CN112536020A - TiO22Preparation method of-graphene photocatalytic composite film - Google Patents
TiO22Preparation method of-graphene photocatalytic composite film Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 96
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 86
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000000758 substrate Substances 0.000 claims abstract description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000010453 quartz Substances 0.000 claims abstract description 66
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000004140 cleaning Methods 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 238000011282 treatment Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000003980 solgel method Methods 0.000 claims abstract description 8
- 238000004528 spin coating Methods 0.000 claims description 117
- 239000000243 solution Substances 0.000 claims description 104
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000003292 glue Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000007664 blowing Methods 0.000 claims description 12
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000003755 preservative agent Substances 0.000 claims description 6
- 230000002335 preservative effect Effects 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000011941 photocatalyst Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000000861 blow drying Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
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- 239000004408 titanium dioxide Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 239000000975 dye Substances 0.000 abstract description 2
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 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 4
- 238000001816 cooling Methods 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
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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
- 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
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J35/39—
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- B01J35/59—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/26—Organic substances containing nitrogen or phosphorus
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
Abstract
The invention belongs to the technical field of new material preparation, and provides a safe, reliable, simple and feasible TiO2-grapheneThe preparation method of the photocatalytic composite film comprises the steps of cleaning and processing a quartz substrate; preparing a titanium dioxide sol solution by adopting a sol-gel method; TiO22Preparing a film; TiO22Performing high-temperature treatment on the film; TiO22Preparing a graphene oxide film on the surface of the film; reducing the graphene oxide film into a graphene film; after reduction, cleaning and drying to obtain TiO2-graphene composite films. The composite film prepared by the invention has stronger photocatalytic performance, the introduction of the graphene layer can obviously enhance the photocatalytic activity of the film, and the photocatalytic activity is increased along with the increase of the thickness of the graphene layer. TiO is subjected to negative zeta potential on the surface of graphene2The graphene composite film has higher degradation efficiency on cationic dyes and good circulation stability, and can be applied to the fields of photocatalytic degradation of organic pollutants and the like.
Description
Technical Field
The invention belongs to the technical field of new material preparation, and particularly relates to TiO2A preparation method of a graphene photocatalytic composite film.
Background
With the development of human civilization, environmental protection and sustainable development are becoming serious problems in various countries around the world. The photocatalytic reaction is an efficient, safe and environment-friendly environmental purification technology which applies light to a reaction system in the presence of a photocatalyst to decompose organic pollutants in the system into water and carbon dioxide, and the photocatalyst is lossless. Photocatalysis was first initiated by the Japanese scientists Fujishima and Honda et al[5]Found that TiO was found by Fujishima et al in the 70 s of the 20 th century2Semiconductor materials can decompose water through photocatalytic reactions, and scientists have started extensive research in the new field of photocatalysis. TiO22The defects of easy recombination of photogenerated electrons and holes, difficult recovery and the like exist, and the application range of the photogenerated electrons and holes is greatly limited. To widen TiO2The photoresponse range of the method, and the inhibition of photo-generated electron-hole recombination, people adopt various methods to TiO2Modification of materials to enhance TiO2The photocatalytic performance degradation efficiency and the degradation reaction rate.
In 2004, the group of domer and chevrochow, manchester, uk, succeeded in separating a nanosheet consisting of only one layer of carbon atoms, namely Graphene, from highly oriented pyrolytic graphite by a micromechanical exfoliation method. Graphene is the first two-dimensional nano-layered material found by humans. The discovery of graphene breaks through the statement that two-dimensional materials cannot exist stably at normal temperature and pressure, and therefore, Gem et al also obtain the Nobel prize in 2010. With the continuous research of two-dimensional materials, people no longer satisfy the research of single two-dimensional material performance, and researchers compound two-dimensional nano-layered materials with other traditional materials to achieve the enhancement effect. Titanium dioxide is a wide band gap semiconductor material and is widely applied to various fields due to the advantages of good biocompatibility, low price, good chemical stability and the like. Titanium dioxide as a photocatalyst has the advantages of good visible light transmittance, high ultraviolet light absorptivity, good light stability and the like, so that the titanium dioxide has attracted extensive attention in the aspect of photocatalytic degradation of organic dyes. Meanwhile, when titanium dioxide is used as a photocatalyst, the application of titanium dioxide in the aspect of catalytic degradation of organic pollutants is greatly limited due to the defects that photo-generated electrons and holes are easy to recombine, difficult to recover, easy to condense and the like. Therefore, studies on titania-based composites have been initiated to solve the above problems.
Disclosure of Invention
The invention aims to solve the technical problems in the prior stage and provide safe, reliable, simple and feasible TiO2A preparation method of a graphene photocatalytic composite film.
The technical scheme provided by the invention is as follows:
a preparation method of a TiO 2-graphene photocatalytic composite film comprises the following steps:
ultrasonically cleaning and blow-drying a quartz substrate, then placing the quartz substrate into a silane coupling agent solution for treatment, cleaning and blow-drying the quartz substrate again, and then adopting TiO on the quartz substrate2Spin coating sol solution, and after the spin coating is finished, TiO is added2Baking the film on a glue baking machine, and drying the moisture on the surface of the sample; spin-coating dried TiO2Putting the film into a resistance furnace, heating the film in an air atmosphere, and taking out the film; in TiO2Spin-coating a layer of graphene oxide film on the surface of the film, and then reducing the graphene oxide into graphene by adopting a hydriodic acid reduction method;and (4) reducing, cleaning and drying to obtain the composite film.
Further, the ultrasonic cleaning step is as follows: and respectively adopting acetone, absolute ethyl alcohol and deionized water to carry out ultrasonic cleaning on the quartz substrate, wherein the ultrasonic time is at least 10min each time.
Further, the silane coupling agent treatment step comprises: measuring a silane coupling agent KH550, adding the silane coupling agent KH550 into absolute ethyl alcohol, uniformly stirring the mixture by using a glass rod, and then putting a cleaned quartz substrate into a solution for treatment; and after the silane coupling agent is treated, taking out the quartz substrate, repeatedly cleaning the quartz substrate by using absolute ethyl alcohol, and then blowing the quartz substrate to dry for later use.
Further, the TiO2The sol solution is prepared by adopting a sol-gel method and tetrabutyl titanate as a titanium source. TiO22The preparation method of the graphene photocatalytic composite film comprises the following steps:
step one, ultrasonic cleaning is carried out on the quartz substrate by respectively adopting acetone, absolute ethyl alcohol and deionized water, the ultrasonic time is at least 10min each time, and the quartz substrate is dried by blowing for standby after cleaning.
And step two, measuring a silane coupling agent KH550, adding the silane coupling agent KH550 into absolute ethyl alcohol, wherein the volume ratio of the silane coupling agent KH550 to the absolute ethyl alcohol is 1: 5-20, uniformly stirring the mixture by using a glass rod, and then putting the cleaned quartz substrate into a solution for treatment, wherein the treatment time of the silane coupling agent is more than 20 min. And after the silane coupling agent is treated, taking out the quartz substrate, repeatedly cleaning the quartz substrate by using absolute ethyl alcohol, and then blowing the quartz substrate to dry for later use.
And step three, preparing titanium dioxide sol by adopting a sol-gel method and taking tetrabutyl titanate as a titanium source. (a) Firstly, measuring butyl titanate: anhydrous ethanol: and (2) glacial acetic acid is (2-4) 1, the solution is put into a magnetic stirrer and stirred for 10-20min at the speed of 400-1000rpm, and the obtained light yellow transparent solution is marked as solution A. (b) Measuring deionized water: anhydrous ethanol: and (5) (10-20) mixing the solution in the volume ratio of 1, and uniformly stirring the mixture by using a glass rod to obtain a solution B. (c) And slowly dripping the solution B into the solution A at a speed of 1-2 drops per second by using a dropper. (d) Stirring the mixed solution with strong magnetic force at the speed of 1000-3000rpm for 2-4h to obtain a light yellow transparent solution which is the titanium dioxide sol. Pouring the sol into a clean beaker, sealing by a preservative film, and aging for 24h for later use.
Step four, on the quartz substrate, to TiO2And spin-coating the sol solution at the rotation speed of 500-2000rpm for 30-90s, and at the spin-coating speed of 3000-4000rpm for 3 s. After the spin coating is finished, TiO is added2And (5) baking the film on a glue baking machine, and drying the surface moisture of the sample. The baking temperature is 120-150 ℃, and the baking time is 30-60 min.
Step five, spin-coating dried TiO2The film is put into a resistance furnace, the temperature is raised to 400-500 ℃ at the heating rate of 3-5 ℃/min, the heat is preserved for 1-3h, and the film is taken out after being cooled to the room temperature along with the furnace.
Step six, in TiO2And spin-coating a layer of graphene oxide film on the surface of the film, dripping 5-10mg/ml graphene oxide dispersion solution on the surface of the pretreated quartz glass, and enabling the solution to be paved on the surface of the substrate. And then spin-coating the graphene oxide at the spin coating speed of 500-2000rpm, and then spin-coating the excessive solution at the spin coating speed of 2000 rpm. Wherein the spin coating time is 60s, and the spin coating time is 5 s. After the spin coating is finished, the sample is placed on a glue baking machine to be baked for 10min at 120 ℃, and the moisture on the surface of the sample is dried. Reducing graphene oxide into graphene by adopting a 30-45 wt.% hydriodic acid reduction method, cleaning the graphene oxide in deionized water, and baking the graphene oxide for 10min at 120 ℃.
And further, spin-coating the TiO2 solution on the quartz substrate at different spin-coating speeds, and then throwing off the redundant solution at a high spin-coating speed. The spin coating speed is 500 plus 2000rpm, the spin coating time is 10-30s, the spin coating speed after spin coating is 2000 plus 5000rpm, and the spin coating time is 5 s.
Further, in the second step, the quartz substrate is placed in a position with a volume ratio of 1: (5-20) treating the silane coupling agent KH550 with an absolute ethanol solution for more than 20min to ensure that TiO2And more readily have a suitable bond with the quartz substrate.
Further, in step three, it is used for TiO2TiO prepared from-graphene photocatalytic composite film2The concentration of the solution is 2-50 mg/ml, TiO2The concentration of the solution must be greater than 2mg/ml in order to ensure a sufficient amount of TiO per unit area of the quartz substrate2Forming a film layer with proper thickness.
Further, TiO2After the film is spin-coated, TiO is added2The film is baked on a baking machine at the baking temperature of 120 ℃ and 150 ℃ for 30-60 min. With the aim of ensuring the formation of TiO2Drying the film to remove TiO2Moisture in the film layer.
Further, in the fifth step, the dried TiO is coated in a spinning mode2The film is put into a resistance furnace, the temperature rise speed is 3-5 ℃/min, the film is heated to 400-500 ℃, and then the film is insulated for 1-3h, so as to obtain TiO with anatase crystal form2A film.
Further, in the sixth step, 5-10mg/ml of graphene oxide dispersion solution is dripped on the surface of the pretreated quartz substrate, and the solution is paved on the surface of the substrate. And then spin-coating the graphene oxide at the spin coating speed of 500-2000rpm, and then spin-coating the excessive solution at the spin coating speed of 2000 rpm. Wherein the spin coating time is 60s, and the spin coating time is 5 s. After the spin coating is finished, the sample is placed on a glue baking machine and baked for 10min at 120 ℃, so that the moisture in the graphene oxide film is removed.
Further, in the sixth step, the graphene oxide is reduced into graphene by adopting a 30-45 wt.% hydriodic acid reduction method, and the graphene oxide is baked for 10min at 120 ℃ after being cleaned in deionized water, so that the graphene oxide is converted into graphene, the graphene oxide is cleaned to remove redundant hydriodic acid, and finally the composite film is dried.
The technical scheme of the invention has the following beneficial effects:
TiO of the invention2A preparation method of the-graphene photocatalytic composite film, which can realize TiO2The preparation and design of multiple components of the graphene photocatalytic composite film are simple; TiO prepared by the invention2The graphene photocatalytic composite film can be prepared on other substrates, and is expected to be applied to the field of photocatalytic organic matter degradation.
Drawings
FIG. 1 shows TiO prepared in example 22-graphene lightXRD patterns before and after the catalytic composite film hydriodic acid reduction;
FIG. 2 shows TiO prepared in example 22-photocatalytic degradation efficiency curves of graphene composite films for Methylene Blue (MB), Neutral Red (NR) and Methyl Orange (MO);
FIG. 3 shows TiO prepared in example 32Kinetics curves of photocatalytic degradation of graphene composite films on Methylene Blue (MB), Neutral Red (NR) and Methyl Orange (MO).
Detailed Description
The following detailed description of the embodiments of the invention, which is provided as part of the specification and which is intended to illustrate the principles of the invention by way of example, features and advantages of the invention will become apparent from the detailed description.
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination between the specific embodiments.
Example 1
TiO22The preparation method of the graphene photocatalytic composite film comprises the following steps:
step one, ultrasonic cleaning is carried out on the quartz substrate by respectively adopting acetone, absolute ethyl alcohol and deionized water, the ultrasonic time is at least 10min each time, and the quartz substrate is dried by blowing for standby after cleaning.
Measuring a silane coupling agent KH550, and adding the silane coupling agent KH550 into absolute ethyl alcohol, wherein the volume ratio of the silane coupling agent KH550 to the absolute ethyl alcohol is 1: (5-20). The treatment time of the silane coupling agent is more than 20 min. And (4) after uniformly stirring by using a glass rod, putting the cleaned quartz substrate into the solution for treatment. And after the silane coupling agent is treated, taking out the quartz substrate, repeatedly cleaning the quartz substrate by using absolute ethyl alcohol, and then blowing the quartz substrate to dry for later use.
And step three, preparing titanium dioxide sol by adopting a sol-gel method and taking tetrabutyl titanate as a titanium source. (a) Firstly, measuring butyl titanate: anhydrous ethanol: and (2) glacial acetic acid is (2-4) 1, the solution is put into a magnetic stirrer and stirred for 10-20min at the speed of 400-1000rpm, and the obtained light yellow transparent solution is marked as solution A. (b) Measuring deionized water: anhydrous ethanol: and (5) (10-20) mixing the solution in the volume ratio of 1, and uniformly stirring the mixture by using a glass rod to obtain a solution B. (c) And slowly dripping the solution B into the solution A at a speed of 1-2 drops per second by using a dropper. (d) Stirring the mixed solution with strong magnetic force at the speed of 1000-3000rpm for 2-4h to obtain a light yellow transparent solution which is the titanium dioxide sol. Pouring the sol into a clean beaker, sealing by a preservative film, and aging for 24h for later use.
Step four, on the quartz substrate, TiO is coated at different glue-homogenizing speeds2And spin-coating the sol solution, and then throwing off redundant solution at a high spin-coating speed. The spin coating speed is 500 plus 2000rpm, the spin coating time is 30-90s, the spin coating speed after spin coating is 3000 plus 4000rpm, and the spin coating time is 3 s. After the spin coating is finished, TiO is added2And (5) baking the film on a glue baking machine, and drying the surface moisture of the sample. The baking temperature is 120-150 ℃, and the baking time is 30-60 min.
Step five, spin-coating dried TiO2The film is put into a resistance furnace and heated in the air atmosphere, the temperature is raised to 400-500 ℃ at the temperature rise speed of 3-5 ℃/min, then the heat is preserved for 1-3h, the film is taken out after being cooled to the room temperature along with the furnace, and the TiO with the anatase crystal form is obtained2The film is then removed.
Step six, in TiO2And spin-coating a layer of graphene oxide film on the surface of the film, and then reducing the graphene oxide into graphene by adopting a hydriodic acid reduction method. 5-10mg/ml of graphene oxide dispersion solution is dripped on the surface of the pretreated quartz glass, and the solution is paved on the surface of the substrate. And then spin-coating the graphene oxide at the spin coating speed of 500-2000rpm, and then spin-coating the excessive solution at the spin coating speed of 2000 rpm. Wherein the spin coating time is 60s, and the spin coating time is 5 s. And after the spin coating is finished, the sample is placed on a glue baking machine to be baked for 10min at 120 ℃, and the moisture on the surface of the sample is dried, so that the composite film can be obtained.
Further, in the second step, the quartz substrate is placed in a position with a volume ratio of 1: (5-20) treating the silane coupling agent KH550 with an absolute ethanol solution for more than 20min to ensure that TiO2And more readily have a suitable bond with the quartz substrate.
Further, in step three, it is used for TiO2-preparation of graphene photocatalytic composite filmTiO2The concentration of the solution is 2-50 mg/ml, TiO2The concentration of the solution must be greater than 2mg/ml in order to ensure a sufficient amount of TiO per unit area of the quartz substrate2Forming a film layer with proper thickness.
Further, TiO2After the film is spin-coated, TiO is added2The film is baked on a baking machine at the baking temperature of 120 ℃ and 150 ℃ for 30-60 min. With the aim of ensuring the formation of TiO2Drying the film to remove TiO2Moisture in the film layer.
Further, in the fifth step, the dried TiO is coated in a spinning mode2The film is put into a resistance furnace, the temperature rise speed is 3-5 ℃/min, the film is heated to 400-500 ℃, and then the film is insulated for 1-3h, so as to obtain TiO with anatase crystal form2A film.
Further, in the sixth step, 5-10mg/ml of graphene oxide dispersion solution is dripped on the surface of the pretreated quartz substrate, and the solution is paved on the surface of the substrate. And then spin-coating the graphene oxide at the spin coating speed of 500-2000rpm, and then spin-coating the excessive solution at the spin coating speed of 2000 rpm. Wherein the spin coating time is 60s, and the spin coating time is 5 s. After the spin coating is finished, the sample is placed on a glue baking machine and baked for 10min at 120 ℃, so that the moisture in the graphene oxide film is removed.
Further, in the sixth step, the graphene oxide is reduced into graphene by adopting a 30-45 wt.% hydriodic acid reduction method, and the graphene oxide is baked for 10min at 120 ℃ after being cleaned in deionized water, so that the graphene oxide is converted into graphene, the graphene oxide is cleaned to remove redundant hydriodic acid, and finally the composite film is dried.
Example 2
TiO22The preparation method of the graphene photocatalytic composite film is characterized by comprising the following steps of:
step one, ultrasonic cleaning is carried out on the quartz substrate by respectively adopting acetone, absolute ethyl alcohol and deionized water, the ultrasonic time is at least 10min each time, and the quartz substrate is dried by blowing for standby after cleaning.
Step two, measuring a silane coupling agent KH550, adding the silane coupling agent KH550 into absolute ethyl alcohol, wherein the volume ratio of the silane coupling agent KH550 to the absolute ethyl alcohol is 1: 10, uniformly stirring the mixture by using a glass rod, and then putting the cleaned quartz substrate into a solution for treatment, wherein the treatment time of the silane coupling agent is more than 20 min. And after the silane coupling agent is treated, taking out the quartz substrate, repeatedly cleaning the quartz substrate by using absolute ethyl alcohol, and then blowing the quartz substrate to dry for later use.
And step three, preparing titanium dioxide sol by adopting a sol-gel method and taking tetrabutyl titanate as a titanium source. (a) Firstly, measuring butyl titanate: anhydrous ethanol: glacial acetic acid is a 2:3:1 volume ratio solution, the solution is placed into a magnetic stirrer and stirred at 1000rpm for 10min, and the resulting pale yellow transparent solution is designated as solution a. (b) Measuring deionized water: anhydrous ethanol: a solution of 5:15:1 by volume nitric acid was stirred uniformly with a glass rod to obtain solution B. (c) And slowly dripping the solution B into the solution A at a speed of 1-2 drops per second by using a dropper. (d) Stirring the mixed solution with strong magnetic force at the speed of 2000rpm for 2-4h to obtain a light yellow transparent solution, namely the titanium dioxide sol. Pouring the sol into a clean beaker, sealing by a preservative film, and aging for 24h for later use.
Step four, on the quartz substrate, to TiO2Spin coating is carried out on the sol solution, the rotation speed of the spin coating is 1500rpm, the spin coating time is 60s, the spin coating speed is 4000rpm after the spin coating, and the spin coating time is 3 s. After the spin coating is finished, TiO is added2And (5) baking the film on a glue baking machine, and drying the surface moisture of the sample. The baking temperature is 120 deg.C, and the baking time is 60 min.
Step five, spin-coating dried TiO2And (3) putting the film into a resistance furnace, raising the temperature to 450 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, cooling the film to room temperature along with the furnace, and taking out the film.
Step six, in TiO2And spin-coating a layer of graphene oxide film on the surface of the film, dripping 5mg/ml graphene oxide dispersion solution on the surface of the pretreated quartz substrate, and enabling the solution to be paved on the surface of the substrate. Subsequently, spin-coating the graphene oxide at a spin-coating speed of 1000rpm, and then throwing off the excessive solution at a spin-coating speed of 2000 rpm. Wherein the spin coating time is 60s, and the spin coating time is 5 s. After the spin coating is finished, the sample is placed on a glue baking machine to be baked for 10min at 120 ℃, and the moisture on the surface of the sample is dried. Reducing graphene oxide to graphene by adopting 45 wt.% hydriodic acid reduction method, and adding deionized waterAfter washing, baking at 120 ℃ for 10 min.
Example 3
TiO22The preparation method of the graphene photocatalytic composite film is characterized by comprising the following steps of:
step one, ultrasonic cleaning is carried out on the quartz substrate by respectively adopting acetone, absolute ethyl alcohol and deionized water, the ultrasonic time is at least 10min each time, and the quartz substrate is dried by blowing for standby after cleaning.
Measuring a silane coupling agent KH550, and adding the silane coupling agent KH550 into absolute ethyl alcohol, wherein the volume ratio of the silane coupling agent KH550 to the absolute ethyl alcohol is 1: and 15, uniformly stirring by using a glass rod, and then putting the cleaned quartz substrate into the solution for treatment, wherein the treatment time of the silane coupling agent is more than 20 min. And after the silane coupling agent is treated, taking out the quartz substrate, repeatedly cleaning the quartz substrate by using absolute ethyl alcohol, and then blowing the quartz substrate to dry for later use.
And step three, preparing titanium dioxide sol by adopting a sol-gel method and taking tetrabutyl titanate as a titanium source. (a) Firstly, measuring butyl titanate: anhydrous ethanol: glacial acetic acid is a 2:4:1 volume ratio solution, the solution is placed into a magnetic stirrer and stirred at 500rpm for 20min, and the resulting pale yellow transparent solution is designated as solution A. (b) Measuring deionized water: anhydrous ethanol: the solution was stirred uniformly with a glass rod at a volume ratio of 5:10:1 nitric acid to give solution B. (c) And slowly dripping the solution B into the solution A at a speed of 1-2 drops per second by using a dropper. (d) Stirring the mixed solution for 4h at 3000rpm under strong magnetic force to obtain a light yellow transparent solution, namely the titanium dioxide sol. Pouring the sol into a clean beaker, sealing by a preservative film, and aging for 24h for later use.
Step four, on the quartz substrate, to TiO2Spin coating is carried out on the sol solution, the rotation speed of the spin coating is 1000rpm, the spin coating time is 90s, the spin coating speed is 4000rpm after the spin coating, and the spin coating time is 3 s. After the spin coating is finished, TiO is added2And (5) baking the film on a glue baking machine, and drying the surface moisture of the sample. The baking temperature is 150 deg.C, and the baking time is 30 min.
Step five, spin-coating dried TiO2Placing the film into a resistance furnace, heating to 500 deg.C at a heating rate of 3 deg.C/min, maintaining for 1h, cooling to room temperature, and cooling to obtain the final productAnd (4) taking out the film.
Step six, in TiO2And spin-coating a layer of graphene oxide film on the surface of the film, dripping 10mg/ml graphene oxide dispersion solution on the surface of the pretreated quartz glass, and enabling the solution to be paved on the surface of the substrate. Subsequently, spin-coating the graphene oxide at a spin-coating speed of 2000rpm, and then throwing off the excessive solution at a spin-coating speed of 2000 rpm. Wherein the spin coating time is 60s, and the spin coating time is 5 s. After the spin coating is finished, the sample is placed on a glue baking machine to be baked for 10min at 120 ℃, and the moisture on the surface of the sample is dried. And reducing the graphene oxide into graphene by adopting a 35 wt.% hydriodic acid reduction method, cleaning the graphene oxide in deionized water, and baking the graphene oxide for 10min at 120 ℃.
Example 4
TiO22The preparation method of the graphene photocatalytic composite film is characterized by comprising the following steps of:
step one, ultrasonic cleaning is carried out on the quartz substrate by respectively adopting acetone, absolute ethyl alcohol and deionized water, the ultrasonic time is at least 10min each time, and the quartz substrate is dried by blowing for standby after cleaning.
And step two, measuring a silane coupling agent KH550, adding the silane coupling agent KH550 into absolute ethyl alcohol, wherein the volume ratio of the silane coupling agent KH550 to the absolute ethyl alcohol is 1:20, uniformly stirring the mixture by using a glass rod, and then putting the cleaned quartz substrate into a solution for treatment, wherein the treatment time of the silane coupling agent is more than 20 min. And after the silane coupling agent is treated, taking out the quartz substrate, repeatedly cleaning the quartz substrate by using absolute ethyl alcohol, and then blowing the quartz substrate to dry for later use.
And step three, preparing titanium dioxide sol by adopting a sol-gel method and taking tetrabutyl titanate as a titanium source. (a) Firstly, measuring butyl titanate: anhydrous ethanol: glacial acetic acid is a 2:2:1 volume ratio solution, the solution is placed into a magnetic stirrer and stirred at 400rpm for 20min, and the resulting pale yellow transparent solution is designated as solution A. (b) Measuring deionized water: anhydrous ethanol: the solution was stirred uniformly with a glass rod at a volume ratio of 5:20:1 nitric acid to give solution B. (c) And slowly dripping the solution B into the solution A at a speed of 1-2 drops per second by using a dropper. (d) Stirring the mixed solution for 4h at the speed of 1000rpm by strong magnetic force to obtain a light yellow transparent solution which is the titanium dioxide sol. Pouring the sol into a clean beaker, sealing by a preservative film, and aging for 24h for later use.
Step four, on the quartz substrate, to TiO2And spin-coating the sol solution, wherein the spin speed of the spin-coating is 1200rpm, the spin-coating time is 60s, the spin-coating speed after the spin-coating is 3500rpm, and the spin-coating time is 3 s. After the spin coating is finished, TiO is added2And (5) baking the film on a glue baking machine, and drying the surface moisture of the sample. The baking temperature is 140 deg.C, and the baking time is 45 min.
Step five, spin-coating dried TiO2And (3) putting the film into a resistance furnace, heating to 480 ℃ at a heating speed of 4 ℃/min, preserving the heat for 2h, cooling to room temperature along with the furnace, and taking out the film.
Step six, in TiO2And spin-coating a layer of graphene oxide film on the surface of the film, dripping 8mg/ml graphene oxide dispersion solution on the surface of the pretreated quartz substrate, and enabling the solution to be paved on the surface of the substrate. Subsequently, the graphene oxide is spin-coated at a spin-coating speed of 1200rpm, and after the spin-coating, the excess solution is spun off at a spin-coating speed of 2000 rpm. Wherein the spin coating time is 60s, and the spin coating time is 5 s. After the spin coating is finished, the sample is placed on a glue baking machine to be baked for 10min at 120 ℃, and the moisture on the surface of the sample is dried. And reducing the graphene oxide into graphene by adopting a 30 wt.% hydriodic acid reduction method, cleaning the graphene oxide in deionized water, and baking the graphene oxide for 10min at 120 ℃.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modifications of the above embodiments according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. TiO22The preparation method of the graphene photocatalytic composite film is characterized by comprising the following steps of:
ultrasonically cleaning and blow-drying a quartz substrate, then placing the quartz substrate into a silane coupling agent solution for treatment, cleaning and blow-drying the quartz substrate again, and then adopting TiO on the quartz substrate2Spin coating sol solution, and after the spin coating is finished, TiO is added2Baking the film on a glue baking machine, and drying the moisture on the surface of the sample; spin-coating dried TiO2Placing the film in a resistance furnace, heating in air atmosphere, and taking out the filmDischarging; in TiO2Spin-coating a layer of graphene oxide film on the surface of the film, and then reducing the graphene oxide into graphene by adopting a hydriodic acid reduction method; and (4) reducing, cleaning and drying to obtain the composite film.
2. The TiO of claim 12The preparation method of the graphene photocatalytic composite film is characterized by comprising the following steps of: and respectively adopting acetone, absolute ethyl alcohol and deionized water to carry out ultrasonic cleaning on the quartz substrate, wherein the ultrasonic time is at least 10min each time.
3. The method for preparing the TiO 2-graphene photocatalytic composite film according to claim 1, wherein the silane coupling agent treatment step comprises: measuring a silane coupling agent KH550, adding the silane coupling agent KH550 into absolute ethyl alcohol, uniformly stirring the mixture by using a glass rod, and then putting a cleaned quartz substrate into a solution for treatment; and after the silane coupling agent is treated, taking out the quartz substrate, repeatedly cleaning the quartz substrate by using absolute ethyl alcohol, and then blowing the quartz substrate to dry for later use.
4. The TiO of claim 12-method for preparing a photocatalytic graphene composite film, characterized in that said TiO is2The sol solution is prepared by adopting a sol-gel method and tetrabutyl titanate as a titanium source.
5. A TiO according to claim 32The preparation method of the graphene photocatalytic composite film is characterized in that the volume ratio of the silane coupling agent KH550 to the absolute ethyl alcohol is 1: (5-20); the treatment time of the silane coupling agent is more than 20 min.
6. A TiO according to claim 12The preparation method of the graphene photocatalytic composite film is characterized by comprising the following steps of: (a) firstly, measuring butyl titanate: anhydrous ethanol: the glacial acetic acid is 2 (2-4) and the solution with the volume ratio of 1 is put into a magnetic stirrer and stirred for 10-20min at the speed of 400 plus 1000rpm to obtain a light yellow transparent solutionMarking as a solution A; (b) measuring deionized water: anhydrous ethanol: the nitric acid is (10-20) 1 volume ratio of the solution, and the solution B is obtained after the solution is uniformly stirred by a glass rod; (c) and slowly dripping the solution B into the solution A at a speed of 1-2 drops per second by using a dropper. (d) Stirring the mixed solution for 2-4h at the speed of 1000-; pouring the sol into a clean beaker, sealing by a preservative film, and aging for 24h for later use.
7. A TiO according to claim 12The preparation method of the graphene photocatalytic composite film is characterized in that the spin coating speed is 500-2000rpm, the spin coating time is 30-90s, the spin coating speed after spin coating is 3000-4000rpm, and the spin coating time is 3 s.
8. A TiO according to claim 12The preparation method of the-graphene photocatalytic composite film is characterized in that TiO is added after the spin coating is finished2Baking the film on a glue baking machine, and drying the moisture on the surface of the sample; the baking temperature is 120-150 ℃, and the baking time is 30-60 min.
9. A TiO according to claim 12The preparation method of the-graphene photocatalytic composite film is characterized in that dried TiO is spin-coated2The film is put into a resistance furnace, the temperature rise speed is 3-5 ℃/min, the film is heated to 400-500 ℃, the heat preservation is carried out for 1-3h, the film is taken out after the film is cooled to the room temperature along with the furnace, and the TiO with the anatase crystal form is obtained2A film.
10. A TiO according to claim 12The preparation method of the-graphene photocatalytic composite film is characterized in that the TiO photocatalyst is prepared from TiO2The method for spin-coating a layer of graphene oxide film on the surface of the film comprises the following steps: dripping 5-10mg/ml graphene oxide dispersion solution on the surface of the pretreated quartz substrate and enabling the solution to be paved on the surface of the substrate; subsequently, spin-coating the graphene oxide at the spin-coating speed of 500-2000rpm, and then throwing off the redundant solution at the spin-coating speed of 2000 rpm; the spin coating time is 60s, and the spin coating time is 5 s; after the spin coating is finished, the coating solution is sprayed on the surface of the substrateAnd (3) baking the sample on a glue baking machine at 120 ℃ for 10min, and drying the surface moisture of the sample.
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