uniform, active material stability is good, is difficult to peel off, thin
Membrane area is easy to control, due to MoS2, CdS and Fe2O3Synergy, makes the light induced electron and hole separation effect of tri compound film
Rate is high, with good photoelectric catalytically active；
(2) by determining, under visible ray photograph, the Fe of preparation2O3-MoS2The photoelectric current phase of-CdS visible light catalytic films
For Fe2O3Film improves about 40 times；Under ultraviolet-visible illumination, photoelectric current is relative to Fe2O3Film improves about 53 times.
(3) method of the invention can be carried out at normal temperatures, applied widely, Fe2O3-MoS2- CdS visible light catalytics are thin
Film can be recycled during the course of the reaction, using the irradiation of visible ray, improves the utilization rate to solar energy, realizes efficient profit
With solar energy, cost is significantly reduced, secondary pollution is reduced；
(4) Fe in the present invention2O3-MoS2It is difficult that-CdS visible light catalytics film can avoid conventional powder photocatalyst from reclaiming
The problem of, improve photocatalysis efficiency can be simultaneously using photoelectric-synergetic technology come degrading waste water, degradation effect is more preferable.
Brief description of the drawings
Fig. 1 is Fe2O3-MoS2- CdS visible light catalytics film, Fe2O3-MoS2Film and Fe2O3Film is molten in 0.1M NaOH
Visible ray in liquid is according to the linear sweep voltammetry curve under alternating；
Fig. 2 is Fe2O3-MoS2- CdS visible light catalytics film, Fe2O3-MoS2Film and Fe2O3Film is molten in 0.1M NaOH
The linear sweep voltammetry curve under ultraviolet-visible illumination alternately in liquid；
Fig. 3 is Fe2O3-MoS2- CdS visible light catalytics film, Fe2O3-MoS2Film and Fe2O3Film is molten in 0.1M NaOH
Electrochemical impedance collection of illustrative plates (EIS collection of illustrative plates) in liquid under dark condition；
Fig. 4 is Fe2O3-MoS2- CdS visible light catalytics film, Fe2O3-MoS2Film and Fe2O3Film is molten in 0.1M NaOH
Electrochemical impedance collection of illustrative plates (EIS collection of illustrative plates) in liquid under visible light conditions；
Fig. 5 is Fe2O3-MoS2- CdS visible light catalytics film, Fe2O3-MoS2Film and Fe2O3IPCE curve (the light of film
Electro-catalysis transformation efficiency curve)；
Fig. 6 is Fe2O3-MoS2- CdS visible light catalytics film, Fe2O3-MoS2Film and Fe2O3The instantaneous photoelectric current of film-
Time (lnD-T) curve map；
Fig. 7 is Fe2O3Film, Fe2O3-MoS2Film and Fe2O3-MoS2- CdS visible light catalytic films are right under visible light
The clearance of pending phenol in wastewater compares；
Fig. 8 is pending phenol wastewater under the conditions of pure electric condition (EC), pure optical condition (PC) and photoelectric-synergetic condition (PEC)
The clearance of middle phenol compares；
Fig. 9 is initial phenol concentration to Fe2O3-MoS2- CdS visible light catalytics film is under visible light to pending waste water
The clearance influence of middle phenol；
Figure 10 is to the degradation rate of phenol in every part of pending phenol wastewater in embodiment 5；
Figure 11 is phenol wastewater pH value to Fe2O3-MoS2The shadow of-CdS visible light catalytic film photoelectric catalysis of phenol clearances
Ring；
Figure 12 is obtained Fe in embodiment 72O3-MoS2- CdS visible light catalytic films, MoS2- CdS film, Fe2O3-
CdS film, CdS film and MoS2Visible ray of the film in 0.1M NaOH solutions is according to the linear sweep voltammetry curve under alternating.
Embodiment
Embodiment 1
The present invention is further detailed explanation below in conjunction with the accompanying drawings and the specific embodiments.
The Fe of the present embodiment2O3-MoS2The preparation method of-CdS visible light catalytic films comprises the following steps：
(1) with Fe2+Precursor solution as electrolyte, use three electrode bodies using CHI660E types electrochemical workstation
System carries out electro-deposition, i.e., with the conductive substrates electro-conductive glass (FTO) after over cleaning, drying and processing for working electrode, graphite
Electrode is that, to electrode, Ag/AgCl electrodes carry out calcining at constant temperature acquisition Fe as reference electrode after it dries naturally2O3Film；
Fe in the implementation case2+Precursor solution preparation method it is as follows：Weigh a certain amount of FeCl2·4H2O is molten
In the ethylene glycol and distilled water of certain volume, Fe2+Precursor solution in, Fe2+Concentration be 0.02M, ethylene glycol with distillation
The volume ratio of water is 1：8.
Electrodeposition technology in the thickness of the catalytic film obtained by electro-deposition process parameter control electro-deposition, the present embodiment
Parameter is as follows：Electrodeposition temperature is 70 DEG C, and operating voltage is 1.36V, and sedimentation time is 5min.Then by the conductive base deposited
Bottom is put into Muffle furnace after drying, and calcining at constant temperature 2h, that is, obtain Fe at 500 DEG C2O3Film.
(2) by Fe made from step (1)2O3After film dries naturally, conductive slant setting up is immersed in MoS2's
In precursor solution, it is placed in autoclave, Fe is made with hydro-thermal method2O3-MoS2Film；
MoS in the present embodiment2Precursor solution be ammonium molybdate ((NH4)6Mo7O24·4H2O), thiocarbamide (H2NCSNH2)
With the mixed solution of water；The concentration of thiocarbamide is 0.025M, and the concentration of ammonium molybdate is 0.002M；
In the present embodiment, Fe is made using hydro-thermal method2O3-MoS2Film, and MoS2The thickness of film is mainly high by controlling
Press in reaction time and the controlling reaction temperature of reactor, the present embodiment, the hydro-thermal reaction time is 2h, and reaction temperature is 220
℃。
(3) by Fe made from step (2)2O3-MoS2Film is placed in Cd2+Precursor solution in, the heating water bath at 60 DEG C
10min, is made Fe2O3-MoS2- CdS visible light catalytic films, the thickness for measuring film is 520nm.
Cd in the present embodiment2+Precursor solution prepared by following methods：Take 2.4ml ammoniacal liquor, 0.028mmol cadmium sulfates
(CdH16O12) and 0.2mmol thiocarbamides (CH S4N2S) it is dissolved in 40ml distilled water.
Fig. 1 is Fe2O3-MoS2- CdS visible light catalytics film, Fe2O3-MoS2Film and Fe2O3Film is molten in 0.1M NaOH
Visible ray in liquid is according to the linear sweep voltammetry curve under alternating；
Fig. 2 is Fe2O3-MoS2- CdS visible light catalytics film, Fe2O3-MoS2Film and Fe2O3Film is molten in 0.1M NaOH
The linear sweep voltammetry curve under ultraviolet-visible illumination alternately in liquid.
As shown in Figure 1, under visible ray photograph, compared to Fe2O3Film, when voltage is 0.45V, MoS2Construct so that light
Electric current (i.e. current density) accordingly improves 13 times, i.e. MoS2The compound catalytic activity for improving film.Compared to Fe2O3It is thin
Film, when voltage is 0.45V, MoS2- CdS's constructs so that Fe2O3-MoS2The photoelectric current of-CdS film accordingly improves 40 times, i.e.,
MoS2The catalytic activity of film is further increased with constructing jointly for CdS.As shown in Figure 2, under ultraviolet-visible illumination, phase
Compared with Fe2O3Film, when voltage is 0.45V, MoS2Construct so that Fe2O3-MoS2The photoelectric current of film compares Fe2O3Film is improved
10 times；Compared to Fe2O3Film, MoS2- CdS's constructs so that Fe2O3-MoS2The photoelectric current of-CdS film accordingly improves 53
Times.
In addition, it will be evident that the moment for being blocked or showing in visible ray or ultraviolet-visible from Fig. 1 and Fig. 2,
Fe2O3The photoelectric current of film can be rapidly reached maximum, then just decay to certain value, and this is due to Fe2O3Film answering in itself
Close larger, light induced electron and hole are soon combined once generation.And construct MoS2Be not in then such a phenomenon, this explanation afterwards
MoS2In Fe2O3Film surface can suppress the compound of light induced electron and hole.After CdS is further constructed, in visible ray or purple
The moment that outer visible ray is blocked or shown, Fe2O3-MoS2The photoelectric current of-CdS film can be rapidly reached maximum, now most
Fe before being worth relatively greatly2O3Film and Fe2O3-MoS2Film has larger lifting, illustrates the Fe of tri compound2O3-MoS2-CdS
Preferably, the photoelectric current of generation is most strong, Fe for photoelectric respone2O3、MoS2Synergy is produced between tri- kinds of materials of CdS.
Fig. 3 is Fe2O3-MoS2- CdS visible light catalytics film, Fe2O3-MoS2Film and Fe2O3Film is molten in 0.1M NaOH
Electrochemical impedance collection of illustrative plates (EIS collection of illustrative plates) in liquid under dark condition；Fig. 4 is Fe2O3-MoS2- CdS visible light catalytics film,
Fe2O3-MoS2Film and Fe2O3(EIS schemes electrochemical impedance collection of illustrative plates of the film in 0.1M NaOH solutions under visible light conditions
Spectrum).The frequency range that electrochemical workstation is set is 106Hz-0.01Hz.From Fig. 3, Fig. 4, either still exist dark
Under the conditions of visible ray shines, Fe2O3-MoS2The impedance ring radius of film is both less than Fe2O3Film, moreover, Fe2O3-MoS2- CdS film
Impedance ring radius be significantly less than Fe2O3-MoS2Film.In electrochemical alternate impedance spectrum, impedance ring radius is smaller, illustrates this
The resistance of material is smaller, and photogenerated charge transfer ability is stronger.It follows that Fe2O3-MoS2- CdS film photo-generate electron-hole energy
Significantly more efficient separation.
Fig. 5 is Fe2O3-MoS2- CdS visible light catalytics film, Fe2O3-MoS2Film and Fe2O3IPCE curve (the light of film
Electro-catalysis transformation efficiency curve).From Fig. 5 IPCE collection of illustrative plates, Fe2O3-MoS2The IPCE values of-CdS film apparently higher than
Fe2O3-MoS2Film and Fe2O3Film.For Fe2O3-MoS2For-CdS film, the response points of IPCE curves be in 575nm,
And Fe2O3-MoS2Film and Fe2O3Film is just begun to respond at 550nm, so Fe2O3-MoS2- CdS film compares Fe2O3-MoS2
Film and simple Fe2O3Film shows broader visible absorption scope.Moreover, at wavelength 400nm, Fe2O3-MoS2-
The IPCE of CdS film is Fe2O3Twice of film IPCE, is higher by Fe2O3-MoS2Film three times are more, and this shows Fe2O3-MoS2-CdS
Laminated film shows significant synergy in terms of photoelectric activity.
Fig. 6 is Fe2O3-MoS2- CdS visible light catalytics film, Fe2O3-MoS2Film and Fe2O3The instantaneous photoelectric current of film-
Time (lnD-T) curve map.In instantaneous photocurrent-time curve figure, for some specific ln D value, if surveying catalysis material
Expect that corresponding t values are bigger, then photo-generated carrier recombination rate is lower in the electrode.Under surveyed applying bias, compare three kinds and urge
Change the curve of film, for any ln D values, Fe2O3-MoS2The corresponding t values of-CdS film are maximum all the time, and photo-generated carrier is combined
Speed is low.It will be appreciated from fig. 6 that as ln D=-1, Fe2O3-MoS2T values corresponding to-CdS film are 3.8s, Fe2O3-MoS2Film
Corresponding t values are 2.3s, Fe2O3T values corresponding to film are 1.2s, the surface photo-generated carrier of the bigger laminated film of t values
Recombination rate is lower.It can thus be concluded that in the bias range entirely applied, Fe2O3-MoS2The compound speed of-CdS film photo-generated carrier
Rate is minimum.
Complex chart 5 and Fig. 6 understand, Fe2O3-MoS2- CdS visible light catalytic films are shown significantly in terms of photoelectric activity
Cooperative effect, the Fe for preparing of the present invention2O3-MoS2There is-CdS visible light catalytic films excellent visible light catalytic to live
Property.
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 Fe made from embodiment 12O3-MoS2The place of the phenol wastewater of-CdS visible light catalytic films
Reason method, processing procedure is as follows：
(S1) pH value of pending phenol wastewater is adjusted to 6.3；
By the way that 1M H are added dropwise2SO4Solution or 1M NaOH solutions adjust the pH value of phenol wastewater.
(S2) to carrying out photoelectrocatalysis processing after regulation pH value.The light positive electrode used during photoelectrocatalysis processing includes conduction
Substrate and the Fe for being coated on conductive substrates surface2O3-MoS2- CdS visible light catalytics film (film effective area is 2cm × 2cm),
Negative electrode is the titanium sheet of identical effective area.
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 light positive electrode and negative electrode is 2.5V, in radiation of visible light
Under the conditions of carry out.
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.
Fe is given in the present embodiment2O3Film and Fe2O3-MoS2Film treat the degraded situation of Phenol-Containing Wastewater Treatment with
Contrasted.
Fig. 7 is Fe2O3Film, Fe2O3-MoS2Film and Fe2O3-MoS2- CdS visible light catalytic films are right under visible light
The clearance of pending phenol in wastewater compares.After 5h photoelectrocatalysis reaction, ternary Fe2O3-MoS2The conduct of-CdS film
The clearance of phenol is up to 90.47% during anode, and simple Fe2O3Fe is combined with binary2O3-MoS2Gone when film is as anode
Except rate is significantly lower than trielement composite material, respectively 54.57% and 69.14%.In addition, degradation process is anti-with first order kinetics is intended
Answer model to be fitted, calculate its reaction rate constant, understood after the Fitting Calculation, under visible ray photograph, Fe2O3-MoS2-CdS
The reaction rate of film is Fe respectively2O3And Fe2O3-MoS23.17 and 2.05 times.To sum up analysis is understood, MoS2With CdS layer pair
All it is had a certain upgrade effect in photoelectric catalysis degrading performance, and builds the visible photoelectricity of trielement composite material of composition for two layers altogether and is urged
Change activity relatively optimal, while phenol clearance is improved, reaction rate is also accelerated.
Embodiment 3
It is same as Example 2, except that treatment conditions are different.In the present embodiment respectively under pure electric and pure optical condition
Carry out, to study Fe2O3-MoS2- CdS visible light catalytics film distinguishes the degraded situation of Pyrogentisinic Acid under different illumination conditions.
Fig. 8 is pending phenol wastewater under the conditions of pure electric condition (EC), pure optical condition (PC) and photoelectric-synergetic condition (PEC)
The clearance of middle phenol compares, and wherein corresponding curve is in the same manner as in Example 2 under the conditions of photoelectric-synergetic condition (PEC).
As shown in figure 8, after reaction 5h, Fe2O3-MoS2The effect of-CdS film photoelectric catalysis degrading phenol is substantially better than list
Pure photocatalysis (19.26%) or electro-catalysis (7.30%), photoelectrocatalysis phenol clearance are 90.47%, photoelectric-synergetic effect
Significantly.In addition, degradation process is fitted with first order kinetics reaction model is intended, its reaction rate constant is calculated, is counted through fitting
Understood after calculation, when catalytic type is different, the reaction rate of photoelectrocatalysis reaction is respectively 38 times of simple photocatalysis and electro-catalysis
With 10.86 times, further demonstrate and there is the effect of significant photoelectric-synergetic during phenol degrading, subsequent degradation experiment exists
Studied under photoelectrocatalysis reaction system.
Embodiment 4
Different phenol wastewater are handled using processing method same as Example 2, that is, carry out adopting during phenolic wastewater treatment
The parameter all same of light positive electrode, processing procedure and wherein each step, except that in pending phenol wastewater
The initial concentration of phenol is different.
The initial concentration of phenol is as follows in pending phenol wastewater in the present embodiment：5mg/L, 10mg/L and 20mg/L.
Fig. 9 is initial phenol concentration to Fe2O3-MoS2- CdS visible light catalytics film is under visible light to pending waste water
The clearance influence of middle phenol.
As seen from the figure, in the range of surveyed pollutant initial concentration, with Fe2O3-MoS2- CdS visible light catalytics film is light
When anode carries out photoelectrocatalysis reaction degradation of phenol, preferable removal effect is suffered from, when concentration is relatively low (5,10mg/L), benzene
The clearance of phenol is more than 90%, and respectively 91.50% and 90.47%, at concentration higher (20mg/L), also have certain
Degradation effect, the clearance of phenol is 50.76%.
Embodiment 5
To the Fe of preparation2O3-MoS2- CdS visible light catalytics film has carried out circulation degradation experiment：Take pending useless containing phenol
Water is simultaneously divided into four parts, using method same as Example 2, using same a pair of photoelectrocatalysielectrode electrodes to waiting to locate to every portion respectively
Reason phenol wastewater is handled.
Figure 10 is the degradation rate to phenol in every part of pending phenol wastewater, according to processing sequence, rear phenol per treatment
Degradation rate curve be respectively run1, run2, run3 and run4.
As seen from the figure, Fe2O3-MoS2After-CdS visible light catalytic film degradations phenol wastewater 4 times, the clearance base of phenol
This holding is constant, 90% or so, and this film of preliminary identification has good reusability and stability.
Embodiment 6
Different phenol wastewater are handled using processing method same as Example 2, that is, carry out adopting during phenolic wastewater treatment
The parameter all same of light positive electrode, processing procedure and wherein each step, except that pending phenol wastewater
Initial pH value is different, that is, presets pH value different.
Adjusted in the present embodiment the pH value of pending phenol wastewater to：3.0th, 6.3 and 9.0.
Figure 11 phenol wastewater pH value is to Fe2O3-MoS2The shadow of-CdS visible light catalytic film photoelectric catalysis of phenol clearances
Ring.
As shown in Figure 11, the pH value of phenol wastewater significantly affects the degradation effect of phenol：When phenol wastewater pH value is 3.0
During with 6.3, preferably, the clearance of phenol is 90% or so for phenol degrading effect；When phenol wastewater pH value for 9.0 in alkalescence
When, the poor degradation effect of phenol is 55.19%.It can be seen that, when pending phenol wastewater pH value is adjusted between 3~6.3,
Fe2O3-MoS2- CdS visible light catalytics film suffers from preferable degradation effect for photoelectric catalysis degrading phenol.
Embodiment 7
Further to investigate effect and the meaning that different cati materials are present, Fe is prepared for2O3-MoS2- CdS visible rays
Catalytic film, MoS2- CdS film, Fe2O3- CdS film, CdS film and MoS2Film is contrasted under the same conditions, specifically
Preparation method is as follows：
(1)Fe2O3-MoS2- CdS visible light catalytic films：Preparation method be the same as Example 1.
(2)MoS2Film：Conductive tilt up of FTO is immersed in MoS2Precursor solution in, be placed on high pressure anti-
Answer in kettle, MoS is made with hydro-thermal method2Film.
MoS2Precursor solution preparation method be the same as Example 1.
(3)MoS2- CdS film：By obtained MoS in (2)2Film is put into Cd2+Precursor solution in, in 60 DEG C of water-baths
Middle reaction 10 minutes, obtains MoS2- CdS film；
Cd2+Precursor solution preparation method be the same as Example 1.
(4)Fe2O3- CdS film：According to Fe made from the step in embodiment 12O3Film is put into Cd2+Precursor solution
In, reacted 10 minutes in 60 DEG C of water-baths, obtain Fe2O3- CdS film；
Cd2+Precursor solution preparation method be the same as Example 1.
(5) CdS film：FTO is put into Cd2+Precursor solution in, in 60 DEG C of water-baths react 10 minutes, obtain CdS
Film.
Cd2+Precursor solution preparation method be the same as Example 1.
Figure 12 is obtained Fe in the present embodiment2O3-MoS2- CdS visible light catalytic films, MoS2- CdS film, Fe2O3-
CdS film, CdS film and MoS2Visible ray of the film in 0.1M NaOH solutions is according to the linear sweep voltammetry curve under alternating.
As shown in Figure 12, under the irradiation of visible ray, in the range of surveyed applying bias, Fe2O3-MoS2The photoelectric current of-CdS film is big
In MoS2- CdS film, this explanation Fe2O3There is certain facilitation to the lifting of photoelectric current for substrate；In addition, MoS2- CdS is thin
The photoelectric current of film is significantly higher than MoS2Film, the effect for further demonstrating CdS layer is notable；Directly by FTO in Cd2+Presoma
The film that chemical thought obtains CdS is carried out in solution, there is certain photoelectric current, but significantly lower than Fe2O3-MoS2- CdS and
MoS2- CdS, also indirect proof Fe2O3And MoS2Effect；When directly by FTO in MoS2Precursor solution in carry out hydro-thermal
React obtained MoS2Film, photoelectric current does not have significant change, illustrates simple MoS2PhotoelectrocatalytiPerformance Performance is poor.Summary
Test result, determines Fe2O3-MoS2Be implicitly present in synergy between three kinds of materials of-CdS photoelectrocatalysithin thin films, make it have compared with
Good photoelectric properties.
Embodiment 8
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare Fe2O3-MoS2- CdS visible light catalytic films
During, in step (1), the temperature of electro-deposition is 40 DEG C, and the voltage of electro-deposition is 1.02V, and the time of electro-deposition is
10min；The temperature of calcination processing is 450 DEG C, and calcination time is 5h.
The Fe prepared under conditions of the present embodiment2O3-MoS2- CdS visible light catalytic film photoelectric chemical properties be inferior to by
Fe made from the condition of embodiment 12O3-MoS2- CdS visible light catalytic films, compared to Fe2O3Film, the Fe of the present embodiment2O3-
MoS2The photoelectric current (i.e. current density) of-CdS visible light catalytic films accordingly improves 35 times；The Pyrogentisinic Acid under visible light conditions
Degradation rate be 85.8%.
Embodiment 9
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare Fe2O3-MoS2- CdS visible light catalytic films
During, in step (2), MoS2Precursor solution in molybdenum salt be four thio ammonium molybdate, the concentration of thiocarbamide is 0.07M, four
The concentration of ammonium thiomolybdate is 0.006M.In step (2), the temperature of hydro-thermal reaction is 200 DEG C, and the reaction time is 5h.
The Fe prepared under conditions of the present embodiment2O3-MoS2- CdS visible light catalytic film photoelectric chemical properties be inferior to by
Fe made from the condition of embodiment 12O3-MoS2- CdS visible light catalytic films, compared to Fe2O3Film, the Fe of the present embodiment2O3-
MoS2The photoelectric current (i.e. current density) of-CdS visible light catalytic films accordingly improves 37 times；The Pyrogentisinic Acid under visible light conditions
Degradation rate be 86.1%.
Embodiment 10
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare Fe2O3-MoS2- CdS visible light catalytic films
During, in step (2), the temperature of hydro-thermal reaction is 250 DEG C, and the reaction time is 3h.
The Fe prepared under conditions of the present embodiment2O3-MoS2- CdS visible light catalytic film photoelectric chemical properties be inferior to by
Fe made from the condition of embodiment 12O3-MoS2- CdS visible light catalytic films, compared to Fe2O3Film, the Fe of the present embodiment2O3-
MoS2The photoelectric current (i.e. current density) of-CdS visible light catalytic films accordingly improves 39 times；The Pyrogentisinic Acid under visible light conditions
Degradation rate be 89.1%.
Embodiment 11
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare Fe2O3-MoS2- CdS visible light catalytic films
During, in step (2), the temperature of hydro-thermal reaction is 400 DEG C, and the reaction time is 1h.
The Fe prepared under conditions of the present embodiment2O3-MoS2- CdS visible light catalytic film photoelectric chemical properties be inferior to by
Fe made from the condition of embodiment 12O3-MoS2- CdS visible light catalytic films, compared to Fe2O3Film, the Fe of the present embodiment2O3-
MoS2The photoelectric current (i.e. current density) of-CdS visible light catalytic films accordingly improves 34 times；The Pyrogentisinic Acid under visible light conditions
Degradation rate be 84.6%.
Embodiment 12
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare Fe2O3-MoS2- CdS visible light catalytic films
During, in step (3), by Fe made from step (2)2O3-MoS2Film is placed in Cd2+Precursor solution in, at 50 DEG C
Heating water bath 20min
The Fe prepared under conditions of the present embodiment2O3-MoS2- CdS visible light catalytic film photoelectric chemical properties be inferior to by
Fe made from the condition of embodiment 12O3-MoS2- CdS visible light catalytic films, compared to Fe2O3Film, the Fe of the present embodiment2O3-
MoS2The photoelectric current (i.e. current density) of-CdS visible light catalytic films accordingly improves 38 times；The Pyrogentisinic Acid under visible light conditions
Degradation rate be 89.2%.
Embodiment 13
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare Fe2O3-MoS2- CdS visible light catalytic films
During, in step (3), by Fe made from step (2)2O3-MoS2Film is placed in Cd2+Precursor solution in, at 80 DEG C
Heating water bath 5min
The Fe prepared under conditions of the present embodiment2O3-MoS2- CdS visible light catalytic film photoelectric chemical properties be inferior to by
Fe made from the condition of embodiment 12O3-MoS2- CdS visible light catalytic films, compared to Fe2O3Film, the Fe of the present embodiment2O3-
MoS2The photoelectric current (i.e. current density) of-CdS visible light catalytic films accordingly improves 32 times；The Pyrogentisinic Acid under visible light conditions
Degradation rate be 83.6%.
Embodiment 14
The operating procedure of Examples 1 and 2 is repeated, difference is to prepare Fe2O3-MoS2- CdS visible light catalytic films
During, in step (3), by Fe made from step (2)2O3-MoS2Film is placed in Cd2+Precursor solution in, at 70 DEG C
Heating water bath 15min
The Fe prepared under conditions of the present embodiment2O3-MoS2- CdS visible light catalytic film photoelectric chemical properties be inferior to by
Fe made from the condition of embodiment 12O3-MoS2- CdS visible light catalytic films, compared to Fe2O3Film, the Fe of the present embodiment2O3-
MoS2The photoelectric current (i.e. current density) of-CdS visible light catalytic films accordingly improves 39 times；The Pyrogentisinic Acid under visible light conditions
Degradation rate be 89.9%.
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. a kind of iron oxide-molybdenum sulfide-cadmium sulfide visible light catalytic film, it is characterised in that comprise the following steps：
(1) three-electrode system is used, with Fe2+Precursor solution as electrolyte, conductive substrates are used as working electrode, graphite electricity
Extremely to electrode, Ag/AgCl electrodes carry out electro-deposition as reference electrode；Fe is made through calcination processing again2O3Film；
(2) by Fe made from step (1)2O3Membranes submerged is in MoS2Precursor solution in carry out hydro-thermal reaction, after reaction terminates
It is scrubbed to obtain Fe2O3-MoS2Film；
(3) by Fe made from step (2)2O3-MoS2Film is placed in Cd2+Precursor solution in, carried out under conditions of heating anti-
Should, Fe is made2O3-MoS2- CdS visible light catalytic films.
2. iron oxide-molybdenum sulfide according to claim 1-cadmium sulfide visible light catalytic film, it is characterised in that step
(1) in, the temperature of electro-deposition is 60~80 DEG C, and the voltage of electro-deposition is 1~1.5V, and the time of electro-deposition is 4~6min.
3. iron oxide-molybdenum sulfide according to claim 1-cadmium sulfide visible light catalytic film, it is characterised in that step
(1) in, the temperature of the calcination processing is 450~550 DEG C, and calcination time is 1~3h.
4. iron oxide-molybdenum sulfide according to claim 1-cadmium sulfide visible light catalytic film, it is characterised in that step
(2) in, the temperature of hydro-thermal reaction is 100~250 DEG C, and the reaction time is 1~3h.
5. iron oxide-molybdenum sulfide according to claim 1-cadmium sulfide visible light catalytic film, it is characterised in that the Cd2 +Precursor solution be formulated by cadmium sulfate, thiocarbamide, ammoniacal liquor and water, wherein, the concentration of cadmium sulfate is 0.1~2mM, thiocarbamide
Concentration be 1~10mM, the mass fraction of ammoniacal liquor is 25~28%.
6. iron oxide-molybdenum sulfide according to claim 1-cadmium sulfide visible light catalytic film, it is characterised in that step
(3) in, the temperature of the reaction is 50~80 DEG C, and the time of reaction is 5~20min.
7. the Fe that a kind of method according to any one of claim 1~6 is prepared2O3-MoS2- CdS visible light catalytics are thin
Film, it is characterised in that gained Fe2O3-MoS2- CdS visible light catalytics film includes being located in conductive substrates from the bottom to top successively
Fe2O3Film and positioned at Fe2O3MoS on film2Film and CdS film.
8. Fe according to claim 72O3-MoS2- CdS visible light catalytic films, it is characterised in that the Fe2O3-
MoS2The thickness of-CdS visible light catalytic films is 500~600nm.
9. the Fe described in a kind of utilization claim 72O3-MoS2- CdS visible light catalytic films answering in Phenol-Containing Wastewater Treatment
With.
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