CN111822001A - Multilayer composite photocatalytic film material and preparation method and application thereof - Google Patents
Multilayer composite photocatalytic film material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111822001A CN111822001A CN202010721027.5A CN202010721027A CN111822001A CN 111822001 A CN111822001 A CN 111822001A CN 202010721027 A CN202010721027 A CN 202010721027A CN 111822001 A CN111822001 A CN 111822001A
- Authority
- CN
- China
- Prior art keywords
- film
- chamber
- zno
- agins
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 122
- 239000011521 glass Substances 0.000 claims abstract description 46
- 239000002351 wastewater Substances 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 229910003373 AgInS2 Inorganic materials 0.000 claims abstract description 24
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 42
- 238000004544 sputter deposition Methods 0.000 claims description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 28
- 239000001301 oxygen Substances 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 28
- 238000004140 cleaning Methods 0.000 claims description 22
- 229910052786 argon Inorganic materials 0.000 claims description 21
- 239000007888 film coating Substances 0.000 claims description 20
- 238000009501 film coating Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 230000001105 regulatory effect Effects 0.000 claims description 13
- 230000001276 controlling effect Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 238000004065 wastewater treatment Methods 0.000 claims description 4
- 230000003115 biocidal effect Effects 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 148
- 239000011787 zinc oxide Substances 0.000 abstract description 74
- 239000011941 photocatalyst Substances 0.000 abstract description 9
- 239000013077 target material Substances 0.000 abstract description 7
- 230000000593 degrading effect Effects 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000002096 quantum dot Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 100
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 22
- 239000010410 layer Substances 0.000 description 21
- LSQZJLSUYDQPKJ-NJBDSQKTSA-N amoxicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 LSQZJLSUYDQPKJ-NJBDSQKTSA-N 0.000 description 18
- 229960003022 amoxicillin Drugs 0.000 description 18
- LSQZJLSUYDQPKJ-UHFFFAOYSA-N p-Hydroxyampicillin Natural products O=C1N2C(C(O)=O)C(C)(C)SC2C1NC(=O)C(N)C1=CC=C(O)C=C1 LSQZJLSUYDQPKJ-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 239000012535 impurity Substances 0.000 description 13
- 229910001868 water Inorganic materials 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000002120 nanofilm Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000004408 titanium dioxide Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- YNXRTZDUPOFFKZ-UHFFFAOYSA-N [In].[Ag]=S Chemical compound [In].[Ag]=S YNXRTZDUPOFFKZ-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 238000005240 physical vapour deposition Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- HVGBBHRFXSRWGN-UHFFFAOYSA-N [In].[Ag](=S)=S Chemical compound [In].[Ag](=S)=S HVGBBHRFXSRWGN-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005234 chemical deposition Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- SWLPASIZBOSQIQ-UHFFFAOYSA-M [O-2].[O-2].[O-2].[OH-].O.O.[Zn+2].[Ta+5] Chemical compound [O-2].[O-2].[O-2].[OH-].O.O.[Zn+2].[Ta+5] SWLPASIZBOSQIQ-UHFFFAOYSA-M 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
-
- 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
- B01J37/06—Washing
-
- 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
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Plasma & Fusion (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention relates to a multilayer composite photocatalytic film material, a preparation method and application thereof, and the material is prepared from AgInS2Film and ZnO filmThe film is multi-layer compounded and has a structural general formula of [ AgInS2(X)/ZnO(y)]nWherein x and y denote AgInS in a single pacing cycle2The thickness of the film and the ZnO film, and 1<x<30nm,1<y<30nm, n is the number of the composite coating film and is 1<n<5. Firstly, the glass substrate is rotated to AgInS2And (3) performing radio frequency magnetron sputtering coating right above the target material, and then rotating a turntable of the glass substrate to the position right above the ZnO target material to obtain the ZnO target material. The invention utilizes ternary AgInS2The quantum dot characteristic and the energy band structure of the binary zinc oxide nano material widen the forbidden band width of the photocatalytic material, realize the expansion of the application of the photocatalyst from ultraviolet light to visible light, and improve the intensity and efficiency of degrading wastewater.
Description
Technical Field
The invention relates to a composite photocatalytic film material, a preparation method thereof and application thereof in wastewater treatment, belonging to the technical field of photocatalytic materials.
Background
The photocatalytic oxidation technology is an environment-friendly green water treatment technology, can thoroughly degrade organic pollutants in wastewater, has no toxicity or toxic byproducts due to the fact that a catalyst of the photocatalytic oxidation technology is nontoxic, can react at normal temperature and normal pressure, thoroughly destroys the molecular structure of organic matters, is used for degrading antibiotic wastewater, and has the characteristics of high treatment efficiency, mild reaction, wide application range and the like, so that the photocatalytic oxidation technology has a good application prospect. Mechanism process of photocatalytic oxidation reactionThe photocatalyst generates photon-generated carriers under the irradiation of a specific light source to enable surrounding water molecules and oxygen to form extremely active free radicals (such as. OH free radicals and. O)2 -Free radical), can oxidize and degrade macromolecular organic matters into H2O and CO2And the like. The photocatalytic semiconductor material widely used at present is mainly TiO2、ZnO、CdS、WO3、SnO2And the like. Some mainstream photocatalytic materials such as titanium dioxide have inefficient separation of photo-generated charges, resulting in large amounts of inefficient recombination of photo-generated electrons and holes, thereby reducing photon efficiency; due to the energy band structure (Eg ═ 3.2ev) of the anatase type titanium dioxide semiconductor material, it is determined that such photocatalyst can only absorb the ultraviolet part (only 4% of sunlight) with the wavelength less than 380nm in sunlight, and the solar energy utilization rate is low. Although the powder catalyst has high catalytic efficiency, the powder catalyst is difficult to continuously recycle, the post-treatment process is complex and the cost is high, therefore, the catalyst needs to be immobilized, but the immobilization of the catalyst can cause the reduction of the specific surface area of the catalyst, the reduction of the catalytic activity and the difficulty in maintaining the high-efficiency photocatalyst loading technology; the catalytic activity of the photocatalyst has a great relationship with the granularity, the smaller the granularity is, the larger the specific surface area is, the higher the photocatalytic activity is, but the granularity is too small, secondary agglomeration is easy to occur, and a powder photocatalytic system is a thermodynamically unstable system and is easy to generate particle agglomeration, so that the practicability is poor; some photocatalysts have poor stability and are often deactivated.
Compared with granular and powdery materials, the film material has the characteristics of being more easily changed into a regular material, being more easily recycled and being more beneficial to catalytic reaction in a catalytic modification mode. The existing photocatalytic film materials are mostly single-component or single-layer photocatalytic materials, and the materials generally have some problems, such as low quantum efficiency and pure single TiO2Materials such as ZnO and the like have high recombination rate of photo-generated electron-hole pairs, and the photocatalytic performance cannot be well exerted; the available spectrum range is very small, is limited to the ultraviolet range with the wavelength less than 400nm, and other spectra occupying a large part of sunlight cannot be used; is provided withFor high-concentration industrial wastewater, such as dye wastewater and pharmaceutical wastewater, the photocatalytic reaction is difficult to occur due to the large amount of impurities, high turbidity and poor light transmittance.
Multilayer composite thin film materials have also been investigated and are limited in many ways by the choice of preparation methods and materials. The preparation method of the single-layer film material is divided into a chemical deposition method (CVD) and a physical deposition method (PVD), wherein the chemical deposition method is a technology for generating a solid film by utilizing a gaseous precursor reactant through an atomic and intermolecular chemical reaction path, the technology can conveniently control the components of the deposit, but the method uses expensive equipment and has higher preparation cost of the film; the Physical Vapor Deposition (PVD) technique is a technique of vaporizing a material source, i.e., a solid or a liquid surface, into gaseous atoms, molecules or partially ionized ions by a Physical method under a vacuum condition, and depositing a thin film having a specific function on a substrate surface by a low-pressure gas (or plasma) process. The main methods of physical vapor deposition include vacuum evaporation, sputter coating, arc plasma coating, ion coating, and molecular beam epitaxy. The sputtering coating refers to a process of bombarding the surface of a target material by particles with kinetic energy under a vacuum condition to enable atoms on the surface of the target material to obtain enough energy to escape, namely sputtering; the sputtered target material is deposited on the surface of the substrate, and the sputtering coating is called; at present, the method is mainly applied to coating films for large-scale architectural decoration and functional coating films of industrial materials, and plating Ni and Ag on the surfaces of foamed plastics and fiber fabrics of coiled materials by TGN-JR type multi-arc or magnetron sputtering. Physical vapor deposition techniques have been developed to date to deposit not only metal films, alloy films, but also compound, ceramic, semiconductor, polymer films, and the like. The preparation of multilayer composite film materials requires a combination of material composition and properties. Chinese patent CN104529184A discloses a zinc oxide-tantalum pentoxide composite nano-film, which uses conductive glass as a substrate and tantalum oxide film as a protective layer to be uniformly coated on the surface of a one-dimensional zinc oxide nano-rod array, and comprises preparing a precursor solution of a ZnO seed crystal layer, preparing a coating of conductive glass with the ZnO seed crystal layer, preparing a solvothermal precursor solution of zinc nitrate and hexamethylenetetramine, and carrying out liquid-phase reactionSynthesizing to obtain ZnO nanorod array film, and depositing Ta by atomic layer2O5The film is uniformly coated on the surface of the ZnO nanorod array to form ZnO/Ta2O5And (3) a nano film. The tantalum oxide film plays a role in protecting a zinc oxide material and passivating the surface state of zinc oxide, and the activity and stability of hydrogen production by photolysis of water are obviously improved. The preparation of the multilayer film material with better catalytic activity by developing and designing the material composition with better semiconductor structure is an important direction for the functionalization of the photocatalytic film.
Disclosure of Invention
The invention aims to solve the problems of the existing photocatalytic materials and provides a multilayer composite photocatalytic film material, a preparation method thereof and application thereof in wastewater treatment.
The invention is realized by the following technical scheme:
a multi-layer composite photocatalytic film material is prepared from AgInS2The film and the ZnO film are compounded in a multilayer way, and the structural general formula is [ AgInS ]2(x)/ZnO(y)]nWherein x and y denote AgInS in a single pacing cycle2The thickness of the film and the ZnO film, and 1<x<30nm,1<y<30nm, n is the number of the composite coating film and is 1<n<5。
The total thickness of the multilayer composite photocatalytic film material is 150-200 nm. AgInS in each coating cycle in the whole composite film material2The mass composition ratio of the film to the ZnO film is preferably 1: 2-200.
The AgInS2The multilayer composite of the film and the ZnO film is prepared by radio frequency magnetron sputtering coating.
The preparation method of the multilayer composite photocatalytic film material comprises the following steps:
(1) cleaning and drying the glass substrate, placing the glass substrate on a mask plate, fixing and sending the glass substrate into a pretreatment chamber; vacuumizing the pretreatment chamber, opening a baffle between the pretreatment chamber and the magnetic control chamber when the magnitude of the vacuum degree of the pretreatment chamber reaches the vacuum degree of the magnetic control chamber, conveying the glass substrate into the magnetic control chamber, and closing the baffle between the magnetic control chamber and the pretreatment chamber; vacuumizing the magnetic control chamber, firstly vacuumizing by using a mechanical pump, then vacuumizing the magnetic control chamber by using a molecular pump, and introducing argon (Ar); glow discharge, when the discharge color is stable and presents a blue-white color, preparing to start coating;
(2) rotating a glass substrate to AgInS2Directly above the target material, the sputtering power is adjusted to 180-300W, the rotation power of the turntable of the glass substrate is adjusted to 2-5W, the temperature of the glass substrate is set to 120-2) Controlling the flow ratio of argon (Ar) to be 1:3-5, simultaneously controlling the working total pressure of gas in a magnetron chamber to be kept at 0.5-2.0Pa, enabling the substrate to be in the range of glow discharge, starting timing film coating, carrying out the film pacing for 0.2-1 h in the atmosphere of stable glow discharge, and sputtering for corresponding time according to the set thickness until the sputtering requirement is met;
b. rotating the turntable of the glass substrate to the position right above the ZnO target, adjusting the sputtering power to 180-300W, adjusting the rotation power of the turntable of the substrate to 2-5W, setting the temperature of the glass substrate to 120-2) Controlling the flow ratio of argon (Ar) to be 1:3-5, simultaneously controlling the working total pressure of gas in a magnetron chamber to be kept at 0.5-2.0Pa, enabling the substrate to be in the range of glow discharge, starting timing film coating, carrying out film coating for 0.5-2.5 h in the atmosphere of stable glow discharge, and sputtering for corresponding time according to the set thickness until the sputtering requirement is met;
c. repeating the steps a and b until the composite multilayer [ AgInS ] is completed2(x)/ZnO(y)]nSetting the total layer number;
(3) after the radio frequency magnetron sputtering is finished, the pressure intensity of the pretreatment chamber and the magnetron chamber is adjusted, and the substrate plated with the film is taken out.
In the preparation method of the multilayer composite photocatalytic film material, the vacuum degree of the magnetic control chamber in the step (1) reaches 6.0 multiplied by 10-4Closing a molecular pump valve of the magnetic control chamber while Pa, opening an argon (Ar) gas tank valve, adjusting the molecular pump valve, observing a vacuum gauge, and when the working pressure of the magnetic control chamber reaches 1.0Pa, controlling the molecular pump valveAnd (5) fixing the position.
Step (2) a, preferably, the sputtering power is 240W, the rotating power of a rotating disc of the substrate is 3W, the temperature of the glass substrate is 150 ℃, and the working total pressure of gas in the magnetron chamber is kept at 1.0 Pa. The plating is preferably carried out in an atmosphere of stable glow discharge for 0.5 h.
And (2) b, preferably, the sputtering power is 240W, the rotating power of a rotating disc of the substrate is 3W, the temperature of the glass substrate is 150 ℃, and the total working pressure of gas in the magnetron chamber is kept at 1.0 Pa. The plating is preferably carried out in an atmosphere of stable glow discharge for 1.5 h.
Composite multilayer AgInS prepared by using method2And ZnO thin film, the photocatalytic performance of which can be improved by including AgInS2And structural parameters including the component content of ZnO, the thickness ratio of the film layers, the number of the film layers and the like are regulated and controlled.
The prepared multilayer composite photocatalytic film material is applied to wastewater treatment, in particular to the treatment of refractory wastewater (such as refractory dye wastewater and refractory antibiotic wastewater).
The invention utilizes ternary AgInS2The quantum dot characteristic and the energy band structure of the binary zinc oxide nano material implement the multi-layer composition of the two materials in the nano scale, and construct the nano composite multi-layer photocatalysis functional film. Compared with the traditional single-component photocatalytic material, the composite multilayer nano photocatalytic film has higher photocatalytic efficiency and longer service life.
The invention has the advantages that:
(1) the composite semiconductor material with multilayer composite film is combined and designed, and ternary AgInS is selected2And the binary ZnO composite film layer fully utilizes the reduction of the energy band structure of the two layers after the two layers are compounded, promotes the separation of photoproduction electrons and holes, and inhibits the compounding of the photoproduction electrons and the holes, thereby improving the quantum efficiency, enlarging the wavelength range of exciting light and improving the stability of the photocatalyst by fully utilizing solar energy;
(2) by utilizing a magnetron sputtering technology, the designed semiconductor material is used for preparing a multilayer composite photocatalytic film by utilizing an efficient double-target and steering target method, so that the load problem and the catalytic efficiency problem of photocatalysis are thoroughly solved, and the application of the photocatalysis technology is greatly promoted;
(3) the bottleneck problems of low efficiency and poor catalytic activity of a photocatalytic system caused by easy dispersion and difficult loading technology of the powder catalyst are solved, and the large-scale application of the difficultly degraded wastewater is facilitated; meanwhile, the composition and the structure of the photocatalyst are improved, the forbidden bandwidth of the photocatalytic material is widened, the application of the photocatalyst is expanded from ultraviolet light to visible light, the intensity and the efficiency of degrading waste water are improved, and a foundation is laid for realizing the high-efficiency treatment of the difficultly-degraded waste water.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) of the composition of a photocatalytic film; (a) scanning electron microscope images of single zinc oxide films; (b) scanning electron microscope images of the indium disulfide silver composite zinc oxide film;
FIG. 2 is a transmission electron micrograph (TEM image) of a thin film composed of indium silver sulfide and zinc oxide at different ratios; (a) the mass ratio of the indium sulfide silver to the zinc oxide is (1: 10); (b) the mass ratio of the indium sulfide silver to the zinc oxide is (5: 10);
FIG. 3 is a photoluminescence spectrum (PL diagram) of a thin film composed of indium silver sulfide and zinc oxide at different ratios, in which AgInS2Abbreviated as AIS;
FIG. 4 shows titanium dioxide and [ AgInS ]2(x)/ZnO(y)]nA degradation contrast curve of the composite film on amoxicillin;
FIG. 5 shows a zinc oxide film, an indium-silver disulfide film and [ AgInS ]2(x)/ZnO(y)]nA degradation contrast curve of the composite film on amoxicillin;
FIG. 6 shows titanium dioxide and [ AgInS ]2(x)/ZnO(y)]nCOD degradation curve of composite film dye to wastewater.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1: composite multilayer nano AgInS2And preparing a photocatalytic functional film of ZnO:
1. cleaning the surface and the back of the glass substrate to remove dust particles, organic and inorganic impurities;
(a) putting the substrate into an acetone solution, and ultrasonically cleaning for 5 minutes to remove organic impurities on the surface of the substrate;
(b) putting the substrate into an alcohol solution, and ultrasonically cleaning for 5 minutes to remove inorganic impurities on the surface of the substrate;
(c) placing the substrate in deionized water, ultrasonically cleaning for 5 minutes, and cleaning the surface again;
(d) taking out the substrate, and drying in a vacuum drying oven for later use.
2. Preparation of [ AgInS ] by magnetron sputtering method2(x)/ZnO(y)]nPreparation of composite multilayer nano-film:
(a) fixing the glass substrate: and (2) placing the cleaned glass substrate on a mask plate, then fixing, opening an air release valve of the pretreatment chamber, opening a window of the pretreatment chamber when the pressure in the pretreatment chamber is consistent with the external atmospheric pressure, placing the mask plate in a tray of the pretreatment chamber, and closing the valve of the pretreatment chamber.
(b) Vacuumizing a pretreatment chamber: after a power supply, a water source and a gas source switch are turned on, a mechanical pump of the pretreatment chamber is turned on, a vacuum gauge of the pretreatment chamber is observed, when the magnitude of the vacuum degree of the pretreatment chamber reaches the vacuum degree of the magnetic control chamber, a baffle between the pretreatment chamber and the magnetic control chamber is opened, a tray rotating shaft in the pretreatment chamber is rotated, the substrate is conveyed into the magnetic control chamber, the substrate is placed on a rotating disk of the substrate by using a mechanical arm of the magnetic control chamber, the tray is conveyed back to the pretreatment chamber, and the baffle between the magnetic control chamber and the pretreatment chamber is closed. The pretreatment chamber mechanical pump was turned off.
(c) Vacuumizing a magnetic control chamber: starting a mechanical pump of a magnetic control chamber, observing a vacuum gauge of the magnetic control chamber, starting a molecular pump switch when the order of magnitude of vacuum degree in the magnetic control chamber reaches zero power, adjusting the rotating speed of the molecular pump, closing a gate valve of the mechanical pump when the rotating speed of the molecular pump reaches 400r/min, opening the gate valve of the molecular pump, driving the molecular pump to operate by the mechanical pump, utilizing the molecular pump to pump high vacuum to the magnetic control chamber, observing an ionization vacuum gauge simultaneously, and when the vacuum degree reaches 6.0 multiplied by 10-4While Pa, the magnetic control chamber is closedMolecular pump valve. And simultaneously opening a valve of an argon (Ar) gas tank, adjusting a valve of the molecular pump, observing the vacuum gauge, and fixing the position of the valve of the molecular pump when the working pressure of the magnetic control chamber reaches 1.0 Pa.
(d) Glow discharge: and (3) turning on a 500W radio frequency working source, adjusting the power of a radio frequency matcher to 80W, finding out glow discharge in the magnetron, pre-sputtering for 10min, and preparing to start coating when the color of the glow discharge is stable and appears bluish white.
3. Preparation of [ AgInS ] by radio frequency magnetron sputtering2(x)/ZnO(y)]nCompounding the multilayer nano film:
(a) rotating the turntable of the substrate to AgInS2Directly above the target, the sputtering power is adjusted to 180W, the rotation power of the turntable of the substrate is adjusted to 4W, the temperature of the glass substrate is set to 180 ℃, a valve of an oxygen tank is opened to introduce oxygen (O) into the magnetron chamber2) While regulating the gas flow meter so that the gas flow meter is oxygen (O)2) And argon (Ar) at a flow ratio of 1:3, adjusting a valve of the molecular pump to keep the total working pressure of gas in the magnetron chamber at 2.0Pa, enabling the substrate to be in a glow discharge range, starting timing film coating, and performing film coating for 1h in a stable glow discharge atmosphere.
(b) Rotating the turntable of the substrate to the position right above the ZnO target, adjusting the sputtering power to 300W, adjusting the rotation power of the turntable of the substrate to 2W, setting the temperature of the glass substrate to 120 ℃, opening a valve of an oxygen tank, and introducing oxygen (O) into the magnetron chamber2) While regulating the gas flow meter so that the gas flow meter is oxygen (O)2) And argon (Ar) at a flow ratio of 1:5, adjusting a valve of the molecular pump to keep the total working pressure of gas in the magnetron chamber at 0.5Pa, enabling the substrate to be in a glow discharge range, starting timing film coating, and performing film coating for 2.5 hours in a stable glow discharge atmosphere.
(c) Repeating the steps (a) and (b) until the composite multilayer [ AgInS ] is completed2(x)/ZnO(y)]nThe total number of layers set.
Example 2: composite multilayer nano AgInS2And preparation of photocatalytic functional thin film of ZnOPreparing:
the steps are the same as example 1, except that step 3 is carried out to prepare the [ AgInS ] by radio frequency magnetron sputtering2(x)/ZnO(y)]nCompound poly
Layer of nano film:
(a) rotating the turntable of the substrate to AgInS2Directly above the target, the sputtering power is adjusted to 300W, the rotation power of the turntable of the substrate is adjusted to 2W, the temperature of the glass substrate is set to 120 ℃, a valve of an oxygen tank is opened to introduce oxygen (O) into the magnetron chamber2) While regulating the gas flow meter so that the gas flow meter is oxygen (O)2) And argon (Ar) at a flow ratio of 1:5, adjusting a valve of the molecular pump to keep the total working pressure of gas in the magnetron chamber at 0.5Pa, enabling the substrate to be in a glow discharge range, starting timing film coating, and performing film coating for 2.5 hours in a stable glow discharge atmosphere.
(b) Rotating the turntable of the substrate to the position right above the ZnO target, regulating the sputtering power to 180W, regulating the rotation power of the turntable of the substrate to 4W, setting the temperature of the glass substrate to 180 ℃, opening a valve of an oxygen tank and introducing oxygen (O) into the magnetron chamber2) While regulating the gas flow meter so that the gas flow meter is oxygen (O)2) And argon (Ar) at a flow ratio of 1:3, adjusting a valve of the molecular pump to keep the total working pressure of gas in the magnetron chamber at 2.0Pa, enabling the substrate to be in a glow discharge range, starting timing film coating, and performing film coating for 1h in a stable glow discharge atmosphere.
(c) Repeating the steps (a) and (b) until the composite multilayer [ AgInS ] is completed2(x)/ZnO(y)]nThe total number of layers set.
Example 3: composite multilayer nano AgInS2And preparing a photocatalytic functional film of ZnO:
1. cleaning the surface and the back of the glass substrate to remove dust particles, organic and inorganic impurities;
(d) putting the substrate into an acetone solution, and ultrasonically cleaning for 5 minutes to remove organic impurities on the surface of the substrate;
(e) putting the substrate into an alcohol solution, and ultrasonically cleaning for 5 minutes to remove inorganic impurities on the surface of the substrate;
(f) placing the substrate in deionized water, ultrasonically cleaning for 5 minutes, and cleaning the surface again;
(d) taking out the substrate, and drying in a vacuum drying oven for later use.
2. Preparation of [ AgInS ] by magnetron sputtering method2(x)/ZnO(y)]nPreparation of composite multilayer nano-film:
(a) fixing the glass substrate: and (2) placing the cleaned glass substrate on a mask plate, then fixing, opening an air release valve of the pretreatment chamber, opening a window of the pretreatment chamber when the pressure in the pretreatment chamber is consistent with the external atmospheric pressure, placing the mask plate in a tray of the pretreatment chamber, and closing the valve of the pretreatment chamber.
(b) Vacuumizing a pretreatment chamber: after a power supply, a water source and a gas source switch are turned on, a mechanical pump of the pretreatment chamber is turned on, a vacuum gauge of the pretreatment chamber is observed, when the magnitude of the vacuum degree of the pretreatment chamber reaches the vacuum degree of the magnetic control chamber, a baffle between the pretreatment chamber and the magnetic control chamber is opened, a tray rotating shaft in the pretreatment chamber is rotated, the substrate is conveyed into the magnetic control chamber, the substrate is placed on a rotating disk of the substrate by using a mechanical arm of the magnetic control chamber, the tray is conveyed back to the pretreatment chamber, and the baffle between the magnetic control chamber and the pretreatment chamber is closed. The pretreatment chamber mechanical pump was turned off.
(c) Vacuumizing a magnetic control chamber: starting a mechanical pump of a magnetic control chamber, observing a vacuum gauge of the magnetic control chamber, starting a molecular pump switch when the order of magnitude of vacuum degree in the magnetic control chamber reaches zero power, adjusting the rotating speed of the molecular pump, closing a gate valve of the mechanical pump when the rotating speed of the molecular pump reaches 400r/min, opening the gate valve of the molecular pump, driving the molecular pump to operate by the mechanical pump, utilizing the molecular pump to pump high vacuum to the magnetic control chamber, observing an ionization vacuum gauge simultaneously, and when the vacuum degree reaches 6.0 multiplied by 10-4And (3) closing the valve of the molecular pump in the magnetic control chamber while Pa is in. And simultaneously opening a valve of an argon (Ar) gas tank, adjusting a valve of the molecular pump, observing the vacuum gauge, and fixing the position of the valve of the molecular pump when the working pressure of the magnetic control chamber reaches 1.0 Pa.
(d) Glow discharge: and (3) turning on a 500W radio frequency working source, adjusting the power of a radio frequency matcher to 80W, finding out glow discharge in the magnetron, pre-sputtering for 10min, and preparing to start coating when the color of the glow discharge is stable and appears bluish white.
3. Preparation of [ AgInS ] by radio frequency magnetron sputtering2(x)/ZnO(y)]nCompounding the multilayer nano film:
(a) rotating the turntable of the substrate to AgInS2Directly above the target, the sputtering power is adjusted to 240W, the rotation power of the turntable of the substrate is adjusted to 3W, the temperature of the glass substrate is set to 150 ℃, a valve of an oxygen tank is opened to introduce oxygen (O) into the magnetron chamber2) While regulating the gas flow meter so that the gas flow meter is oxygen (O)2) And argon (Ar) at a flow ratio of 1:4, adjusting a valve of the molecular pump to keep the total working pressure of gas in the magnetron chamber at 1.0Pa, placing the substrate in a glow discharge range, starting timing film coating, and performing film coating for 0.1h in a stable glow discharge atmosphere.
(b) Rotating the turntable of the substrate to the position right above the ZnO target, adjusting the sputtering power to 240W, adjusting the rotation power of the turntable of the substrate to 3W, setting the temperature of the glass substrate to 150 ℃, opening a valve of an oxygen tank, and introducing oxygen (O) into the magnetron chamber2) While regulating the gas flow meter so that the gas flow meter is oxygen (O)2) And argon (Ar) at a flow ratio of 1:4, adjusting a valve of the molecular pump to keep the total working pressure of gas in the magnetron chamber at 1.0Pa, enabling the substrate to be in a glow discharge range, starting timing film coating, and performing film coating for 2.5 hours in a stable glow discharge atmosphere. The mass ratio of AIS to ZnO is 1:200, and the thickness of the film layer in single circulation is 40 nm.
(c) Repeating the steps (a) and (b) until the composite multilayer [ AgInS ] is completed2(x)/ZnO(y)]nThe total number of layers set. The total thickness of the prepared film product was 200nm, and the final film stack addition number n was 5.
4. Taking out the substrate plated with the film: and after the radio frequency magnetron sputtering is finished, adjusting the power of the radio frequency matcher to be zero, and simultaneously closing the 500W radio frequency working source. The valves for the argon and oxygen tanks were closed while the gas flow meter was adjusted to zero. The valve of the molecular pump is closed, the rotating speed of the molecular pump is adjusted to zero, the valve of the mechanical pump is opened, when the vacuum degrees of the pretreatment chamber and the magnetic control chamber are in one order of magnitude, the baffle between the pretreatment chamber and the magnetic control chamber is opened, then the tray of the pretreatment chamber is sent into the magnetic control chamber, the mask plate is taken down by using a mechanical arm and placed into the tray, and the tray is conveyed back to the pretreatment chamber. And closing a baffle between the pretreatment chamber and the magnetic control chamber, and simultaneously closing a valve of a mechanical pump of the magnetic control chamber and a power supply of a vacuum gauge of the mechanical pump. And opening an air discharging valve of the pretreatment chamber, opening a window of the pretreatment chamber when the pressure in the pretreatment chamber is equal to the external atmospheric pressure, taking out the mask plate, unloading the substrate plated with the film from the mask plate, and storing the substrate in a vacuum drying box. Subsequent application tests were carried out as related products.
Example 4: composite multilayer nano AgInS2And preparing a photocatalytic functional film of ZnO:
the steps are the same as example 3, except that step 3(a) is carried out for 0.25h, and step (b) is carried out for 2.0h, so as to obtain the film with the mass ratio of AIS to ZnO of 1:100, the film thickness of single cycle of 50nm, and the final film stacking number n of 4.
Example 5: composite multilayer nano AgInS2And preparing a photocatalytic functional film of ZnO:
the steps are the same as example 3, except that step 3(a) is carried out for sputtering for 0.4h, and step (b) is carried out for sputtering for 2.0h, so as to obtain the film with the mass ratio of AIS to ZnO being 1:20, the thickness of the film layer in a single cycle being 40nm, and the final film layer stacking number n being 5.
Example 6: composite multilayer nano AgInS2And preparing a photocatalytic functional film of ZnO:
the steps are the same as example 3, except that step 3(a) is carried out for 0.5h, and step (b) is carried out for 1.5h, so as to obtain the film with the mass ratio of AIS to ZnO of 1:10, the film thickness of single cycle of 50nm, and the final film stacking number n of 4.
Example 7: composite multilayer nano AgInS2And preparing a photocatalytic functional film of ZnO:
the procedure was the same as example 3 except that sputtering was carried out for 1 hour in step 3(a) and for 2.5 hours in step b, to obtain a film having a mass ratio of AIS to ZnO of 5:10, a film thickness of 70nm in a single cycle, and an additional n of 3 in the final film stack.
Comparative example 1: preparing single zinc oxide multilayer film with total thickness of 200 nm.
1. Cleaning the surface and the back of the glass substrate to remove dust particles, organic and inorganic impurities;
(a) putting the substrate into an acetone solution, and ultrasonically cleaning for 5 minutes to remove organic impurities on the surface of the substrate;
(b) putting the substrate into an alcohol solution, and ultrasonically cleaning for 5 minutes to remove inorganic impurities on the surface of the substrate;
(c) placing the substrate in deionized water, ultrasonically cleaning for 5 minutes, and cleaning the surface again;
(d) taking out the substrate, and drying in a vacuum drying oven for later use.
2. Preparing a ZnO multilayer nano film by adopting a magnetron sputtering method:
(a) fixing the glass substrate: and (3) placing the cleaned glass substrate on a mask plate, and then fixing. And opening an air release valve of the pretreatment chamber, opening a window of the pretreatment chamber when the pressure in the pretreatment chamber is consistent with the external atmospheric pressure, putting the mask plate into a tray of the pretreatment chamber, and closing a valve of the pretreatment chamber.
(b) Vacuumizing a pretreatment chamber: after a power supply, a water source and a gas source switch are turned on, a mechanical pump of the pretreatment chamber is turned on, a vacuum gauge of the pretreatment chamber is observed, when the magnitude of the vacuum degree of the pretreatment chamber reaches the vacuum degree of the magnetic control chamber, a baffle between the pretreatment chamber and the magnetic control chamber is opened, a tray rotating shaft in the pretreatment chamber is rotated, the substrate is conveyed into the magnetic control chamber, the substrate is placed on a rotating disk of the substrate by using a mechanical arm of the magnetic control chamber, the tray is conveyed back to the pretreatment chamber, and the baffle between the magnetic control chamber and the pretreatment chamber is closed. The pretreatment chamber mechanical pump was turned off.
(c) Vacuumizing a magnetic control chamber: starting the mechanical pump of the magnetic control chamber, observing the vacuum gauge of the magnetic control chamber, starting the molecular pump switch when the magnitude of the vacuum degree in the magnetic control chamber reaches zero power, adjusting the rotating speed of the molecular pump, and when the rotating speed of the molecular pump reaches zero powerAt 400r/min, closing the gate valve of the mechanical pump, opening the gate valve of the molecular pump, driving the molecular pump to operate by the mechanical pump, pumping high vacuum to the magnetic control chamber by the molecular pump, observing the ionization vacuum gauge, and when the vacuum degree reaches 6.0 multiplied by 10-4And (3) closing the valve of the molecular pump in the magnetic control chamber while Pa is in. And simultaneously opening a valve of an argon (Ar) gas tank, adjusting a valve of the molecular pump, observing the vacuum gauge, and fixing the position of the valve of the molecular pump when the working pressure of the magnetic control chamber reaches 1.0 Pa.
(d) Glow discharge. And (3) turning on a 500W radio frequency working source, adjusting the power of a radio frequency matcher to 80W, finding out glow discharge in the magnetron, pre-sputtering for 10min, and preparing to start coating when the color of the glow discharge is stable and appears bluish white.
3. Preparing a ZnO composite multilayer nano film by radio frequency magnetron sputtering:
(a) rotating the turntable of the substrate to the position right above the ZnO target, adjusting the sputtering power to 240W, adjusting the rotation power of the turntable of the substrate to 3W, setting the temperature of the glass substrate to 150 ℃, opening a valve of an oxygen tank, and introducing oxygen (O) into the magnetron chamber2) While regulating the gas flow meter so that the gas flow meter is oxygen (O)2) And argon (Ar) with the flow ratio of 1:4, simultaneously adjusting a valve of a molecular pump to keep the working total pressure of gas in a magnetic control chamber at 1.0Pa, enabling the substrate to be in the range of glow discharge, starting timing coating, performing coating for 0.2-2 h in the atmosphere of stable glow discharge, and controlling the coating time to be 1.2 h to obtain the film thickness of 40 nm.
(b) And repeating the steps until the total number of layers set by the multilayer ZnO is 5. The total thickness of the prepared film product is 200 nm.
Comparative example 2: preparing single indium disulfide silver multilayer film, and the total thickness is 200 nm.
1. Cleaning the surface and the back of the glass substrate to remove dust particles, organic and inorganic impurities;
(a) putting the substrate into an acetone solution, and ultrasonically cleaning for 5 minutes to remove organic impurities on the surface of the substrate;
(b) putting the substrate into an alcohol solution, and ultrasonically cleaning for 5 minutes to remove inorganic impurities on the surface of the substrate;
(c) placing the substrate in deionized water, ultrasonically cleaning for 5 minutes, and cleaning the surface again;
(d) taking out the substrate, and drying in a vacuum drying oven for later use.
2. Preparing a multilayer nano film by adopting a magnetron sputtering method:
(a) fixing the glass substrate: and (3) placing the cleaned glass substrate on a mask plate, and then fixing. And opening an air release valve of the pretreatment chamber, opening a window of the pretreatment chamber when the pressure in the pretreatment chamber is consistent with the external atmospheric pressure, putting the mask plate into a tray of the pretreatment chamber, and closing a valve of the pretreatment chamber.
(b) Vacuumizing a pretreatment chamber: after a power supply, a water source and a gas source switch are turned on, a mechanical pump of the pretreatment chamber is turned on, a vacuum gauge of the pretreatment chamber is observed, when the magnitude of the vacuum degree of the pretreatment chamber reaches the vacuum degree of the magnetic control chamber, a baffle between the pretreatment chamber and the magnetic control chamber is opened, a tray rotating shaft in the pretreatment chamber is rotated, the substrate is conveyed into the magnetic control chamber, the substrate is placed on a rotating disk of the substrate by using a mechanical arm of the magnetic control chamber, the tray is conveyed back to the pretreatment chamber, and the baffle between the magnetic control chamber and the pretreatment chamber is closed. The pretreatment chamber mechanical pump was turned off.
(c) Vacuumizing a magnetic control chamber: starting a mechanical pump of a magnetic control chamber, observing a vacuum gauge of the magnetic control chamber, starting a molecular pump switch when the order of magnitude of vacuum degree in the magnetic control chamber reaches zero power, adjusting the rotating speed of the molecular pump, closing a gate valve of the mechanical pump when the rotating speed of the molecular pump reaches 400r/min, opening the gate valve of the molecular pump, driving the molecular pump to operate by the mechanical pump, utilizing the molecular pump to pump high vacuum to the magnetic control chamber, observing an ionization vacuum gauge simultaneously, and when the vacuum degree reaches 6.0 multiplied by 10-4And (3) closing the valve of the molecular pump in the magnetic control chamber while Pa is in. And simultaneously opening a valve of an argon (Ar) gas tank, adjusting a valve of the molecular pump, observing the vacuum gauge, and fixing the position of the valve of the molecular pump when the working pressure of the magnetic control chamber reaches 1.0 Pa.
(d) Glow discharge: and (3) turning on a 500W radio frequency working source, adjusting the power of a radio frequency matcher to 80W, finding out glow discharge in the magnetron, pre-sputtering for 10min, and preparing to start coating when the color of the glow discharge is stable and appears bluish white.
3. Preparation of AgInS by radio frequency magnetron sputtering2Compounding the multilayer nano film:
(a) rotating the turntable of the substrate to AgInS2Directly above the target, the sputtering power is adjusted to 240W, the rotation power of the turntable of the substrate is adjusted to 3W, the temperature of the glass substrate is set to 150 ℃, a valve of an oxygen tank is opened to introduce oxygen (O) into the magnetron chamber2) While regulating the gas flow meter so that the gas flow meter is oxygen (O)2) And argon (Ar) with the flow ratio of 1:4, adjusting a valve of a molecular pump to keep the working total pressure of gas in a magnetic control chamber at 1.0Pa, enabling the substrate to be in the range of glow discharge, starting timing coating, performing coating for 1-2 h in the atmosphere of stable glow discharge, and controlling the coating time to be 1.5h to obtain the film thickness of 40 nm.
(b) Repeating the steps until the multilayer AgInS is finished2The total number of layers set is 5. The total thickness of the prepared film product is 200 nm.
Testing of relevant properties:
firstly, the composite multilayer nano AgInS obtained in the example2(x)/ZnO(y)]nAnd carrying out corresponding structure and performance detection on the single zinc oxide multilayer film and the indium-silver disulfide multilayer film in the comparative examples 1 and 2, and obtaining results shown in the attached figures 1, 2 and 3. The test results show that the prepared composite multilayer nano-AgInS2(x)/ZnO(y)]nThe film has uniform composition, stronger visible light response capability, narrower band gap energy, more photon-generated carriers and the like. From fig. 3, it can be determined that the PL peak of the optical material of the film material of our invention is about 425-475 nm (the PL peak of pure indium-silver-disulfide in the upper small window, which is 650nm) according to the calculation formula of the forbidden band width: the Eg is 1260 ev/lambda, and the forbidden band width of the composite film material is 2.65-2.95 ev, while the forbidden band width of the pure indium disulfide silver is 1.9ev, which is obviously improved compared with 3.2ev of titanium dioxide, and proves that the composite film material is under visible lightCan exert photocatalysis.
(II) composite multilayer nano AgInS obtained in example2(x)/ZnO(y)]nRespectively treating and applying the film, the single zinc oxide film and the indium-silver disulfide film in the comparative proportions 1 and 2 to difficultly-degraded wastewater, and evaluating the composite multilayer nano [ AgInS ] by using a flat plate type reactor2(x)/ZnO(y)]nThe film photocatalytically degrades different types of difficultly degraded waste water.
a. The invention relates to a composite multilayer nano [ AgInS ]2(x)/ZnO(y)]nThe film can be used for degrading the amoxicillin medical wastewater by visible light catalysis. The photocatalytic film (corresponding to the product of example 5) was placed on the plate of the reactor, with an aqueous solution of amoxicillin (5.0X 10)-5mol.L-1500mL) is circulated on the surface of the catalyst under the drive of a peristaltic pump, and the flow rate is 200 mL/min; a xenon lamp light source is utilized, a filter is utilized to filter out a light-visible region, so that the light source only emits visible light, the wavelength range is 420-800 nm, and the illumination intensity is 200mw/cm2And (3) continuously flowing for reaction for 1 hour, and measuring the sample concentration of amoxicillin in different time periods by using high performance liquid chromatography to calculate the degradation rate. FIGS. 4 and 5 are the degradation curves of amoxicillin, and it can be seen from the graphs that the amoxicillin concentration is almost completely degraded after 50 minutes of reaction. After the membrane is removed, the membrane is recycled under the same water quality condition, and experiments show that after 10 cycles, the catalytic activity (based on the efficiency of degrading amoxicillin) of the membrane is reduced by less than 0.1%. In the same amoxicillin medical wastewater, the pure zinc oxide film in the comparative example 1 basically degrades the amoxicillin concentration after the reaction is nearly 60 minutes, the efficiency is obviously lower than that of a composite product, and the pure zinc oxide film is cleaned again after being used and recycled under the same water quality condition, and experiments show that the catalytic activity of the film is obviously reduced to 65% after 4 cycles, which indicates that the anti-pollution capability of the film is obviously poorer than that of the composite product; the indium sulfide silver film of the comparative example 2 has reaction efficiency in amoxicillin wastewater, and the amoxicillin is basically degraded in 50 minutes, which is similar to that of a composite product; meanwhile, the pure indium-silver sulfide film is reusedThe catalyst is cleaned and recycled under the same water quality condition, and experiments show that the catalytic activity of the catalyst is obviously reduced to 60 percent after 5 times of circulation, which indicates that the pollution resistance of the catalyst is obviously poorer than that of a composite product. The relevant comparison is shown in FIG. 5.
b. The invention relates to a composite multilayer nano [ AgInS ]2(x)/ZnO(y)]nThe film catalyzes and degrades dye wastewater by sunlight.
A photocatalytic film (corresponding to the product of example 5) is placed on a flat plate of a reactor, and a dye wastewater aqueous solution (COD3000mg/L,500mL) is driven by a peristaltic pump to circularly flow through the surface of the catalyst at the flow rate of 200 mL/min; the xenon lamp light source is utilized to simulate the wavelength of sunlight, the wavelength range is 190-800 nm, and the illumination intensity is 300mw/cm2And continuously flowing for 1 hour, and measuring the COD concentration in the wastewater to calculate the degradation rate. FIG. 6 is a COD degradation curve of the dye wastewater, and it can be seen from the graph that after 1 hour of reaction, the COD in the wastewater is only 400mg/L, and the degradation effect is very obvious. After the membrane is removed, the membrane is recycled under the same water quality condition, and experiments show that after 10 cycles, the catalytic activity (based on the efficiency of degrading amoxicillin) of the membrane is reduced by less than 0.1%.
Comparative example 3: titanium dioxide powder particles are adopted to degrade the amoxicillin medical wastewater under the catalysis of visible light.
Adopts a semi-continuous reactor and an amoxicillin aqueous solution (5.0 multiplied by 10)-5mol.L-1500ml), adding 20 g of titanium dioxide powder catalyst, using a xenon lamp light source, using a filter to filter out a light-visible region, so that the light source only emits visible light, the wavelength range is 420-800 nm, and the illumination intensity is 200mw/cm2And continuously stirring for reaction for 1 hour, and measuring the sample concentration of amoxicillin in different time periods by using high performance liquid chromatography to calculate the degradation rate. FIG. 4 is a graph showing the degradation of amoxicillin, and it can be seen that the concentration of amoxicillin is not substantially degraded after 50 minutes of reaction.
Comparative example 4: titanium dioxide powder particles are adopted to degrade dye wastewater by sunlight catalysis. Adopting a semi-continuous reactor, adding 20 g of titanium dioxide powder catalyst into dye wastewater aqueous solution (COD is 3000mg/L,500ml), and utilizing a xenon lamp light source and a moldThe quasi-solar light has a wavelength of 190-800 nm and an illumination intensity of 300mw/cm2And continuously flowing for 1 hour, and measuring the COD concentration in the wastewater to calculate the degradation rate. FIG. 6 is a curve comparing the COD degradation of the dye wastewater, and it can be seen from the graph that after 1 hour of reaction, the COD in the wastewater is 2600mg/L, and there is substantially no degradation effect.
Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A multi-layer composite photocatalytic film material is prepared from AgInS2The film and the ZnO film are compounded in a multilayer way, and the structural general formula is [ AgInS ]2(X)/ZnO(y)]nWherein x and y denote AgInS in a single pacing cycle2The thickness of the film and the ZnO film, and 1<x<30nm,1<y<30nm, n is the number of the composite coating film and is 1<n<5。
2. The multilayer composite photocatalytic film material as set forth in claim 1, wherein the total thickness of the multilayer composite photocatalytic film material is 150-200 nm.
3. The multi-layer composite photocatalytic film material as set forth in claim 1, wherein AgInS is present in each coating cycle of the composite film material2The mass composition ratio of the film to the ZnO film is 1: 2-200.
4. The multilayer composite photocatalytic film material as set forth in claim 1, wherein the AgInS is2The multilayer composite of the film and the ZnO film is prepared by radio frequency magnetron sputtering coating.
5. The method for preparing the multilayer composite photocatalytic film material as recited in any one of claims 1-4, characterized by comprising the steps of:
(1) cleaning and drying the glass substrate, placing the glass substrate on a mask plate, fixing and sending the glass substrate into a pretreatment chamber; vacuumizing the pretreatment chamber, opening a baffle between the pretreatment chamber and the magnetic control chamber when the magnitude of the vacuum degree of the pretreatment chamber reaches the vacuum degree of the magnetic control chamber, conveying the glass substrate into the magnetic control chamber, and closing the baffle between the magnetic control chamber and the pretreatment chamber; vacuumizing the magnetic control chamber, firstly vacuumizing by using a mechanical pump, then vacuumizing the magnetic control chamber by using a molecular pump, and introducing argon; glow discharge, when the discharge color is stable and presents a blue-white color, preparing to start coating;
(2) rotating a glass substrate to AgInS2Directly above the target, regulating the sputtering power to 180-class 300W, regulating the rotation power of a turntable of the glass substrate to 2-5W, setting the temperature of the glass substrate to 120-class 180 ℃, introducing gas into the magnetron chamber to enable the flow ratio of oxygen and argon of a gas flowmeter to be 1:3-5, simultaneously controlling the total working pressure of the gas in the magnetron chamber to be kept at 0.5-2.0Pa, enabling the substrate to be in the range of glow discharge, starting timing film coating, and performing film coating for 1-2 hours in the atmosphere of stable glow discharge;
b. rotating a turntable of a glass substrate to be right above a ZnO target, adjusting the sputtering power to be 180-class 300W, adjusting the rotation power of the turntable of the substrate to be 2-5W, setting the temperature of the glass substrate to be 120-class 180 ℃, introducing gas into a magnetron chamber to enable the flow ratio of oxygen and argon of a gas flowmeter to be 1:3-5, simultaneously controlling the working total pressure of the gas in the magnetron chamber to be kept at 0.5-2.0Pa, enabling the substrate to be in the range of glow discharge, starting timing film coating, and performing film coating for 1-2 h in the atmosphere of stable glow discharge;
c. repeating the steps a and b until the composite multilayer [ AgInS ] is completed2(X)/ZnO(y)]nSetting the total layer number;
(3) after the radio frequency magnetron sputtering is finished, the pressure intensity of the pretreatment chamber and the magnetron chamber is adjusted, and the substrate plated with the film is taken out.
6. According to the claimsThe preparation method of the multilayer composite photocatalytic film material in the step (5) is characterized in that the current vacuum degree of the magnetron chamber in the step (1) reaches 6.0 multiplied by 10-4And (3) closing a valve of the molecular pump in the magnetic control chamber, opening a valve of the argon gas tank, adjusting the valve of the molecular pump, observing the vacuum gauge, and fixing the position of the valve of the molecular pump when the working pressure of the magnetic control chamber reaches 1.0 Pa.
7. The method for preparing a multilayer composite photocatalytic film material according to claim 5, wherein in the step (2), the sputtering power is 240W, the rotation power of a turntable of a substrate is 3W, the temperature of a glass substrate is 150 ℃, the total working pressure of gas in a magnetron chamber is kept at 1.0Pa, and the film coating is carried out for 0.5h in the atmosphere of stable glow discharge.
8. The method for preparing a multilayer composite photocatalytic film material according to claim 5, wherein in the step (2) b, the sputtering power is 240W, the rotation power of a turntable of a substrate is 3W, the temperature of a glass substrate is 150 ℃, the total working pressure of gas in a magnetron chamber is kept at 1.0Pa, and the film is coated for 1.5 hours in a stable glow discharge atmosphere.
9. Use of the multilayer composite photocatalytic film material of any one of claims 1-4 in wastewater treatment.
10. Use of the multi-layer composite photocatalytic film material of any one of claims 1-4 in treatment of dye wastewater or antibiotic wastewater.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010721027.5A CN111822001B (en) | 2020-07-24 | 2020-07-24 | Multilayer composite photocatalytic film material and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010721027.5A CN111822001B (en) | 2020-07-24 | 2020-07-24 | Multilayer composite photocatalytic film material and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111822001A true CN111822001A (en) | 2020-10-27 |
CN111822001B CN111822001B (en) | 2021-05-11 |
Family
ID=72926234
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010721027.5A Active CN111822001B (en) | 2020-07-24 | 2020-07-24 | Multilayer composite photocatalytic film material and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111822001B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113003815A (en) * | 2021-03-19 | 2021-06-22 | 山东建筑大学 | Continuous photocatalytic ultrafiltration cup, preparation method of fiber ball and preparation method of ultrafiltration membrane |
CN114540762A (en) * | 2022-03-02 | 2022-05-27 | 山东建筑大学 | Composite film material and preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101162743A (en) * | 2007-11-29 | 2008-04-16 | 北京航空航天大学 | Preparation method of microgrid structure a photocatalyst |
CN101608300A (en) * | 2009-07-16 | 2009-12-23 | 浙江大学 | The TiO of highlight catalytic active 2The preparation method of-ZnO double-layer compound film |
CN103361631A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of zinc oxide doped titanium oxide film for photocatalysis |
US20150182950A1 (en) * | 2013-12-31 | 2015-07-02 | Industrial Technology Research Institute | Photocatalytic film structure |
CN109621979A (en) * | 2018-12-13 | 2019-04-16 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of ZnO/ zinc indium sulphur nano heterojunction |
-
2020
- 2020-07-24 CN CN202010721027.5A patent/CN111822001B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101162743A (en) * | 2007-11-29 | 2008-04-16 | 北京航空航天大学 | Preparation method of microgrid structure a photocatalyst |
CN101608300A (en) * | 2009-07-16 | 2009-12-23 | 浙江大学 | The TiO of highlight catalytic active 2The preparation method of-ZnO double-layer compound film |
CN103361631A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of zinc oxide doped titanium oxide film for photocatalysis |
US20150182950A1 (en) * | 2013-12-31 | 2015-07-02 | Industrial Technology Research Institute | Photocatalytic film structure |
CN109621979A (en) * | 2018-12-13 | 2019-04-16 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of ZnO/ zinc indium sulphur nano heterojunction |
Non-Patent Citations (4)
Title |
---|
MARÍA C. NEVÁREZ MARTÍNEZ等: ""Synergy between AgInS2 quantum dots and ZnO nanopyramids for photocatalytic hydrogen evolution and phenol degradation"", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
MINKI BAEK等: ""Environmentally benign synthesis of CuInS2/ZnO heteronanorods visible light activated photocatalysis of organic pollutant/bacteria and study of its mechanism"", 《PHOTOCHEM. PHOTOBIOL. SCI.》 * |
姜兆化: "《固体界面物理化学原理及应用》", 31 January 2017, 哈尔滨工业大学出版社 * |
曹茂盛等: "《纳米材料导论》", 31 August 2001, 哈尔滨工业大学出版社 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113003815A (en) * | 2021-03-19 | 2021-06-22 | 山东建筑大学 | Continuous photocatalytic ultrafiltration cup, preparation method of fiber ball and preparation method of ultrafiltration membrane |
CN113003815B (en) * | 2021-03-19 | 2022-05-17 | 山东建筑大学 | Continuous photocatalytic ultrafiltration cup, preparation method of fiber ball and preparation method of ultrafiltration membrane |
CN114540762A (en) * | 2022-03-02 | 2022-05-27 | 山东建筑大学 | Composite film material and preparation method and application thereof |
CN114540762B (en) * | 2022-03-02 | 2023-09-22 | 山东建筑大学 | Composite film material and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN111822001B (en) | 2021-05-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Yamagishi et al. | Thin film TiO2 photocatalyst deposited by reactive magnetron sputtering | |
Yu et al. | Photocatalytic activity and characterization of the sol-gel derived Pb-doped TiO 2 thin films | |
CN111822001B (en) | Multilayer composite photocatalytic film material and preparation method and application thereof | |
Wong et al. | Influence of crystallinity and carbon content on visible light photocatalysis of carbon doped titania thin films | |
Ohno et al. | Plasma emission control of reactive sputtering process in mid-frequency mode with dual cathodes to deposit photocatalytic TiO2 films | |
Ogawa et al. | Growth of TiO2 thin film by reactive RF magnetron sputtering using oxygen radical | |
Song et al. | Crystallinity and photocatalytic activity of TiO2 films deposited by reactive sputtering with radio frequency substrate bias | |
Badillo-Ávila et al. | Cu2O thin films obtained from sol-gel cuo films using a simple argon/dry-air microwave plasma | |
Grao et al. | Crystalline TiO2 supported on stainless steel mesh deposited in a one step process via pulsed DC magnetron sputtering for wastewater treatment applications | |
Ohno et al. | Photocatalytic TiO2 films deposited by reactive magnetron sputtering with unipolar pulsing and plasma emission control systems | |
JP2000096212A (en) | Photocatalyst film coated member and its production | |
Chiu et al. | Tailoring superhydrophilicity and photocatalysis of sputter deposited TiO2/WO3 thin films on super white glass by process and chemical composition optimization | |
Perekrestov et al. | The comparative study of electrical, optical and catalytic properties of Co3O4 thin nanocrystalline films prepared by reactive high-power impulse and radio frequency magnetron sputtering | |
Ohno et al. | Photocatalytic properties of TiO2 films deposited by reactive sputtering in mid-frequency mode with dual cathodes | |
Sirghi | Plasma synthesis of photocatalytic TiOx thin films | |
Zheng et al. | Photocatalytic activity study of TiO2 thin films with and without Fe ion implantation | |
Wang et al. | Investigation of the photoreactivity of nanocrystalline TiO2 thin film by ion-implantation technique | |
Bai et al. | Effect of Zn and Ti mole ratio on microstructure and photocatalytic properties of magnetron sputtered TiO2–ZnO heterogeneous composite film | |
Maicu et al. | Photocatalytic properties of TiO2 thin films modified with Ag and Pt nanoparticles deposited by gas flow sputtering | |
Pulsipher et al. | O2 plasma treatment of mesoporous and compact TiO2 photovoltaic films: Revealing and eliminating effects of Si incorporation | |
Noguchi et al. | Relationship between the photocatalytic characteristics and the oxygen partial pressure of TiO2 thin films prepared by a DC reactive sputtering method | |
CN112156769B (en) | Al/WO 3 Nano composite film, preparation method and application thereof | |
Han et al. | Preparation of TiO 2/ITO film electrode by AP-MOCVD for photoelectrocatalytic application | |
Hajkova et al. | The influence of surface treatment on photocatalytic activity of PE CVD TiO2 thin films | |
Zhang et al. | Antibacterial properties of nanometer Fe3+-TiO2 thin films |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |