CN113426434B - SnO (stannic oxide)2/Ag2(1-x)NixFe2O4Preparation method of composite film material - Google Patents
SnO (stannic oxide)2/Ag2(1-x)NixFe2O4Preparation method of composite film material Download PDFInfo
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 240
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 74
- 238000002360 preparation method Methods 0.000 claims abstract description 62
- 238000001035 drying Methods 0.000 claims abstract description 49
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 238000007747 plating Methods 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012528 membrane Substances 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 108
- 239000010408 film Substances 0.000 claims description 103
- 238000003756 stirring Methods 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 32
- 238000009210 therapy by ultrasound Methods 0.000 claims description 32
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 20
- 239000010409 thin film Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000006121 base glass Substances 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 11
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000013329 compounding Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000002791 soaking Methods 0.000 abstract description 6
- 230000003595 spectral effect Effects 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000001782 photodegradation Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- 238000000089 atomic force micrograph Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 229910017727 AgNi Inorganic materials 0.000 description 2
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910004160 TaO2 Inorganic materials 0.000 description 1
- 229910003069 TeO2 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- NQKXFODBPINZFK-UHFFFAOYSA-N dioxotantalum Chemical compound O=[Ta]=O NQKXFODBPINZFK-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8966—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses SnO2/Ag2(1‑x)NixFe2O4Preparation method of composite film material, Ag2(1‑x)NixFe2O4Wherein x is 0.05-0.5, and the method comprises the following steps: s1: pretreating a glass substrate; s2: preparation of modified SnO2Sol: s201: preparation of SnO2Sol; s202: preparation of nano TiO2Modified SnO2Sol; s3: preparation of Ag2‑xNixFe2O4Precursor solution; s4: preparation of SnO2/Ag2(1‑x)NixFe2O4And (3) composite membrane: s401: soaking the glass substrate pretreated by S1 in modified SnO2Treating in sol for 10min, slowly taking out at a pulling speed of 1mm/s, drying at 80 deg.C for 10min, and marking as plated modified SnO2Film 1 layer; s402: repeating the operation S401 for 0-4 times; s403: calcining; s404: plating with Ag2(1‑x)NixFe2O4Film 1 layer; s405: repeating S404 operation for 0-4 times; s406: calcining for 2 hours at 450-600 ℃. According to the invention, by constructing a heterojunction structure, the transfer path of electrons is changed, the number of photo-generated electron-hole pairs is reduced, and the photocatalytic activity and stability of the composite material are further improved; meanwhile, the spectral response range to visible light is wide.
Description
Technical Field
The invention belongs to the field of photocatalytic materials, and particularly relates to SnO2/Ag2(1-x)NixFe2O4A preparation method of a composite film material.
Background
SnO2It exists in nature mainly in the form of the mineral cassiterite, which, like other metal oxides, has a rutile crystalline structure, such as TeO2，TiO2，TaO2，RuO2，PbO2。SnO2Is formed due to the symmetry of its tetragonal structure.
SnO2The semiconductor has a valence band and a conduction band structure, wherein the valence band and the conduction band both have energy which is higher than that of the conduction band, the conduction band is the highest energy band in the semiconductor, and the valence band is filled with free electrons. The forbidden band width is the energy difference between the energy band and the valence band, and the forbidden band width value is 3.6 eV. And because the relation between the forbidden band width and the transmission wavelength is as follows:
E＝1240/λ
from this relationship, it is possible to excite an electron in the valence band to the conduction band only when the wavelength of the irradiation light is 344.5nm or less, generate a photogenerated electron having strong reducibility in the conduction band, and generate a photogenerated hole having strong oxidizability in the valence band due to disappearance of the transition of the electron. The photogenerated hole and the photogenerated electron are quickly compounded, and the rest parts are mutually separated and transferred to react with water and oxygen in the air to generate carboxyl free radicals with strong oxidizing property. The generated strong oxidizing free radical is adsorbed on SnO2The organic contaminants on the surface undergo a redox reaction and the contaminants are reduced to break down into water and carbon dioxide. The reaction steps are as follows:
h++H2O→·OH+H+
2HO2·→O2+H2O2
h++OH-→·OH
OH + org (organic) → … → CO2+H2O
h++org→…→CO2+H2O
After the element reaction, the material is adsorbed on SnO2Pollutants on the surface are degraded into water and carbon dioxide, the degradation process is pollution-free, the energy consumption is low, the reaction operation is simple and easy, and the superiority of photocatalysis pollutants is embodied.
However, since SnO2The forbidden band value is wide, when the material is used as a photocatalytic material, the minimum absorption wavelength lambda is less than or equal to 1240/Eg, the maximum absorption wavelength lambda is less than or equal to 340mm, the spectral response range is narrow, and visible light in sunlight cannot be utilized; meanwhile, photoproduction holes and photoproduction electrons cannot be separated in time, and are very easy to combine, so that the photocatalytic degradation performance is reduced.
The spinel type ferrite has a narrow forbidden band width, such as the forbidden band width of silver ferrite is only 1.15-1.7 eV, and the forbidden band width of nickel ferrite is 1.5-1.63 eV, so that the spinel type ferrite has good response performance to visible light; meanwhile, the unique spinel structure provides a feasible basis for improving the photocatalytic efficiency, and the utilization efficiency of the spinel structure to visible light can be improved by optimizing and modifying the crystal lattice.
Therefore, how to develop the nano tin oxide/hybrid ferrite composite photocatalytic material with high visible light catalytic activity, high photoproduction electron-hole separation efficiency and high stability has important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide SnO2/ Ag2(1-x)NixFe2O4A preparation method of a composite film material.
The technical scheme of the invention is summarized as follows:
SnO (stannic oxide)2/Ag2(1-x)NixFe2O4Preparation method of composite film material, Ag2(1-x)NixFe2O4Wherein x is 0.05-0.5, and the method comprises the following steps:
s1: pretreatment of the glass substrate: placing the glass substrate in distilled water, carrying out ultrasonic treatment for 10min, drying, then placing in acetone, carrying out ultrasonic treatment for 20min, drying, then placing in absolute ethyl alcohol, carrying out ultrasonic treatment for 20min, drying, then placing the glass substrate in a mixture of ammonia water, hydrogen peroxide and distilled water according to a ratio of 1: 1: 5, carrying out ultrasonic treatment for 60min, and then drying;
s2: preparation of modified SnO2Sol:
s201: preparation of SnO2Sol: adding stannous chloride dihydrate into absolute ethyl alcohol at room temperature of 25 ℃, stirring and dissolving, then dropwise adding a potassium persulfate solution, magnetically stirring for 6 hours at the temperature of 78 ℃, then naturally cooling, standing and aging for 36 hours for later use to obtain SnO2Sol;
s202: preparation of modified SnO2Sol: mixing nanometer TiO2Adding SnO2Magnetically stirring in sol for 1h to obtain modified SnO2Sol;
the stannous chloride dihydrate, the absolute ethyl alcohol, the potassium persulfate solution and the nano TiO2The dosage ratio of (4-5) mmol to (20 mL to 2mL to (2 mmol);
s3: preparation of Ag2(1-x)NixFe2O4Precursor solution:
s301: dissolving silver nitrate, nickel nitrate hexahydrate and ferric nitrate nonahydrate in deionized water at 25 ℃ and room temperature, adding citric acid, and stirring for 10-15 min to obtain a solution A;
s302: at the room temperature of 25 ℃, dropwise adding triethanolamine into 2mol/L sodium hydroxide solution, and stirring uniformly to prepare solution B;
s303: slowing the solution BSlowly dripping the solution A for 30min, and magnetically stirring the solution A for 0.5 to 1 hour to obtain Ag2(1-x)NixFe2O4Precursor solution;
the dosage ratio of the silver nitrate, the nickel nitrate hexahydrate, the ferric nitrate nonahydrate, the deionized water, the citric acid, the sodium hydroxide solution and the triethanolamine is (1-1.9) mmol, (0.05-0.5) mmol, 2mmol, 20mL, (0.05-0.1) g, 5mL and 1 mL;
s4: preparation of SnO2/Ag2(1-x)NixFe2O4And (3) composite membrane:
s401: immersing the pretreated glass substrate S1 in the modified SnO obtained from S22Treating in sol for 10min, slowly taking out at a pulling speed of 1mm/s, drying at 80 deg.C for 10min, and marking as plated modified SnO2Film 1 layer;
s402: repeating S401 for 0-4 times to obtain modified SnO plated with different layers2A film;
s403: the modified SnO coated with the S4022Putting the glass substrate of the film into a muffle furnace, heating to 450-600 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature to obtain the modified SnO2A glass sheet of film;
s404: mixing Ag with water2(1-x)NixFe2O4Transferring the precursor solution into a reaction kettle, and then plating the modified SnO obtained from S4032Immersing the glass sheet of the film into the precursor solution, reacting at 120-160 ℃ for 0.5-1 h, cooling to room temperature, slowly taking the glass sheet out of the liquid level at the pulling speed of 1mm/s, drying at 80 ℃ for 10min, and marking as Ag plating2(1-x)NixFe2O4Film 1 layer;
s405: repeating S404 operation for 0-4 times to obtain Ag plated with different layers2(1-x)NixFe2O4SnO of thin film2A base glass sheet;
s406: plating the Ag obtained in S4052(1-x)NixFe2O4SnO of thin film2Putting the base glass sheet into a muffle furnace, heating to 450-600 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature along with the furnace, namelyObtaining glass-based laminated SnO2/Ag2(1-x)NixFe2O4And (3) compounding the film.
Preferably, the mass percentage concentration of the ammonia water is 10-20%.
Preferably, the mass percentage concentration of the hydrogen peroxide is 20-30%.
Preferably, the concentration of the potassium persulfate solution is 0.05-0.2 mol/L.
Preferably, the nano TiO2The particle size of (A) is in the range of 5 to 30 nm.
Preferably, the SnO2Film and Ag2(1-x)NixFe2O4The total number of layers of the film was 6.
The invention has the beneficial effects that:
the invention utilizes sol-gel method to prepare nano SnO2Sol and further use of nano TiO2Doping modification for improving cured SnO2The photocatalysis performance and the wear resistance of the film are improved, and the nano AgFeO is further grown in situ by a hydrothermal method2-NiFe2O4Hybrid film of the general formula Ag2(1-x)NixFe2O4And x is 0.05-0.5, a heterojunction structure is constructed, the transfer path of electrons is changed, the photoproduction electrons and holes are transferred along different directions at a heterojunction interface, the number of photoproduction electron-hole pairs is reduced, and the photocatalytic activity and the stability of the composite material are improved; at the same time, Ag2(1-x)NixFe2O4The forbidden band width is less than 1.7eV, the spectral response range to visible light is wide, and the nano SnO2The composite material can effectively improve the sunlight absorption rate and the effective utilization rate, and further improve the photocatalytic performance.
Drawings
FIG. 1 is a SnO of the present invention2/Ag2(1-x)NixFe2O4A flow chart of a preparation method of the composite film material;
FIG. 2 is SnO prepared in example 12/Ag1.9Ni0.05Fe2O4(SnO2Number of layers of5) AFM image of thin film material;
FIG. 3 is SnO prepared in example 12/Ag1.4Ni0.3Fe2O4(SnO2Number of layers of 3) AFM image of the thin film material;
FIG. 4 is SnO prepared in example 12/AgNi0.5Fe2O4(SnO2Number of layers of 1) AFM images of thin film materials.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
The invention provides an embodiment of SnO2/Ag2(1-x)NixFe2O4Preparation method of composite film material, Ag2(1-x)NixFe2O4Wherein x is 0.05-0.5, and the method comprises the following steps:
s1: pretreatment of the glass substrate: placing the glass substrate in distilled water, carrying out ultrasonic treatment for 10min, drying, then placing in acetone, carrying out ultrasonic treatment for 20min, drying, then placing in absolute ethyl alcohol, carrying out ultrasonic treatment for 20min, drying, then placing the glass substrate in a mixture of 10-20% by mass of ammonia water, 20-30% by mass of hydrogen peroxide and distilled water according to a proportion of 1: 1: 5, carrying out ultrasonic treatment for 60min, and then drying;
s2: preparation of modified SnO2Sol:
s201: preparation of SnO2Sol: adding stannous chloride dihydrate into absolute ethyl alcohol at room temperature of 25 ℃, stirring and dissolving, then dropwise adding a potassium persulfate solution, magnetically stirring for 6 hours at the temperature of 78 ℃, then naturally cooling, standing and aging for 36 hours for later use to obtain SnO2Sol;
s202: preparation of modified SnO2Sol: nano TiO with the particle size range of 5-30 nm2Adding SnO2Magnetically stirring in sol for 1h to obtain modified SnO2Sol;
the stannous chloride dihydrate, the absolute ethyl alcohol, the potassium persulfate solution and the nano TiO2The dosage ratio of (4-5) mmol to (20 mL to 2mL to (2 mmol);
s3: preparation of Ag2(1-x)NixFe2O4Precursor solution:
s301: dissolving silver nitrate, nickel nitrate hexahydrate and ferric nitrate nonahydrate in deionized water at 25 ℃ and room temperature, adding citric acid, and stirring for 10-15 min to obtain a solution A;
s302: at the room temperature of 25 ℃, dropwise adding triethanolamine into 2mol/L sodium hydroxide solution, and stirring uniformly to prepare solution B;
s303: slowly dripping the solution B into the solution A for 30min, and magnetically stirring for 0.5-1 h to obtain Ag2(1-x)NixFe2O4Precursor solution;
the dosage ratio of the silver nitrate, the nickel nitrate hexahydrate, the ferric nitrate nonahydrate, the deionized water, the citric acid, the sodium hydroxide solution and the triethanolamine is (1-1.9) mmol, (0.05-0.5) mmol, 2mmol, 20mL, (0.05-0.1) g, 5mL and 1 mL;
s4: preparation of SnO2/Ag2(1-x)NixFe2O4And (3) composite membrane:
s401: immersing the pretreated glass substrate S1 in the modified SnO obtained from S22Treating in sol for 10min, slowly taking out at a pulling speed of 1mm/s, drying at 80 deg.C for 10min, and marking as plated modified SnO2Film 1 layer;
s402: repeating S401 for 0-4 times to obtain modified SnO plated with different layers2A film;
s403: the modified SnO coated with the S4022Putting the glass substrate of the film into a muffle furnace, heating to 450-600 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature to obtain the modified SnO2A glass sheet of film;
s404: mixing Ag with water2(1-x)NixFe2O4Transferring the precursor solution into a reaction kettle, and then plating the modified SnO obtained from S4032Immersing the glass sheet of the film into the precursor solution, reacting at 120-160 ℃ for 0.5-1 h, cooling to room temperature, and slowly pulling at a pulling speed of 1mm/sTaking out the liquid surface, drying at 80 deg.C for 10min, and recording as Ag plating2(1-x)NixFe2O4Film 1 layer;
s405: repeating S404 operation for 0-4 times and controlling SnO2Film and Ag2(1-x)NixFe2O4The total number of the layers of the film is 6, and the Ag plated with different layers is obtained2(1-x)NixFe2O4SnO of thin film2A base glass sheet;
s406: plating the Ag obtained in S4052(1-x)NixFe2O4SnO of thin film2Putting the base glass sheet into a muffle furnace, heating to 450-600 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature along with the furnace to obtain the glass-based laminated SnO2/Ag2(1-x)NixFe2O4And (3) compounding the film.
Example 15 SnO2/1Ag1.9Ni0.05Fe2O4
SnO (stannic oxide)2/Ag1.9Ni0.05Fe2O4Method for preparing composite film material, namely Ag2(1-x)NixFe2O4Wherein x is 0.05, comprising the following steps:
s1: pretreatment of the glass substrate: placing a glass substrate with the specification of 5cm multiplied by 5cm in distilled water, carrying out ultrasonic treatment for 10min, drying, then placing in acetone, carrying out ultrasonic treatment for 20min, drying, then placing in absolute ethyl alcohol, carrying out ultrasonic treatment for 20min, drying, then placing the glass substrate in a mixture of 10 mass percent ammonia water, 20 mass percent hydrogen peroxide and distilled water according to the proportion of 1: 1: 5, carrying out ultrasonic treatment for 60min, and then drying;
s2: preparation of modified SnO2Sol:
s2: preparation of modified SnO2Sol:
s201: preparation of SnO2Sol: at room temperature of 25 ℃, adding 20mmol of stannous chloride dihydrate into 100mL of absolute ethyl alcohol, stirring for dissolving, then dropwise adding 10mL of 0.05mol/L potassium persulfate solution, and magnetically stirring for 6h at 78 DEG CThen naturally cooling, standing and aging for 36h for later use to obtain SnO2Sol;
s202: preparation of modified SnO2Sol: nano TiO with the particle size of 5-30 nm in 10mmol2Adding SnO obtained in S2012Magnetically stirring in sol for 1h to obtain modified SnO2Sol;
s3: preparation of Ag1.9Ni0.05Fe2O4Precursor solution:
s301: dissolving 9.5mmol of silver nitrate, 0.25mmol of nickel nitrate hexahydrate and 10mmol of ferric nitrate nonahydrate in 100mL of deionized water at room temperature of 25 ℃, adding 0.25g of citric acid, and stirring for 10min to obtain a solution A;
s302: at the room temperature of 25 ℃, 5mL of triethanolamine is dropwise added into 25mL of 2mol/L sodium hydroxide solution, and after the triethanolamine is uniformly stirred, solution B is prepared;
s303: slowly dripping the solution B into the solution A for 30min, and magnetically stirring for 0.5h to obtain Ag1.9Ni0.05Fe2O4Precursor solution;
s4: preparation of SnO2/Ag1.9Ni0.05Fe2O4And (3) composite membrane:
s401: soaking the glass substrate pretreated by S1 in modified SnO2Treating in sol for 10min, slowly taking out at a pulling speed of 1mm/s, drying at 80 deg.C for 10min, and marking as plated modified SnO2Film 1 layer;
s402: repeating the S401 operation for 4 times to obtain the modified SnO coated with 5 layers2A film;
s403: the modified SnO coated with the S4022Putting the glass substrate of the film into a muffle furnace, heating to 450 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature to obtain the modified SnO2A glass sheet of film;
s404: mixing Ag with water1.9Ni0.05Fe2O4Transferring the precursor solution into a reaction kettle, and then plating the modified SnO obtained from S4032Immersing the glass sheet of the film into the precursor solution, reacting at 120 ℃ for 0.5h, cooling to room temperature, and then pulling at a pulling speed of 1mm/sSlowly taking out the solution, drying at 80 deg.C for 10min to obtain Ag coated with 1 layer1.9Ni0.05Fe2O4SnO of thin film2A base glass sheet;
s405: plating the Ag obtained in S4041.9Ni0.05Fe2O4SnO of thin film2Putting the base glass sheet into a muffle furnace, heating to 450 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature along with the furnace to obtain the glass-based laminated SnO2/Ag1.9Ni0.05Fe2O4And (3) compounding the film.
Example 24 SnO2/2Ag1.8Ni0.1Fe2O4
SnO (stannic oxide)2/Ag1.8Ni0.1Fe2O4Preparation method of composite film material, Ag2(1-x)NixFe2O4Wherein x is 0.1, comprising the steps of:
s1: pretreatment of the glass substrate: placing a glass substrate with the specification of 5cm multiplied by 5cm in distilled water, carrying out ultrasonic treatment for 10min, drying, then placing in acetone, carrying out ultrasonic treatment for 20min, drying, then placing in absolute ethyl alcohol, carrying out ultrasonic treatment for 20min, drying, then placing the glass substrate in a mixture of 15 mass percent ammonia water, 25 mass percent hydrogen peroxide and distilled water according to the proportion of 1: 1: 5, carrying out ultrasonic treatment for 60min, and then drying;
s2: preparation of modified SnO2Sol:
s201: preparation of SnO2Sol: adding 22.5mmol stannous chloride dihydrate into 100mL absolute ethyl alcohol at room temperature of 25 ℃, stirring for dissolving, then dropwise adding 10mL 0.1mol/L potassium persulfate solution, magnetically stirring for 6h at 78 ℃, then naturally cooling, standing and aging for 36h for later use to obtain SnO2Sol;
s202: preparation of modified SnO2Sol: nano TiO with the particle size of 5-30 nm in 10mmol2Adding SnO obtained in S2012Magnetically stirring in sol for 1h to obtain modified SnO2Sol;
s3: preparation Ag1.8Ni0.1Fe2O4Precursor solution:
s301: dissolving 9mmol of silver nitrate, 0.5mmol of nickel nitrate hexahydrate and 10mmol of ferric nitrate nonahydrate in 100mL of deionized water at the room temperature of 25 ℃, adding 0.4g of citric acid, and stirring for 15min to obtain a solution A;
s302: at the room temperature of 25 ℃, 5mL of triethanolamine is dropwise added into 25mL of 2mol/L sodium hydroxide solution, and after the triethanolamine is uniformly stirred, solution B is prepared;
s303: slowly dripping the solution B into the solution A for 30min, and magnetically stirring for 1h to obtain Ag1.8Ni0.1Fe2O4Precursor solution;
s4: preparation of SnO2/Ag1.8Ni0.1Fe2O4And (3) composite membrane:
s401: soaking the glass substrate pretreated by S1 in modified SnO2Treating in sol for 10min, slowly taking out at a pulling speed of 1mm/s, drying at 80 deg.C for 10min, and marking as plated modified SnO2Film 1 layer;
s402: repeating the S401 operation for 3 times to obtain the modified SnO coated with 4 layers2A film;
s403: the modified SnO coated with the S4022Putting the glass substrate of the film into a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature to obtain the modified SnO2A glass sheet of film;
s404: mixing Ag with water1.8Ni0.1Fe2O4Transferring the precursor solution into a reaction kettle, and then plating the modified SnO obtained from S4032Immersing the glass sheet of the film into the precursor solution, reacting at 130 ℃ for 1h, cooling to room temperature, slowly taking the glass sheet out of the liquid level at the pulling speed of 1mm/s, drying at 80 ℃ for 10min, and marking as Ag plating1.8Ni0.1Fe2O4Film 1 layer;
s405: repeating the operation S404 for 1 time to obtain the Ag plated with 2 layers1.8Ni0.1Fe2O4SnO of thin film2A base glass sheet;
s406: obtained in S405Plated with Ag1.8Ni0.1Fe2O4SnO of thin film2Putting the base glass sheet into a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature along with the furnace to obtain the glass-based laminated SnO2/Ag1.8Ni0.1Fe2O4And (3) compounding the film.
Example 33 SnO2/3Ag1.4Ni0.3Fe2O4
SnO (stannic oxide)2/Ag1.4Ni0.3Fe2O4Preparation method of composite film material, Ag2(1-x)NixFe2O4Wherein x is 0.3, comprising the steps of:
s1: pretreatment of the glass substrate: placing a glass substrate with the specification of 5cm multiplied by 5cm in distilled water, carrying out ultrasonic treatment for 10min, drying, then placing in acetone, carrying out ultrasonic treatment for 20min, drying, then placing in absolute ethyl alcohol, carrying out ultrasonic treatment for 20min, drying, then placing the glass substrate in a mixture of 15 mass percent ammonia water, 25 mass percent hydrogen peroxide and distilled water according to the proportion of 1: 1: 5, carrying out ultrasonic treatment for 60min, and then drying;
s2: preparation of modified SnO2Sol:
s201: preparation of SnO2Sol: adding 22.5mmol stannous chloride dihydrate into 100mL absolute ethyl alcohol at room temperature of 25 ℃, stirring for dissolving, then dropwise adding 10mL 0.1mol/L potassium persulfate solution, magnetically stirring for 6h at 78 ℃, then naturally cooling, standing and aging for 36h for later use to obtain SnO2Sol;
s202: preparation of modified SnO2Sol: nano TiO with the particle size of 5-30 nm in 10mmol2Adding SnO obtained in S2012Magnetically stirring in sol for 1h to obtain modified SnO2Sol;
s3: preparation of Ag1.4Ni0.3Fe2O4Precursor solution:
s301: dissolving 7mmol of silver nitrate, 1.5mmol of nickel nitrate hexahydrate and 10mmol of ferric nitrate nonahydrate in 100mL of deionized water at the room temperature of 25 ℃, adding 0.4g of citric acid, and stirring for 15min to obtain a solution A;
s302: at the room temperature of 25 ℃, 5mL of triethanolamine is dropwise added into 25mL of 2mol/L sodium hydroxide solution, and after the triethanolamine is uniformly stirred, solution B is prepared;
s303: slowly dropwise adding the solution B into the solution A for 30min, and magnetically stirring for 0.5-1 h to obtain SnO2/Ag1.4Ni0.3Fe2O4Precursor solution;
s4: preparation of SnO2/Ag1.4Ni0.3Fe2O4And (3) composite membrane:
s401: soaking the glass substrate pretreated by S1 in modified SnO2Treating in sol for 10min, slowly taking out at a pulling speed of 1mm/s, drying at 80 deg.C for 10min, and marking as plated modified SnO2Film 1 layer;
s402: repeating the S401 operation for 2 times to obtain the modified SnO coated with 3 layers2A film;
s403: the modified SnO coated with the S4022Putting the glass substrate of the film into a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature to obtain the modified SnO2A glass sheet of film;
s404: mixing Ag with water1.4Ni0.3Fe2O4Transferring the precursor solution into a reaction kettle, and then plating the modified SnO obtained from S4032Immersing the glass sheet of the film into the precursor solution, reacting at 140 ℃ for 1h, cooling to room temperature, slowly taking the glass sheet out of the liquid level at the pulling speed of 1mm/s, drying at 80 ℃ for 10min, and marking as Ag plating1.4Ni0.3Fe2O4Film 1 layer;
s405: repeating the operation S404 for 2 times to obtain the Ag plated with 3 layers1.4Ni0.3Fe2O4SnO of thin film2A base glass sheet;
s406: plating the Ag obtained in S4051.4Ni0.3Fe2O4SnO of thin film2Putting the base glass sheet into a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature along with the furnaceTo obtain the glass-based laminated SnO2/Ag1.4Ni0.3Fe2O4And (3) compounding the film.
Example 42 SnO2/4Ag1.2Ni0.4Fe2O4
SnO (stannic oxide)2/Ag1.2Ni0.4Fe2O4Preparation method of composite film material, Ag2(1-x)NixFe2O4Wherein x is 0.4, comprising the steps of:
s1: pretreatment of the glass substrate: placing a glass substrate with the specification of 5cm multiplied by 5cm in distilled water, carrying out ultrasonic treatment for 10min, drying, then placing in acetone, carrying out ultrasonic treatment for 20min, drying, then placing in absolute ethyl alcohol, carrying out ultrasonic treatment for 20min, drying, then placing the glass substrate in a mixture of 20 mass percent ammonia water, 30 mass percent hydrogen peroxide and distilled water according to the proportion of 1: 1: 5, carrying out ultrasonic treatment for 60min, and then drying;
s2: preparation of modified SnO2Sol:
s201: preparation of SnO2Sol: at room temperature of 25 ℃, adding 25mmol of stannous chloride dihydrate into 100mL of absolute ethyl alcohol, stirring and dissolving, then dropwise adding 10mL of 0.2mol/L potassium persulfate solution, magnetically stirring at 78 ℃ for 6h, then naturally cooling, standing and aging for 36h for later use to obtain SnO2Sol;
s202: preparation of modified SnO2Sol: nano TiO with the particle size of 5-30 nm in 10mmol2Adding SnO obtained in S2012Magnetically stirring in sol for 1h to obtain modified SnO2Sol;
s3: preparation of SnO2/Ag1.2Ni0.4Fe2O4Precursor solution:
s301: dissolving 6mmol of silver nitrate, 2mmol of nickel nitrate hexahydrate and 10mmol of ferric nitrate nonahydrate in 100mL of deionized water at 25 ℃ and room temperature, adding 0.45g of citric acid, and stirring for 15min to obtain a solution A;
s302: at the room temperature of 25 ℃, 5mL of triethanolamine is dropwise added into 25mL of 2mol/L sodium hydroxide solution, and after the triethanolamine is uniformly stirred, solution B is prepared;
s303: slowly dripping the solution B into the solution A for 30min, and magnetically stirring for 0.5-1 h to obtain Ag1.2Ni0.4Fe2O4Precursor solution;
s4: preparation of SnO2/Ag1.2Ni0.4Fe2O4And (3) composite membrane:
s401: soaking the glass substrate pretreated by S1 in modified SnO2Treating in sol for 10min, slowly taking out at a pulling speed of 1mm/s, drying at 80 deg.C for 10min, and marking as plated modified SnO2Film 1 layer;
s402: repeating the S401 operation for 1 time to obtain the modified SnO coated with 2 layers2A film;
s403: the modified SnO coated with the S4022Putting the glass substrate of the film into a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature to obtain the modified SnO2A glass sheet of film;
s404: mixing Ag with water1.2Ni0.4Fe2O4Transferring the precursor solution into a reaction kettle, and then plating the modified SnO obtained from S4032Immersing the glass sheet of the film into the precursor solution, reacting for 1h at 150 ℃, cooling to room temperature, slowly taking the glass sheet out of the liquid level at the pulling speed of 1mm/s, drying for 10min at 80 ℃, and marking as Ag plating1.2Ni0.4Fe2O4Film 1 layer;
s405: repeating the operation S404 for 3 times to obtain the Ag plated with 4 layers1.2Ni0.4Fe2O4SnO of thin film2A base glass sheet;
s406: plating the Ag obtained in S4051.2Ni0.4Fe2O4SnO of thin film2Putting the base glass sheet into a muffle furnace, heating to 500 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature along with the furnace to obtain the glass-based laminated SnO2/Ag1.2Ni0.4Fe2O4And (3) compounding the film.
Example 51 SnO2/5AgNi0.5Fe2O4
SnO (stannic oxide)2/AgNi0.5Fe2O4Method for preparing composite film material, namely Ag2(1-x)NixFe2O4Wherein x is 0.5, comprising the steps of:
s1: pretreatment of the glass substrate: placing a glass substrate with the specification of 5cm multiplied by 5cm in distilled water, carrying out ultrasonic treatment for 10min, drying, then placing in acetone, carrying out ultrasonic treatment for 20min, drying, then placing in absolute ethyl alcohol, carrying out ultrasonic treatment for 20min, drying, then placing the glass substrate in a mixture of 20 mass percent ammonia water, 30 mass percent hydrogen peroxide and distilled water according to the proportion of 1: 1: 5, carrying out ultrasonic treatment for 60min, and then drying;
s2: preparation of modified SnO2Sol:
s201: preparation of SnO2Sol: at room temperature of 25 ℃, adding 25mmol of stannous chloride dihydrate into 100mL of absolute ethyl alcohol, stirring and dissolving, then dropwise adding 10mL of 0.2mol/L potassium persulfate solution, magnetically stirring at 78 ℃ for 6h, then naturally cooling, standing and aging for 36h for later use to obtain SnO2Sol;
s202: preparation of modified SnO2Sol: nano TiO with the particle size of 5-30 nm in 10mmol2Adding SnO obtained in S2012Magnetically stirring in sol for 1h to obtain modified SnO2Sol;
s3: preparation of AgNi0.5Fe2O4Precursor solution:
s301: dissolving 5mmol of silver nitrate, 2.5mmol of nickel nitrate hexahydrate and 10mmol of ferric nitrate nonahydrate in 100mL of deionized water at 25 ℃ at room temperature, adding 0.5g of citric acid, and stirring for 15min to obtain a solution A;
s302: at the room temperature of 25 ℃, 5mL of triethanolamine is dropwise added into 25mL of 2mol/L sodium hydroxide solution, and after the triethanolamine is uniformly stirred, solution B is prepared;
s303: slowly dripping the solution B into the solution A for 30min, and magnetically stirring for 1h to obtain AgNi0.5Fe2O4Precursor solution;
s4: preparation of SnO2/AgNi0.5Fe2O4And (3) composite membrane:
s401: soaking the glass substrate pretreated by S1 in modified SnO2Treating in sol for 10min, slowly taking out at a pulling speed of 1mm/s, drying at 80 deg.C for 10min, and marking as plated modified SnO2Film 1 layer;
s402: the modified SnO coated with the S4012Putting the glass substrate of the film into a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature to obtain the modified SnO2A glass sheet of film;
s403: AgNi0.5Fe2O4Transferring the precursor solution into a reaction kettle, and then plating the modified SnO obtained from S4022Immersing the glass sheet of the film into the precursor solution, reacting at 160 ℃ for 1h, cooling to room temperature, slowly taking the glass sheet out of the liquid level at the pulling speed of 1mm/s, drying at 80 ℃ for 10min, and marking as AgNi plating0.5Fe2O4Film 1 layer;
s404: repeating the operation of S403 for 4 times to obtain the 5-layer-coated AgNi0.5Fe2O4SnO of thin film2A base glass sheet;
s405: the AgNi plated film obtained in S4040.5Fe2O4SnO of thin film2Putting the base glass sheet into a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature along with the furnace to obtain the glass-based laminated SnO2/AgNi0.5Fe2O4And (3) compounding the film.
SnO prepared according to examples 1 to 52/Ag2(1-x)NixFe2O4Composite film material for performance test
Test one: light transmittance test
The light transmittance haze tester used in the first test is a WGT-B type light transmittance haze tester of Shanghai prism technology Limited; adjusting 0 and 100 before testing, then placing the glass sheet plated with the composite film into an instrument for multi-point testing, measuring each glass sheet at 5 points, and finally taking the average value. The final measured transmittance results are shown in table 1.
TABLE 1 composite film transmittance table
| Grouping | Film layer | Transmittance (a) |
| Example 1 | 5SnO2/1Ag1.9Ni0.05Fe2O4 | 89.8 |
| Example 2 | 4SnO2/2Ag1.8Ni0.1Fe2O4 | 82.66 |
| Example 3 | 3SnO2/3Ag1.4Ni0.3Fe2O4 | 81.94 |
| Example 4 | 2SnO2/4Ag1.2Ni0.4Fe2O4 | 76.82 |
| Example 5 | 1SnO2/5AgNi0.5Fe2O4 | 72.16 |
As can be seen from Table 1, from SnO2/Ag2(1-x)NixFe2O4Film layer ratio analysis, when 5 layers of modified SnO are plated2When the film is made, the light transmittance is highest, and 4SnO is secondly2/2Ag1.8Ni0.1Fe2O4And 3SnO2/3Ag1.4Ni0.3Fe2O4From 5SnO of example 12/1Ag1.9Ni0.05Fe2O41SnO to example 52/5AgNi0.5Fe2O4The light transmittance of the composite film is gradually decreased.
And (2) test II: hydrophilicity test
The contact angle measuring instrument used in test two was a JYC-2 type instrument of sovereign instruments ltd; the hydrophilicity test is respectively carried out under the conditions of three light sources of sunlight, ultraviolet light and dark environment, the illumination intensity of the fluorescent lamp is 100Lux, and the radiation intensity of the ultraviolet light is 50 mu W/cm2The test results are shown in table 2:
TABLE 2 contact angle of the composite film with water
As can be seen from Table 2, the effect of the light source on the contact angle of the composite film is not very large, and generally, the composite film has better hydrophilicity under ultraviolet irradiation; nano TiO 22Modified SnO2Film and Ag2(1-x)NixFe2O4The number of the composite layers of the film has a certain influence on the contact angle of the composite film, and the nano TiO is used2Modified SnO2With Ag2(1-x)NixFe2O4The film is prepared by compounding, and single nanometer TiO can be improved2Modified SnO2Or Ag2(1-x)NixFe2O4Hydrophilic property of filmAnd the optimal composite layer ratio of the two is 1: 1, i.e. 3SnO2/3Ag1.4Ni0.3Fe2O4When the hydrophilic property of the composite film is the best.
And (3) test III: photodegradation rate test
The method for testing the photodegradation rate comprises the following steps: firstly, under the dark condition, respectively adding the composite film materials of the embodiments 1-5 into 5 groups of 200ml 50mg/L methylene blue solutions, uniformly stirring, then turning on a 500W xenon lamp light source, enabling visible light with the wavelength of more than 420nm to pass through a visible light filter, irradiating the visible light into a reaction system, sampling and analyzing at 10min, 20min, 40min, 60min, 90min and 100min, measuring the concentration C of the methylene blue in the degradation process, and calculating the light degradation rate of 100% × (C)0-C)/C0，C0At 50mg/L, the results are shown in Table 3:
TABLE 3 photodegradation rates of composite films
As is clear from Table 3, 3SnO of example 32/3Ag1.4Ni0.3Fe2O4The composite film showed the best photodegradation efficiency and the best photocatalytic degradation effect on methylene blue, and 5SnO in example 12/1Ag1.9Ni0.05Fe2O4The worst photodegradation rate of the film indicates that the modified SnO2With Ag2(1-x)NixFe2O4The number of composite layers of the film affects the photocatalytic performance, from 5SnO of example 12/1Ag1.9Ni0.05Fe2O41SnO to example 52/5AgNi0.5Fe2O4The photocatalytic degradation performance of the composite film tends to increase and decrease as a whole.
Examples 1 to 5 preparation of Nano SnO first by Sol-gel method2Sol and further use of nano TiO2Doping modification for improving cured SnO2Photocatalytic and abrasion resistance of the film, and furtherIn-situ growth of nano AgFeO by hydrothermal method2-NiFe2O4Hybrid film of the general formula Ag2(1-x)NixFe2O4And x is 0.05-0.5, a heterojunction structure is constructed, the transfer path of electrons is changed, the photoproduction electrons and holes are transferred along different directions at a heterojunction interface, the number of photoproduction electron-hole pairs is reduced, and the photocatalytic activity and the stability of the composite material are improved; at the same time, Ag2(1-x)NixFe2O4The forbidden band width is less than 1.7eV, the spectral response range to visible light is wide, and the nano SnO2The composite material can effectively improve the sunlight absorption rate and the effective utilization rate, and further improve the photocatalytic performance.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (6)
1. SnO (stannic oxide)2/Ag2(1-x)NixFe2O4The preparation method of the composite film material is characterized in that the Ag is2(1-x)NixFe2O4Wherein x is 0.05-0.5, and the method comprises the following steps:
s1: pretreatment of the glass substrate: placing the glass substrate in distilled water, carrying out ultrasonic treatment for 10min, drying, then placing in acetone, carrying out ultrasonic treatment for 20min, drying, then placing in absolute ethyl alcohol, carrying out ultrasonic treatment for 20min, drying, then placing the glass substrate in a mixture of ammonia water, hydrogen peroxide and distilled water according to a ratio of 1: 1: 5, carrying out ultrasonic treatment for 60min, and then drying;
s2: preparation of modified SnO2Sol:
s201: preparation of SnO2Sol: at the room temperature of 25 ℃, adding stannous chloride dihydrate into absolute ethyl alcohol, stirring and dissolving, and then dropwise adding potassium persulfate solutionMagnetically stirring at 78 deg.C for 6 hr, naturally cooling, standing and aging for 36 hr to obtain SnO2Sol;
s202: preparation of modified SnO2Sol: mixing nanometer TiO2Adding SnO2Magnetically stirring in sol for 1h to obtain modified SnO2Sol;
s3: preparation of Ag2(1-x)NixFe2O4Precursor solution:
s301: dissolving silver nitrate, nickel nitrate hexahydrate and ferric nitrate nonahydrate in deionized water at 25 ℃ and room temperature, adding citric acid, and stirring for 10-15 min to obtain a solution A;
s302: at the room temperature of 25 ℃, dropwise adding triethanolamine into 2mol/L sodium hydroxide solution, and stirring uniformly to prepare solution B;
s303: slowly dripping the solution B into the solution A for 30min, and magnetically stirring for 0.5-1 h to obtain Ag2(1-x)NixFe2O4Precursor solution;
the dosage ratio of the silver nitrate, the nickel nitrate hexahydrate, the ferric nitrate nonahydrate, the deionized water, the citric acid, the sodium hydroxide solution and the triethanolamine is (1-1.9) mmol, (0.05-0.5) mmol, 2mmol, 20mL, (0.05-0.1) g, 5mL and 1 mL;
s4: preparation of SnO2/Ag2(1-x)NixFe2O4And (3) composite membrane:
s401: immersing the pretreated glass substrate S1 in the modified SnO obtained from S22Treating in sol for 10min, slowly taking out at a pulling speed of 1mm/s, drying at 80 deg.C for 10min, and marking as plated modified SnO2Film 1 layer;
s402: repeating S401 for 0-4 times to obtain modified SnO plated with different layers2A film;
s403: the modified SnO coated with the S4022Putting the glass substrate of the film into a muffle furnace, heating to 450-600 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature to obtain the modified SnO2A glass sheet of film;
s404: mixing Ag with water2(1-x)NixFe2O4Precursor bodyTransferring the solution into a reaction kettle, and then plating modified SnO obtained from S4032Immersing the glass sheet of the film into the precursor solution, reacting at 120-160 ℃ for 0.5-1 h, cooling to room temperature, slowly taking the glass sheet out of the liquid level at the pulling speed of 1mm/s, drying at 80 ℃ for 10min, and marking as Ag plating2(1-x)NixFe2O4Film 1 layer;
s405: repeating S404 operation for 0-4 times to obtain Ag plated with different layers2(1-x)NixFe2O4SnO of thin film2A base glass sheet;
s406: plating the Ag obtained in S4052(1-x)NixFe2O4SnO of thin film2Putting the base glass sheet into a muffle furnace, heating to 450-600 ℃ at the speed of 5 ℃/min, calcining at constant temperature for 2h, and cooling to room temperature along with the furnace to obtain the glass-based laminated SnO2/Ag2(1-x)NixFe2O4And (3) compounding the film.
2. A SnO according to claim 12/Ag2(1-x)NixFe2O4The preparation method of the composite film material is characterized in that the mass percentage concentration of the ammonia water is 10-20%.
3. A SnO according to claim 12/Ag2(1-x)NixFe2O4The preparation method of the composite film material is characterized in that the mass percentage concentration of hydrogen peroxide is 20-30%.
4. A SnO according to claim 12/Ag2(1-x)NixFe2O4The preparation method of the composite film material is characterized in that the concentration of the potassium persulfate solution is 0.05-0.2 mol/L.
5. A SnO according to claim 12/Ag2(1-x)NixFe2O4The preparation method of the composite film material is characterized in that,the nano TiO2The particle size of (A) is in the range of 5 to 30 nm.
6. A SnO according to claim 12/Ag2(1-x)NixFe2O4The preparation method of the composite film material is characterized in that the SnO2Film and Ag2(1-x)NixFe2O4The total number of layers of the film was 6.
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