CN107020140B - 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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- CN107020140B CN107020140B CN201710157433.1A CN201710157433A CN107020140B CN 107020140 B CN107020140 B CN 107020140B CN 201710157433 A CN201710157433 A CN 201710157433A CN 107020140 B CN107020140 B CN 107020140B
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 98
- 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 9
- 238000002360 preparation method Methods 0.000 title abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 153
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 130
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 106
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 106
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 238000004070 electrodeposition Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 238000012545 processing Methods 0.000 claims abstract description 12
- 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 260
- 238000006243 chemical reaction Methods 0.000 claims description 28
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 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 6
- 239000010409 thin film Substances 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 238000007146 photocatalysis Methods 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 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 39
- 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 25
- 238000006731 degradation reaction Methods 0.000 description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 230000015556 catabolic process Effects 0.000 description 21
- 239000000463 material Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 15
- 238000006555 catalytic reaction Methods 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 10
- 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
- 230000008569 process Effects 0.000 description 7
- 230000000593 degrading effect Effects 0.000 description 6
- 238000005516 engineering process Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 150000002751 molybdenum Chemical class 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
- 239000008236 heating water Substances 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
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- -1 moreover Substances 0.000 description 3
- 230000005622 photoelectricity Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002904 solvent Substances 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
- 238000004364 calculation method Methods 0.000 description 2
- 238000004140 cleaning 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
- 239000013078 crystal Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 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
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000004044 response Effects 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
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 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
- 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
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 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
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 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
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 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
- 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
- 238000005303 weighing Methods 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- B01J35/39—
-
- B01J35/59—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a kind of iron oxide-molybdenum sulfide-cadmium sulfide visible light catalytic film preparation methods: (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, Fe is made with hydro-thermal method2O3‑MoS2Film；(3) by above-mentioned Fe2O3‑MoS2Film is placed in Cd2+Precursor solution in, heating react be made Fe2O3‑MoS2- CdS visible light catalytic film.The invention also includes 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 process of the present invention is simple, and repeatability is high, and economic cost is lower.By the combination of three kinds of photochemical catalysts with different band structures, synergistic effect is formed, photocatalysis performance is substantially increased.
Description
Technical field
The present invention relates to photoelectrocatalysimaterial material technical fields, visible more particularly to a kind of iron oxide-molybdenum sulfide-cadmium sulfide
Photocatalysis film and its preparation method and application.
Background technique
Now, as energy and environmental problem increasingly aggravates, seek the environmental-friendly pollutant abatement technology of effective, harmless
Have become mankind's project urgently to be resolved.The features such as photo-electrocatalytic technology is efficient with its, harmless, low energy consumption, environmental-friendly and it is standby
It attracts 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 efficient, stable photocatalysis film.However, the photocatalysis material that development is efficient and practical application is strong
Material is still a huge challenge.
Fe2O3As a kind of visible-light response type semiconductor material, band-gap energy 2.2eV, 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
It helps the advantages such as at low cost, low to environmental hazard.But Fe2O3Material disadvantage is light induced electron and hole easily compound and light absorption
Coefficient is small, causes photocatalytic activity lower.In recent years, by Fe2O3Catalyst is doped or composite modified improves
Fe2O3The research of photocatalytic activity is come into being.
MoS2It is good two-dimensional sheet nano material, due to its excellent electrical and optical properties in photocatalysis, lithium
The fields such as ion battery and opto-electronic device receive significant attention, large specific surface area, can be a variety of as base material fixation
Material.In addition, CdS is a kind of very potential semiconductor (band gap width 2.4eV), band gap width and Fe2O3It is close.
In order to improve visible light catalyst activity, inhibit the compound of photo-generate electron-hole, currently, usually by two kinds of energy bands
The semiconductors coupling of structure matching forms the composite photo-catalyst of heterojunction structure.It can generally take modified doping and semiconductor multiple
The methods of close.Wherein, it is compound to be that the different photochemical catalysts that are mutually matched two or more band gap carry out for semiconductors coupling, is formed
The composite photo-catalyst of heterojunction structure, and its catalytic activity is also much higher than the catalytic performance of single semiconductor material.But different half
There is larger differences for energy band and structure etc. between conductor, two or more for being only mutually matched valence band and conduction band positions
Catalysis material progress is compound, could reduce the compound of electrons and holes to the greatest extent, promotes photocatalysis effect.Therefore, it seeks
It is crucial for looking for the semiconductor that can be mutually matched to carry out the compound photochemical catalyst to form efficient stable.
For how to promote photocatalysis performance, the electric conductivity of different materials itself, band-gap energy, valence band (or conduction band) position
Equal many factors can all influence it, and the compound of two kinds of semiconductors is paid attention in most researchs at present, and photocatalysis effect is not
It is fully up to expectations, and the total compound research of a variety of semiconductors is less.However, a variety of semiconductors are codoping modified can to obtain collaboration work
With effect, catalyst performance is made to obtain the promotion of matter.
Summary 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 catalytic is thin
Film and preparation method thereof, composite photocatalyst material shows higher photocatalytic activity and stability, and preparation method simply passes through
Ji.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that:
A method of iron oxide-molybdenum sulfide-cadmium sulfide visible light catalytic film is prepared, is included the following steps:
(1) three-electrode system is used, with Fe2+Precursor solution as electrolyte, conductive substrates are as working electrode, stone
Electrode ink is to electrode, and Ag/AgCl electrode carries 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 washs to obtain Fe2O3-MoS2Film；
(3) by Fe made from step (2)2O3-MoS2Film is placed in Cd2+Precursor solution in, under heating conditions into
Row reaction, is made Fe2O3-MoS2- CdS visible light catalytic film.
Being formed a film using photocatalysis film made from electro-deposition, hydro-thermal reaction, the method for heating reaction, uniform, stability is good,
Active constituent is not easy to peel off；Film size is easy to control.Obtained Fe2O3-MoS2The light induced electron of CdS film and hole separation
It is high-efficient, there is good photoelectric catalytically active.
In above-mentioned preparation route, the concrete technology condition of each step is as follows:
(1) in step (1):
The conductive substrates are electro-conductive glass (FTO) etc..
Pre-cleaning, drying conductive substrates are needed before electro-deposition.
The Fe2+Precursor solution be formulated by soluble ferrite and solvent A, soluble ferrite can be nitric acid
Ferrous iron, frerrous chloride, ferrous sulfate, ferrous acetate or ferrous oxalate etc., solvent A are ethylene glycol, methanol, one in second alcohol and water
Kind is several.
Preferably, soluble ferrite is frerrous chloride, solvent A is the mixed liquor of ethylene glycol and water, ethylene glycol and water
Volume ratio be 1:4~12.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 related with film thickness, and film thickness is too thin or too thick,
It will affect the migration of the photolytic activity and photo-generated carrier of film, and only when film thickness is moderate, light not only excites generation
Carrier, and the migration rate of carrier can be improved, to improve the photoelectric catalytically active of film.
In preparation method of the invention the overall thickness of photocatalyst film be substantially equal to electro-deposition formation film thickness,
Hydro-thermal method reacts the sum of the film thickness formed with heating.Temperature, time and the operating voltage of electro-deposition are directly related to electrolysis
The quality (i.e. the thickness of electrodeposited film) of the product of the product and formation of deposition.After the completion of electro-deposition, high-temperature calcination need to be passed through
Further oxidation, and calcination temperature and time also directly affect the Fe of generation2O3Crystal phase, urged so as to influence the light of composite membrane
Change performance.
Film forming effective area and quality can be controlled by regulation electro-deposition parameter and calcination parameter.
Preferably, in step (1), the temperature of electro-deposition is 40~90 DEG C, and the voltage of electro-deposition is 1~2V, electro-deposition
Time is 0.5~15min；
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 for the catalytic film that electro-deposition obtains, film thickness are controlled by electro-deposition process parameter
It is too thin, it cannot be fully absorbed light, and when as substrate, its catalytic activity cannot be given full play to；Film is too thick, influences photoproduction load
Flow the migration of son.When film thickness is moderate, light, which not only excites, generates carrier, and can improve the migration rate of carrier, from
And improve the photoelectric catalytically active of film.
Preferably, the temperature of the calcination processing is 300~600 DEG C, and calcination time is 0.5~5h；Further preferably, it forges
The temperature for burning processing is 450~550 DEG C, and calcination time is 1~3h, controls catalytic film by calcining at constant temperature temperature and time
Crystallinity.Under preferred calcination temperature, material has good crystallinity, and crystal phase is α-Fe2O3, crystallinity is good, photocatalysis
Activity is higher.When calcination temperature is lower, the crystallinity of material is very poor, greatly limitation photocatalytic activity；When calcination temperature mistake
Gao Shi can influence the formation of film because of the limitation of the heat resisting temperature of conductive substrates.
(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 the effect of gravity, conductive more advantageous up
In natural subsidence, film surface obtained is uniform；When conductive face-down, MoS2Growth is uneven on the base layer for layer, thus
The photoelectric properties of film are influenced to a certain extent.
In the present invention, Fe is made using hydro-thermal method2O3-MoS2Film, and MoS2The thickness of film mainly passes through control hydro-thermal
Time of reaction and temperature control, it is preferable that the temperature of hydro-thermal reaction is 100~400 DEG C, and the reaction time is 1~5h；Into one
Preferably, the temperature of hydro-thermal reaction is 100~250 DEG C to step, and the reaction time is 1~3h；Most preferably, hydrothermal temperature 220
DEG C, reaction time 2h；
(3) in step (3):
Preferably, the Cd2+Precursor solution by cadmium sulfate (CdH16O12S), thiocarbamide (CH4N2S), ammonium hydroxide and water are prepared
It forms.
Preferably, the Cd2+Precursor solution in, the concentration of cadmium sulfate is 0.1~2mM, and the mass fraction of ammonium hydroxide 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 ammonium hydroxide
It is 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, the time of reaction is 5~15min.
The photoelectric catalytically active of photocatalysis film is related with film thickness, the too thick migration for influencing photo-generated carrier of film.Thickness
Moderate doping can excite the generation of carrier, moreover it is possible to the migration rate of carrier be improved, to improve the photoelectricity of doping
Catalytic activity.
The present invention also provides a kind of Fe prepared by the above method2O3-MoS2- CdS visible light catalytic film, institute
Obtain Fe2O3-MoS2- CdS visible light catalytic film successively includes the Fe in conductive substrates from the bottom to top2O3Film and it is located at
Fe2O3MoS on film2Film and CdS film.
The photoelectric catalytically active of photocatalysis film is related with film thickness, the too thick migration for influencing photo-generated carrier of film.Thickness
Moderate doping can excite the generation of carrier, moreover it is possible to the migration rate of carrier be improved, to improve the photoelectricity of doping
Catalytic activity.
In preparation method of the invention the overall thickness of photocatalyst film be substantially equal to electro-deposition formation film thickness,
Hydro-thermal method reacts the sum of the film thickness formed with heating.
The Fe2O3-MoS2- CdS visible light catalytic film with a thickness of 500~600nm.Under the thickness, Fe2O3-MoS2-
CdS visible light catalytic film can excite the generation of carrier, moreover it is possible to the migration rate of carrier be improved, to improve doping
Photoelectric catalytically active.
Obtained Fe is utilized the invention also includes a kind of2O3-MoS2- CdS visible light catalytic film is in Phenol-Containing Wastewater Treatment
In application.
Compared with prior art, the invention has the following advantages:
(1) Fe produced by the present invention2O3-MoS2CdS film surface is uniform, active material stability is good, is not easy to peel off, thin
Membrane area is easy to control, due to MoS2, CdS and Fe2O3Synergistic effect makes the light induced electron and hole separation effect of tri compound film
Rate is high, has good photoelectric catalytically active；
(2) pass through measurement, under visible light photograph, the Fe of preparation2O3-MoS2The photoelectric current phase of-CdS visible light catalytic film
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 carry out at normal temperature, applied widely, Fe2O3-MoS2- CdS visible light catalytic is thin
Film can be recycled during the reaction, using the irradiation of visible light, improves the utilization rate to solar energy, realizes efficient benefit
With solar energy, cost is significantly reduced, reduces secondary pollution；
(4) Fe in the present invention2O3-MoS2It is difficult that-CdS visible light catalytic film can avoid previous powder photocatalyst recycling
The problem of, improve photocatalysis efficiency can be simultaneously using photoelectric-synergetic technology come degrading waste water, degradation effect is more preferable.
Detailed description of the invention
Fig. 1 is Fe2O3-MoS2- CdS visible light catalytic film, Fe2O3-MoS2Film and Fe2O3Film is molten in 0.1M NaOH
Visible light in liquid is according to the linear sweep voltammetry curve under alternating；
Fig. 2 is Fe2O3-MoS2- CdS visible light catalytic 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 catalytic film, Fe2O3-MoS2Film and Fe2O3Film is molten in 0.1M NaOH
Electrochemical impedance map (EIS map) in liquid under dark condition；
Fig. 4 is Fe2O3-MoS2- CdS visible light catalytic film, Fe2O3-MoS2Film and Fe2O3Film is molten in 0.1M NaOH
Electrochemical impedance map (EIS map) in liquid under visible light conditions；
Fig. 5 is Fe2O3-MoS2- CdS visible light catalytic film, Fe2O3-MoS2Film and Fe2O3IPCE curve (the light of film
Electro-catalysis transformation efficiency curve)；
Fig. 6 is Fe2O3-MoS2- CdS visible light catalytic film, Fe2O3-MoS2Film and Fe2O3The instantaneous photoelectric current-of film
Time (lnD-T) curve graph；
Fig. 7 is Fe2O3Film, Fe2O3-MoS2Film and Fe2O3-MoS2- CdS visible light catalytic film is right under visible light
The removal rate of phenol in wastewater to be processed compares；
Fig. 8 is phenol wastewater to be processed under the conditions of pure electric condition (EC), pure striation part (PC) and photoelectric-synergetic condition (PEC)
The removal rate of middle phenol compares；
Fig. 9 is initial phenol concentration to Fe2O3-MoS2- CdS visible light catalytic film is under visible light to waste water to be processed
The removal rate of middle phenol influences；
Figure 10 is the degradation rate in embodiment 5 to phenol in every part of phenol wastewater to be processed；
Figure 11 is phenol wastewater pH value to Fe2O3-MoS2The shadow of-CdS visible light catalytic film photoelectric catalysis of phenol removal rate
It rings；
Figure 12 is Fe obtained in embodiment 72O3-MoS2- CdS visible light catalytic film, MoS2CdS film, Fe2O3-
CdS film, CdS film and MoS2Film is in the visible light in 0.1M NaOH solution according to the linear sweep voltammetry curve under alternating.
Specific embodiment
Embodiment 1
The present invention is described in further detail 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 film includes the following steps:
(1) with Fe2+Precursor solution as electrolyte, use three electrode bodies using CHI660E type 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 to electrode, and Ag/AgCl electrode carries out calcining at constant temperature after natural drying as reference electrode, to it and obtains Fe2O3Film；
Fe in the implementation case2+Precursor solution the preparation method is as follows: weighing 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 and distillation
The volume ratio of water is 1:8.
The thickness for the catalytic film that electro-deposition obtains, electrodeposition technology in the present embodiment are controlled by electro-deposition process parameter
Parameter is as follows: electrodeposition temperature is 70 DEG C, operating voltage 1.36V, sedimentation time 5min.Then the conductive base that will have been deposited
Bottom is put into Muffle furnace after drying, at 500 DEG C calcining at constant temperature 2h to get arrive Fe2O3Film.
(2) by Fe made from step (1)2O3After natural drying, conductive face-up slant setting is immersed in MoS to film2's
It in precursor solution, places it 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 MoS2It is high that the thickness of film mainly passes through control
Reaction time and the controlling reaction temperature for pressing reaction kettle, in the present embodiment, the hydro-thermal reaction time 2h, reaction temperature 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
Fe is made in 10min2O3-MoS2- CdS visible light catalytic film, measure film with a thickness of 520nm.
Cd in the present embodiment2+Precursor solution prepared by following methods: take 2.4ml ammonium hydroxide, 0.028mmol cadmium sulfate
(CdH16O12) and 0.2mmol thiocarbamide (CH S4N2S it) is dissolved in 40ml distilled water.
Fig. 1 is Fe2O3-MoS2- CdS visible light catalytic film, Fe2O3-MoS2Film and Fe2O3Film is molten in 0.1M NaOH
Visible light in liquid is according to the linear sweep voltammetry curve under alternating；
Fig. 2 is Fe2O3-MoS2- CdS visible light catalytic 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 light photograph, compared to Fe2O3Film, when voltage is 0.45V, MoS2Construct so that light
Electric current (i.e. current density) has correspondinglyd increase 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 correspondinglys increase 40 times, i.e.,
MoS2The catalytic activity of film is further improved 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 ratio Fe of film2O3Film improves
10 times；Compared to Fe2O3Film, MoS2- CdS's constructs so that Fe2O3-MoS2The photoelectric current of CdS film correspondinglys increase 53
Times.
In addition, it will be evident that in the moment that visible light or ultraviolet-visible are blocked or show from Fig. 1 and Fig. 2,
Fe2O3The photoelectric current of film can be rapidly reached maximum value, then just decay to certain value, this is because Fe2O3Film itself is answered
Close larger, light induced electron and hole are soon compound once generating.And construct MoS2It is afterwards then not in such phenomenon, this explanation
MoS2In Fe2O3Film surface can inhibit the compound of light induced electron and hole.After further constructing CdS, in visible light or purple
The moment that outer visible light is blocked or shows, Fe2O3-MoS2The photoelectric current of CdS film can be rapidly reached maximum value, at this time most
Fe before being worth relatively greatly2O3Film and Fe2O3-MoS2Film has biggish promotion, illustrates the Fe of tri compound2O3-MoS2-CdS
Photoelectric respone is best, and the photoelectric current of generation is most strong, Fe2O3、MoS2Synergistic effect is generated between tri- kinds of materials of CdS.
Fig. 3 is Fe2O3-MoS2- CdS visible light catalytic film, Fe2O3-MoS2Film and Fe2O3Film is molten in 0.1M NaOH
Electrochemical impedance map (EIS map) in liquid under dark condition；Fig. 4 is Fe2O3-MoS2- CdS visible light catalytic film,
Fe2O3-MoS2Film and Fe2O3Electrochemical impedance map (EIS figure of the film in 0.1M NaOH solution under visible light conditions
Spectrum).The frequency range of electrochemical workstation setting is 106Hz-0.01Hz.By Fig. 3, Fig. 4 it is found that either still existing dark
Under the conditions of visible light shines, Fe2O3-MoS2The impedance ring radius of film is both less than Fe2O3Film, moreover, Fe2O3-MoS2CdS 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-MoS2CdS film photo-generate electron-hole energy
Significantly more efficient separation.
Fig. 5 is Fe2O3-MoS2- CdS visible light catalytic film, Fe2O3-MoS2Film and Fe2O3IPCE curve (the light of film
Electro-catalysis transformation efficiency curve).By the IPCE map of Fig. 5 it is found that Fe2O3-MoS2The IPCE value of CdS film is apparently higher than
Fe2O3-MoS2Film and Fe2O3Film.For Fe2O3-MoS2For CdS film, the response point of IPCE curve be in 575nm,
And Fe2O3-MoS2Film and Fe2O3Film is just begun to respond at 550nm, so Fe2O3-MoS2CdS film ratio Fe2O3-MoS2
Film and simple Fe2O3Film shows broader visible absorption range.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, this shows Fe2O3-MoS2-CdS
Laminated film shows significant synergy in terms of photoelectric activity.
Fig. 6 is Fe2O3-MoS2- CdS visible light catalytic film, Fe2O3-MoS2Film and Fe2O3The instantaneous photoelectric current-of film
Time (lnD-T) curve graph.In instantaneous photocurrent-time curve figure, for some specific ln D value, if surveying catalysis material
Expect that corresponding t value is bigger, then photo-generated carrier recombination rate is lower in the electrode.Under surveyed applying bias, compares three kinds and urge
The curve for changing film, for any ln D value, Fe2O3-MoS2The corresponding t value of CdS film is maximum always, and photo-generated carrier is compound
Rate is low.It will be appreciated from fig. 6 that working as ln D=-1, Fe2O3-MoS2T value corresponding to CdS film is 3.8s, Fe2O3-MoS2Film
Corresponding t value is 2.3s, Fe2O3T value corresponding to film is 1.2s, the surface photo-generated carrier of the bigger laminated film of t value
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 are it is found that Fe2O3-MoS2- CdS visible light catalytic film is shown significantly in terms of photoelectric activity
Synergistic effect, the Fe that the present invention is prepared2O3-MoS2- CdS visible light catalytic film has excellent visible light catalytic living
Property.
Embodiment 2
Waste water to be processed is phenolic waste water in the present embodiment, and wherein the initial concentration of phenol is 10mg/L.
The present embodiment based on Fe made from embodiment 12O3-MoS2The place of the phenol wastewater of-CdS visible light catalytic film
Reason method, treatment process are as follows:
(S1) pH value of phenol wastewater to be processed is adjusted to 6.3；
By the way that 1M H is added dropwise2SO4Solution or 1M NaOH solution adjust the pH value of phenol wastewater.
(S2) to progress photoelectrocatalysis processing after adjusting pH value.The light positive electrode used when photoelectrocatalysis processing includes conduction
Substrate and the Fe for being coated on conductive substrates surface2O3-MoS2- CdS visible light catalytic film (film effective area is 2cm × 2cm),
Cathode is the titanium sheet of identical effective area.
When photoelectrocatalysis is handled in the present embodiment, before photochemical catalyst electrode is to operating voltage is applied, also to waste water to be processed
Dark adsorption treatment is carried out, the dark adsorption treatment time is 30min.
The operating voltage being applied between light positive electrode and cathode when photoelectrocatalysis processing is 2.5V, in radiation of visible light
Under the conditions of carry out.
To guarantee waste water to be processed even concentration during the reaction, in photoelectrocatalysis treatment process, to be processed useless
Water carries out magnetic agitation.
Fe is given in the present embodiment2O3Film and Fe2O3-MoS2Film treat the degradation situation of Phenol-Containing Wastewater Treatment with
It compares.
Fig. 7 is Fe2O3Film, Fe2O3-MoS2Film and Fe2O3-MoS2- CdS visible light catalytic film is right under visible light
The removal rate of phenol in wastewater to be processed compares.After the reaction of the photoelectrocatalysis of 5h, ternary Fe2O3-MoS2CdS film conduct
The removal rate of phenol is up to 90.47% when anode, and simple Fe2O3With the compound Fe of binary2O3-MoS2It is gone when film is as anode
Except rate be significantly lower than trielement composite material, respectively 54.57% and 69.14%.In addition, degradation process is anti-with quasi- first order kinetics
It answers model to be fitted, calculates its reaction rate constant, after the Fitting Calculation it is found that under visible light photograph, Fe2O3-MoS2-CdS
The reaction rate of film is Fe respectively2O3And Fe2O3-MoS23.17 and 2.05 times.From the analysis above, we can see that MoS2With CdS layer pair
It all has a certain upgrade effect in photoelectric catalysis degrading performance, and the visible photoelectricity of trielement composite material for building composition for two layers altogether is urged
It is relatively optimal to change activity, while phenol removal rate improves, 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 the conditions of pure electricity and pure light
It carries out, to study Fe2O3-MoS2- CdS visible light catalytic film distinguishes the degradation situation of Pyrogentisinic Acid under different illumination conditions.
Fig. 8 is phenol wastewater to be processed under the conditions of pure electric condition (EC), pure striation part (PC) and photoelectric-synergetic condition (PEC)
The removal rate 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 removal rate are 90.47%, photoelectric-synergetic effect
Significantly.In addition, degradation process is fitted with quasi- first order kinetics reaction model, its reaction rate constant is calculated, is counted through fitting
After calculation it is found that when catalytic type difference, the reaction rate of photoelectrocatalysis reaction is respectively 38 times of simple photocatalysis and electro-catalysis
With 10.86 times, further demonstrate during phenol degrading there are the effect of significant photoelectric-synergetic, subsequent degradation experiment exists
It is studied under photoelectrocatalysis reaction system.
Embodiment 4
Different phenol wastewater is handled using processing method same as Example 2, that is, carries out adopting when phenolic wastewater treatment
The parameter of light positive electrode, treatment process and wherein each step is all the same, except that in phenol wastewater to be processed
The initial concentration of phenol is different.
The initial concentration of phenol is as follows in phenol wastewater to be processed in the present embodiment: 5mg/L, 10mg/L and 20mg/L.
Fig. 9 is initial phenol concentration to Fe2O3-MoS2- CdS visible light catalytic film is under visible light to waste water to be processed
The removal rate of middle phenol influences.
As seen from the figure, in surveyed pollutant initial concentration range, with Fe2O3-MoS2- CdS visible light catalytic film is light
When anode carries out photoelectrocatalysis reaction degradation of phenol, preferable removal effect is suffered from, (5,10mg/L), benzene when concentration is lower
The removal rate of phenol 90% or more, respectively 91.50% and 90.47%, at concentration higher (20mg/L), also has certain
Degradation effect, the removal rate of phenol are 50.76%.
Embodiment 5
To the Fe of preparation2O3-MoS2- CdS visible light catalytic film has carried out circulation degradation experiment: taking to be processed useless containing phenol
Water is simultaneously divided into four parts, using method same as Example 2, using same a pair of of photoelectrocatalysielectrode electrode to respectively to every portion wait locate
Reason phenol wastewater is handled.
Figure 10 is the degradation rate to phenol in every part of phenol wastewater to be processed, 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 degradation phenol wastewater 4 times, the removal rate base of phenol
Originally it remains unchanged, 90% or so, this film of preliminary identification has good reusability and stability.
Embodiment 6
Different phenol wastewater is handled using processing method same as Example 2, that is, carries out adopting when phenolic wastewater treatment
The parameter of light positive electrode, treatment process and wherein each step is all the same, except that phenol wastewater to be processed
Initial pH value is different, i.e., default pH value is different.
Adjusted in the present embodiment the pH value of phenol wastewater to be processed to: 3.0,6.3 and 9.0.
Figure 11 phenol wastewater pH value is to Fe2O3-MoS2The shadow of-CdS visible light catalytic film photoelectric catalysis of phenol removal rate
It rings.
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
When with 6.3, phenol degrading effect is preferable, and the removal rate of phenol is 90% or so；When phenol wastewater pH value is 9.0 in alkalinity
When, the poor degradation effect of phenol is 55.19%.As it can be seen that when phenol wastewater pH value to be processed is adjusted between 3~6.3,
Fe2O3-MoS2- CdS visible light catalytic film suffers from preferable degradation effect for photoelectric catalysis degrading phenol.
Embodiment 7
Further to investigate effect and meaning existing for different cati materials, it is prepared for Fe2O3-MoS2- CdS visible light
Catalytic film, MoS2CdS film, Fe2O3CdS film, CdS film and MoS2Film compares under the same conditions, specifically
The preparation method is as follows:
(1)Fe2O3-MoS2- CdS visible light catalytic film: the preparation method is the same as that of Example 1.
(2)MoS2Film: the conductive inclination up of FTO is immersed in MoS2Precursor solution in, it is anti-to place it in high pressure
It answers in kettle, MoS is made with hydro-thermal method2Film.
MoS2Precursor solution the preparation method is the same as that of Example 1.
(3)MoS2CdS film: by MoS obtained in (2)2Film is put into Cd2+Precursor solution in, in 60 DEG C of water-baths
Middle reaction 10 minutes, obtains MoS2CdS film；
Cd2+Precursor solution the preparation method is the same as that of Example 1.
(4)Fe2O3CdS film: according to Fe made from the step in embodiment 12O3Film is put into Cd2+Precursor solution
In, it is reacted 10 minutes in 60 DEG C of water-baths, obtains Fe2O3CdS film；
Cd2+Precursor solution the preparation method is the same as that of Example 1.
(5) FTO CdS film: is put into Cd2+Precursor solution in, reacted 10 minutes in 60 DEG C of water-baths, obtain CdS
Film.
Cd2+Precursor solution the preparation method is the same as that of Example 1.
Figure 12 is Fe obtained in the present embodiment2O3-MoS2- CdS visible light catalytic film, MoS2CdS film, Fe2O3-
CdS film, CdS film and MoS2Film is in the visible light in 0.1M NaOH solution according to the linear sweep voltammetry curve under alternating.
As shown in Figure 12, under the irradiation of visible light, within the scope of surveyed applying bias, Fe2O3-MoS2The photoelectric current of CdS film is big
In MoS2CdS film, this illustrates Fe2O3There is certain facilitation to the promotion 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 are significant；Directly by FTO in Cd2+Presoma
Chemical thought is carried out in solution and obtains the film of CdS, has certain photoelectric current, but be 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 do not have significant change, illustrate simple MoS2PhotoelectrocatalytiPerformance Performance is poor.In summary
Test result determines Fe2O3-MoS2Be implicitly present in synergistic effect between three kinds of materials of-CdS photoelectrocatalysithin thin film, make it have compared with
Good photoelectric properties.
Embodiment 8
The operating procedure of Examples 1 and 2 is repeated, the difference is that preparation Fe2O3-MoS2- CdS visible light catalytic film
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, calcination time 5h.
The Fe prepared under conditions of the present embodiment2O3-MoS2- CdS visible light catalytic film photoelectric chemical property be inferior to by
Fe made from 1 condition of embodiment2O3-MoS2- CdS visible light catalytic film, compared to Fe2O3Film, the Fe of the present embodiment2O3-
MoS2The photoelectric current (i.e. current density) of-CdS visible light catalytic film has correspondinglyd increase 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, the difference is that preparation Fe2O3-MoS2- CdS visible light catalytic film
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, reaction time 5h.
The Fe prepared under conditions of the present embodiment2O3-MoS2- CdS visible light catalytic film photoelectric chemical property be inferior to by
Fe made from 1 condition of embodiment2O3-MoS2- CdS visible light catalytic film, compared to Fe2O3Film, the Fe of the present embodiment2O3-
MoS2The photoelectric current (i.e. current density) of-CdS visible light catalytic film has correspondinglyd increase 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, the difference is that preparation Fe2O3-MoS2- CdS visible light catalytic film
During, in step (2), the temperature of hydro-thermal reaction is 250 DEG C, reaction time 3h.
The Fe prepared under conditions of the present embodiment2O3-MoS2- CdS visible light catalytic film photoelectric chemical property be inferior to by
Fe made from 1 condition of embodiment2O3-MoS2- CdS visible light catalytic film, compared to Fe2O3Film, the Fe of the present embodiment2O3-
MoS2The photoelectric current (i.e. current density) of-CdS visible light catalytic film has correspondinglyd increase 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, the difference is that preparation Fe2O3-MoS2- CdS visible light catalytic film
During, in step (2), the temperature of hydro-thermal reaction is 400 DEG C, reaction time 1h.
The Fe prepared under conditions of the present embodiment2O3-MoS2- CdS visible light catalytic film photoelectric chemical property be inferior to by
Fe made from 1 condition of embodiment2O3-MoS2- CdS visible light catalytic film, compared to Fe2O3Film, the Fe of the present embodiment2O3-
MoS2The photoelectric current (i.e. current density) of-CdS visible light catalytic film has correspondinglyd increase 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, the difference is that preparation Fe2O3-MoS2- CdS visible light catalytic film
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 property be inferior to by
Fe made from 1 condition of embodiment2O3-MoS2- CdS visible light catalytic film, compared to Fe2O3Film, the Fe of the present embodiment2O3-
MoS2The photoelectric current (i.e. current density) of-CdS visible light catalytic film has correspondinglyd increase 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, the difference is that preparation Fe2O3-MoS2- CdS visible light catalytic film
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 property be inferior to by
Fe made from 1 condition of embodiment2O3-MoS2- CdS visible light catalytic film, compared to Fe2O3Film, the Fe of the present embodiment2O3-
MoS2The photoelectric current (i.e. current density) of-CdS visible light catalytic film has correspondinglyd increase 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, the difference is that preparation Fe2O3-MoS2- CdS visible light catalytic film
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 property be inferior to by
Fe made from 1 condition of embodiment2O3-MoS2- CdS visible light catalytic film, compared to Fe2O3Film, the Fe of the present embodiment2O3-
MoS2The photoelectric current (i.e. current density) of-CdS visible light catalytic film has correspondinglyd increase 39 times；The Pyrogentisinic Acid under visible light conditions
Degradation rate be 89.9%.
Technical solution of the present invention and beneficial effect is described in detail in above-described specific embodiment, Ying Li
Solution is not intended to restrict the invention the foregoing is merely presently most preferred embodiment of the invention, all in principle model of the invention
Interior done any modification, supplementary, and equivalent replacement etc. are enclosed, should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of prepare iron oxide-molybdenum sulfide-cadmium sulfide visible light catalytic film method, which is characterized in that including walking as follows
It is rapid:
(1) three-electrode system is used, with Fe2+Precursor solution as electrolyte, conductive substrates are as working electrode, graphite electricity
Extremely to electrode, Ag/AgCl electrode carries 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
It is washed to obtain Fe2O3-MoS2Film；The temperature of the hydro-thermal reaction is 100~250 DEG C, and the reaction time is 1~3h；
(3) by Fe made from step (2)2O3-MoS2Film is placed in Cd2+Precursor solution in, carry out under heating conditions anti-
It answers, Fe is made2O3-MoS2- CdS visible light catalytic film；The Cd2+Precursor solution by cadmium sulfate, thiocarbamide, ammonium hydroxide and
Water is formulated, wherein the concentration of cadmium sulfate is 0.1~2mM, and the concentration of thiocarbamide is 1~10mM, and the mass fraction of ammonium hydroxide is 25
~28%；The temperature of the reaction is 50~80 DEG C, and the time of reaction is 5~20min.
2. according to claim 1 prepare iron oxide-molybdenum sulfide-cadmium sulfide visible light catalytic film method, feature
It is, in step (1), the temperature of electro-deposition is 60~80 DEG C, and the voltage of electro-deposition is 1~1.5V, the time of electro-deposition is 4~
6min。
3. according to claim 1 prepare iron oxide-molybdenum sulfide-cadmium sulfide visible light catalytic film method, feature
It is, in step (1), the temperature of the calcination processing is 450~550 DEG C, and calcination time is 1~3h.
4. a kind of Fe that methods described in any item according to claim 1~3 are prepared2O3-MoS2- CdS visible light catalytic is thin
Film, which is characterized in that gained Fe2O3-MoS2- CdS visible light catalytic film successively includes being located in conductive substrates from the bottom to top
Fe2O3Film and be located at Fe2O3MoS on film2Film and CdS film.
5. Fe according to claim 42O3-MoS2- CdS visible light catalytic film, which is characterized in that the Fe2O3-
MoS2- CdS visible light catalytic film with a thickness of 500~600nm.
6. a kind of utilize Fe as claimed in claim 42O3-MoS2- CdS visible light catalytic film answering in Phenol-Containing Wastewater Treatment
With.
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| KR102627617B1 (en) * | 2021-09-30 | 2024-01-23 | 울산대학교 산학협력단 | Tungsten doped alpha fe2o3 and mos2 composition, photocatalyst including the composition and the method of preparing the same |
| CN114280369B (en) * | 2021-12-22 | 2023-12-05 | 广东南海启明光大科技有限公司 | Method for detecting reliability of electrocardio electrode |
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