CN117065739A - GO/TiO 2 Composite catalyst and preparation method thereof - Google Patents
GO/TiO 2 Composite catalyst and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 49
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 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 claims description 18
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 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 claims description 14
- 229940012189 methyl orange Drugs 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 238000002835 absorbance Methods 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 239000011265 semifinished product Substances 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000011160 research Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 abstract description 7
- 230000006872 improvement Effects 0.000 abstract description 5
- 239000011943 nanocatalyst Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
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- 238000005054 agglomeration Methods 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
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- 239000006228 supernatant Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
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Classifications
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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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Thermal Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Catalysts (AREA)
Abstract
The invention provides a GO/TiO 2 The preparation method of the composite catalyst comprises the following steps: s1: preparation of GO, tiO 2 A certain amount of GO and TiO 2 Mixing with deionized water; s2: the sample obtained by S1 is subjected to ultrasonic treatment, stirred and reacted for 12 hours at 180 ℃ in a polytetrafluoroethylene hydrothermal reaction kettle; s3: after the completion, cooling to room temperature, washing the sample, drying at room temperature and the like to finally obtain the GO/TiO 2 A composite material. The book is provided withThe invention provides GO/TiO 2 GO/TiO prepared by composite catalyst preparation method 2 The composite material realizes the improvement of the photocatalytic activity of dye wastewater, and the GO/TiO 2 The adsorption performance of the composite material is also improved, and the technical scheme provided by the invention lays a foundation for further reasonably designing the efficient doped nano catalyst.
Description
Technical Field
The invention relates to the technical field of preparation of doped nano-crystal catalysts, in particular to a GO/TiO 2 A composite catalyst and a preparation method thereof.
Background
Along with the improvement of the living standard of people, the industrialization process is accelerated, so that the water pollution problem is severe, the organic pollutant content of the dye wastewater is high, the components are complex, the biotoxicity is high, the difficulty of treating the dye wastewater is further increased, and the water pollution crisis is solved.
Various methods have been developed to treat dye wastewater, including mainly physical, chemical and biological methods. The physical method mainly adopts an adsorption method, and the method is simple and effective, but has the defects of large adsorbent consumption and high cost in the treatment process. The biological method mainly utilizes microorganisms to degrade dye molecules in water, and the method is environment-friendly, free of secondary pollution, good in effect and long in time consumption. In recent years, photocatalytic technology in chemical processes has been advanced to treat dye wastewater. Photocatalytic technology is capable of utilizing semiconductor materials to absorb light and generate strong oxidants, thereby facilitating degradation of dye molecules.
Photocatalysis has achieved great success as the dominant technology for current air purification and sewage treatment. The photocatalyst firstly absorbs the energy of light, is stimulated and activated to generate electrons and holes which participate in redox reaction, and in the process, the organic polymer is cracked into inorganic small molecules, the electrons and the holes are recombined, and the photocatalyst is restored to a stable state.
TiO 2 As a popular photocatalytic material, the material has the advantages of stable performance, no environmental damage, no toxicity, no secondary pollution and the like, and is widely applied to photosensitive materialsMaterials, photocatalysts, etc., and is advantageous over other processes in treating water pollution problems. But TiO 2 The material has the problems of high surface energy, strong polarity, easy agglomeration, easy recombination of photo-generated electrons and holes, low visible light utilization rate and the like, and severely limits the application of the material in practical production and service life.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, the object of the present invention is to prepare GO/TiO 2 The composite catalyst realizes the improvement of the photocatalytic activity of the dye wastewater and researches the GO/TiO 2 Adsorption performance of the composite catalyst.
To achieve the above object, the present invention provides a GO/TiO 2 The preparation method of the composite catalyst comprises the following steps:
s1: preparation of GO, tiO 2 A certain amount of GO and TiO 2 Mixing with deionized water;
s2: the sample obtained by S1 is subjected to ultrasonic treatment, stirred and reacted for 12 hours at 180 ℃ in a polytetrafluoroethylene hydrothermal reaction kettle;
s3: after the completion, cooling to room temperature, washing the sample, drying at room temperature and the like to finally obtain the GO/TiO 2 A composite material.
In some embodiments, the preparation method of GO in S1 includes the following steps:
step one: slowly adding sulfuric acid solution into graphite and NaNO 3 Stirring under ice bath conditions;
step two: slowly adding proper amount of potassium permanganate into beaker, reacting at room temperature, adding proper amount of deionized water, continuing the reaction, stopping heating, gradually cooling to about 60deg.C, and adding proper amount of H 2 O 2 After the temperature of the solution is reduced to room temperature, sealing the solution by using a sealing film;
step three: and (3) centrifugally separating the graphene mixed solution obtained in the step (II), washing, freeze-drying, grinding, and sieving to obtain GO powder.
Wherein, in the first step, the stirring time is 30min.
And in the second step, a proper amount of potassium permanganate is slowly added into a beaker, the reaction is carried out for 2 hours at room temperature, a proper amount of deionized water is added, the reaction is continued for 1 hour at 95 ℃, and the heating is stopped.
In some of these embodiments, the TiO in S1 2 The preparation method of the (C) comprises the following steps:
step one: adding absolute ethyl alcohol and butyl titanate into a beaker for reaction, stirring at room temperature, and adding glacial acetic acid to obtain a solution A;
step two: stirring the solution A for 15min until the color becomes transparent, adding NH into the solution A 4 NO 3 Distilled water and absolute ethyl alcohol to obtain a solution C;
step three: adding the solution C into the solution B, regulating pH, reacting to form gel state, standing the semi-finished product at room temperature, centrifuging with a centrifuge, washing with deionized water for multiple times until neutral, and calcining to obtain pure white TiO 2 And (3) powder.
Wherein, in the first step, the stirring time is 15min.
Wherein, in the third step, the following steps are specific: adding the solution C into the solution B, regulating pH, reacting at 40deg.C for 30min to form gel state, standing the semi-finished product at room temperature for 12 hr, centrifuging with a centrifuge, washing with deionized water for multiple times until neutral, and calcining at 300deg.C for 3 hr to obtain pure white TiO 2 And (3) powder.
The invention also provides a GO/TiO 2 Composite catalyst, GO/TiO as described above 2 The preparation method of the composite catalyst is used for preparing the catalyst.
The invention further provides a GO/TiO 2 The application of the composite catalyst to the research of the photocatalytic performance of MO (methyl orange) is characterized in that: at different times, GO/TiO 2 Influence of the composite on the change in MO absorbance.
The invention also provides a GO/TiO 2 The application of the composite catalyst to MB (methylene blue) adsorption is characterized in that: the specific reaction conditions are as follows: GO/TiO 2 The composite material and MB are evenly mixed and then are placed in a cuvette, and the cuvette is placed in ultravioletIn a spectrophotometer, GO/TiO is reflected by the change of absorbance 2 Adsorption capacity of composite materials for MB.
Compared with the prior art, the invention has the following advantages:
the GO/TiO provided by the invention 2 GO/TiO prepared by composite catalyst preparation method 2 The composite material realizes the improvement of the photocatalytic activity of dye wastewater, and the GO/TiO 2 The adsorption performance of the composite material is also improved, and the technical scheme provided by the invention lays a foundation for further reasonably designing the efficient doped nano catalyst.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 (a) is an SEM image of GO prepared in example 1 of the invention;
FIG. 1 (b) shows TiO according to example 2 of the present invention 2 SEM images of (a);
FIG. 1 (c) shows GO/TiO as prepared in example 3 of the present invention 2 SEM images of the composite;
FIG. 2 (d) is an XRD pattern of GO prepared in example 1 of the present invention;
FIG. 2 (e) shows TiO's prepared in examples 2 and 3 of the present invention 2 And GO/TiO 2 XRD pattern of the composite catalyst;
FIG. 3 (a) shows GO/TiO according to an embodiment of the present invention 2 A relation chart of degradation rate and time of the photocatalytic MO of the composite catalyst;
FIG. 3 (b) shows GO/TiO as an example of the present invention 2 And (3) an adsorption amount and temperature relation chart of the MB adsorbed by the composite catalyst.
Detailed Description
The following detailed description of the present invention is provided with reference to the accompanying drawings and specific embodiments, so as to further understand the purpose, the scheme and the effects of the present invention, but not to limit the scope of the appended claims.
The embodiment of the invention provides a GO/TiO 2 The preparation method of the composite catalyst comprises the following steps:
s1: preparation of GO, tiO 2 A certain amount of GO and TiO 2 Mixing with deionized water;
s2: the sample obtained by S1 is subjected to ultrasonic treatment, stirred and reacted for 12 hours at 180 ℃ in a polytetrafluoroethylene hydrothermal reaction kettle;
s3: after the completion, cooling to room temperature, washing the sample, drying at room temperature and the like to finally obtain the GO/TiO 2 A composite material.
The preparation method of the GO in the S1 comprises the following steps:
step one: slowly adding sulfuric acid solution into graphite and NaNO 3 Stirring under ice bath conditions;
step two: slowly adding proper amount of potassium permanganate into beaker, reacting at room temperature, adding proper amount of deionized water, continuing the reaction, stopping heating, gradually cooling to about 60deg.C, and adding proper amount of H 2 O 2 After the temperature of the solution is reduced to room temperature, sealing the solution by using a sealing film;
step three: and (3) centrifugally separating the graphene mixed solution obtained in the step (II), washing, freeze-drying, grinding, and sieving to obtain GO powder.
Specifically, in the first step, the stirring time is 30min.
Specifically, in the second step, a proper amount of potassium permanganate is slowly added into a beaker, the reaction is carried out for 2 hours at room temperature, a proper amount of deionized water is added, the reaction is continued for 1 hour at 95 ℃, and the heating is stopped.
The GO prepared in this example is in a sheet structure, and the surface of the sheet has wrinkles.
Wherein, tiO in S1 2 The preparation method of the (C) comprises the following steps:
step one: adding absolute ethyl alcohol and butyl titanate into a beaker for reaction, stirring at room temperature, and adding glacial acetic acid to obtain a solution A;
step two: stirring the solution A for 15min until the color becomes transparent, adding NH into the solution A 4 NO 3 Distilled water and absolute ethyl alcohol to obtain a solution C;
step three: adding the solution C into the solution B, regulating pH, reacting to form gel state, standing the semi-finished product at room temperature, centrifuging with a centrifuge, washing with deionized water for multiple times until neutral, and calcining to obtain pure white TiO 2 And (3) powder.
Specifically, in the first step, the stirring time is 15min.
The third step is specifically: adding the solution C into the solution B, regulating pH, reacting at 40deg.C for 30min to form gel state, standing the semi-finished product at room temperature for 12 hr, centrifuging with a centrifuge, washing with deionized water for multiple times until neutral, and calcining at 300deg.C for 3 hr to obtain pure white TiO 2 And (3) powder. TiO prepared in this example 2 Is in a spherical particle structure and has obvious agglomeration phenomenon.
Another embodiment of the present invention provides a GO/TiO 2 Composite catalyst, GO/TiO as described above 2 The preparation method of the composite catalyst is used for preparing the catalyst.
Another embodiment of the present invention provides a GO/TiO 2 Application of composite catalyst to research on photocatalytic performance of MO (methyl orange), and GO/TiO under different time 2 The influence of the composite material on the MO absorbance change can be as follows: and carrying out catalytic reaction for 9h under ultraviolet irradiation.
Another embodiment of the present invention provides a GO/TiO 2 The application of the composite catalyst to MB (methylene blue) adsorption is characterized in that: the specific reaction conditions are as follows: GO/TiO 2 The composite material and MB are evenly mixed and then are placed in a cuvette, the cuvette is placed in an ultraviolet spectrophotometer, and the GO/TiO is reflected by the change of absorbance 2 Adsorption capacity of composite materials for MB. Specific processing conditions may be: oscillating at 25deg.C for 12h, 35 deg.C for 12h, and 45 deg.C for 12h. 1% GO/TiO in the present invention 2 The adsorption performance of the composite material is best, and the reaction temperature is 25 ℃.
The embodiment provided by the invention adopts a modified mode to treat TiO 2 Is optimized by using Graphene (GO) and TiO 2 Compounding to improve photocatalytic performance, GO is a hexagonal two-dimensional honeycomb carbon material formed by closely stacking single-layer carbon atoms, and has been widely used in the fields of photocatalysis, micro-nano sensors, and the like. Graphene has the excellent properties of large specific surface area, excellent conductivity, easy control of doping modified energy, stronger light absorption capacity and the like. Due to the advantages of large specific surface area and two-dimensional lamellar structure, the doped GO is beneficial to controlling the energy band, the reaction area is increased, the light absorption performance is improved, and the light absorption range is enlarged. The accumulation of chemical bonds between organic pollutants and aromatic graphene rings promotes the adsorption performance of the photocatalyst on the pollutants, and enhances the pollutant removal effect. With high conductivity of GO, GO and TiO 2 After combination, the photo-generated electron and the photo-generator cavity can be prolonged, the photo-catalytic activity can be improved, and the TiO can be regulated 2 And therefore GO is TiO 2 A potential support for the photocatalyst.
The invention further carries out XRD and SEM characterization on the prepared GO, carries out XRD and SEM characterization on the prepared TiO2, and carries out XRD and SEM characterization on the prepared GO/TiO2 composite catalyst.
Example 1
Firstly, 5.0g of graphite and 3.0g of NaNO are weighed 3 In a 1000mL beaker, 120.0mL of sulfuric acid was measured and added to the 1000mL beaker, and stirred for 30min under ice bath conditions. Weighing 20.0g of potassium permanganate, slowly adding into a 1000mL beaker, reacting at room temperature for 2H, adding 600mL of deionized water, heating to 95 ℃ for continuous reaction for 1H, stopping heating, gradually reducing the temperature to about 60 ℃, and adding 15mL of 30% H 2 O 2 After the temperature of the solution is reduced to room temperature, sealing the solution by using a sealing film; centrifuging the obtained graphene mixed solution at 1000rpm/min for 5min, pouring out supernatant, washing with 5% HCl for three times, and removing SO 4 2- Washing with deionized water, centrifuging to neutrality, lyophilizing the lower precipitate, grinding, and sieving to obtain GO powder.
SEM and XRD characterization of the prepared GO
Example 2
In a 200mL beaker, 40.0mL of absolute ethyl alcohol and 15.0mL of butyl titanate are added for reaction, and after stirring for 15min at room temperature, 6.0mL of glacial acetic acid is added into the beaker to obtain a solution A. Stirring solution A for 15min until the color becomes transparent, adding 3.4. 3.4gNH to solution A 4 NO 3 12mL of distilled water and 10mL of absolute ethanol gave solution C. Solution C was added to solution B, adjusting ph=4.0. The reaction was carried out at 40℃for 30min to form a gel state. Placing the semi-finished product at room temperature for 12h, centrifuging with a centrifuge, washing with deionized water for multiple times until neutral, and calcining at 300 ℃ for 3h to obtain pure white TiO 2 And (3) powder.
For the prepared TiO 2 Catalyst SEM, XRD characterization
Example 3
Firstly, five parts of 20.0mg of prepared TiO are weighed 2 Adding 1.0mg, 2.0mg, 10.0mg, 15.0mg GO (GO amounts are respectively TiO) 2 0.5%, 1%, 5%, 7.5%) of (A) were placed in 50mL beakers, 30mL of deionized water was added, labeled 1, 2, 3, 4, and GO powder and TiO were added 2 Mixing the powder with distilled water by ultrasonic, stirring, pouring the mixed reactant into a polytetrafluoroethylene hydrothermal reaction kettle, and carrying out hydrothermal treatment for 12 hours at 180 ℃. After completion, it was allowed to cool naturally to room temperature and the impurities were separated by filtration. Then washing the sample, drying at room temperature, and the like to finally obtain the final product of 0.5%, 1%, 5%, 7.5% GO/TiO 2 A composite material.
For the prepared GO/TiO 2 Catalyst SEM, XRD characterization
Example 4
TiO 2 The composite behavior of the catalyst can improve its catalytic effect, so to further improve the catalyst performance, the effect produced during the composite catalysis is studied more intensively, in this example, GO/TiO is utilized 2 The composite material was tested for MB adsorption performance. Respectively weighing 10.0mg of GO/TiO 2 (0.5%, 1%, 5%, 7.5%) compositeThe material is added into 10mL of MO solution with the concentration of 10mg/L, and is fully degraded under the ultraviolet light condition, and the absorbance of the supernatant liquid at the wavelength of 460nm is measured by an ultraviolet spectrophotometer. Data were recorded once every 1h interval. From the experimental results, it was found that the ratio was compared to 0.5% GO/TiO 2 Composite material, 1% GO/TiO 2 The adsorption rate of the composite material to MB is faster. During the equilibrium, 1% GO/TiO 2 The equilibrium adsorption capacity of the composite material to MB is more than 0.5 percent of GO/TiO 2 A composite material. In other words, the addition of GO significantly improves TiO 2 The adsorption performance and adsorption rate of the photocatalyst. Important information of the relation between the GO content and the adsorption performance is provided for us, and the optimization of the material formula and the process is facilitated for us, so that the adsorption performance of the adsorbent is further improved.
Example 5
By GO/TiO 2 And (3) carrying out catalytic performance test on the MO by the composite material, selecting the composite materials with different proportions, placing the MO in a cuvette, and detecting the absorbance of the solution by an external spectrophotometer. Respectively weighing 10mg of TiO 2 、0.5％GO/TiO 2 Composite material, 1% GO/TiO 2 The composite material was measured by measuring 10mL of MB solution having a concentration of 0.01mmol/L in a glass vial, and shaking the solution in a constant temperature shaker at 25℃for 12 hours until the adsorption equilibrium was reached, and measuring the absorbance of MB at this time by an ultraviolet-visible spectrophotometer at intervals. The other conditions were unchanged, the temperature was changed to 35℃and 45℃and two groups were measured. From the experimental results, it was found that 0.5% GO/TiO 2 The composite material has the best degradation effect on MO and the most sufficient degradation degree, and is along with GO/TiO 2 The proportion of the composite material is increased, and the degradation effect is reduced. GO/TiO 2 The improvement in catalytic performance of the composite is mainly due to TiO 2 Uniformly attached to the GO sheet layer, has good dispersion degree and no obvious agglomeration phenomenon, thereby improving the TiO 2 The photocatalytic performance of the catalyst improves the chemical property and defect structure of the surface of the catalyst, is favorable for the adsorption and activation of oxygen and improves the catalytic activity.
The present invention is not limited to the above-mentioned embodiments, and any equivalent embodiments which can be changed or modified by the technical content disclosed above can be applied to other fields, but any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical substance of the present invention without departing from the technical content of the present invention still belong to the protection scope of the technical solution of the present invention.
Claims (10)
1. GO/TiO 2 The preparation method of the composite catalyst is characterized by comprising the following steps: the method comprises the following steps:
s1: preparation of GO, tiO 2 A certain amount of GO and TiO 2 Mixing with deionized water;
s2: the sample obtained by S1 is subjected to ultrasonic treatment, stirred and reacted for 12 hours at 180 ℃ in a polytetrafluoroethylene hydrothermal reaction kettle;
s3: after the completion, cooling to room temperature, washing the sample, drying at room temperature and the like to finally obtain the GO/TiO 2 A composite material.
2. The GO/TiO as defined in claim 1 2 The preparation method of the composite catalyst is characterized by comprising the following steps: the preparation method of the GO in the S1 comprises the following steps:
step one: slowly adding sulfuric acid solution into graphite and NaNO 3 Stirring under ice bath conditions;
step two: slowly adding proper amount of potassium permanganate into beaker, reacting at room temperature, adding proper amount of deionized water, continuing the reaction, stopping heating, gradually cooling to about 60deg.C, and adding proper amount of H 2 O 2 After the temperature of the solution is reduced to room temperature, sealing the solution by using a sealing film;
step three: and (3) centrifugally separating the graphene mixed solution obtained in the step (II), washing, freeze-drying, grinding, and sieving to obtain GO powder.
3. The GO/TiO according to claim 2 2 The preparation method of the composite catalyst is characterized by comprising the following steps: in the step oneThe stirring time was 30min.
4. The GO/TiO according to claim 2 2 The preparation method of the composite catalyst is characterized by comprising the following steps: and in the second step, a proper amount of potassium permanganate is slowly added into a beaker, the reaction is carried out for 2 hours at room temperature, a proper amount of deionized water is added, the reaction is continued for 1 hour at 95 ℃, and the heating is stopped.
5. The GO/TiO as defined in claim 1 2 The preparation method of the composite catalyst is characterized by comprising the following steps: tiO in S1 2 The preparation method of the (C) comprises the following steps:
step one: adding absolute ethyl alcohol and butyl titanate into a beaker for reaction, stirring at room temperature, and adding glacial acetic acid to obtain a solution A;
step two: stirring the solution A for 15min until the color becomes transparent, adding NH into the solution A 4 NO 3 Distilled water and absolute ethyl alcohol to obtain a solution C;
step three: adding the solution C into the solution B, regulating pH, reacting to form gel state, standing the semi-finished product at room temperature, centrifuging by using a centrifuge, washing for a plurality of times by using deionized water until the solution is neutral, and calcining to obtain pure white TiO2 powder.
6. The GO/TiO according to claim 5 2 The preparation method of the composite catalyst is characterized by comprising the following steps: and in the first step, the stirring time is 15min.
7. The GO/TiO according to claim 5 2 The preparation method of the composite catalyst is characterized by comprising the following steps: the third step is specifically: adding the solution C into the solution B, regulating the pH, reacting for 30min at 40 ℃ to form a gel state, standing the semi-finished product at room temperature for 12h, centrifuging by using a centrifuge, washing with deionized water for multiple times until the solution is neutral, and calcining for 3h at 300 ℃ to obtain pure white TiO2 powder.
8. GO/TiO 2 A composite catalyst characterized in that: using the GO/TiO as defined in any one of claims 1-7 2 The preparation method of the composite catalyst is used for preparing the catalyst.
9. GO/TiO 2 The application of the composite catalyst to the research of the photocatalytic performance of MO (methyl orange) is characterized in that: at different times, GO/TiO 2 Influence of the composite on the change in MO absorbance.
10. GO/TiO 2 The application of the composite catalyst to MB (methylene blue) adsorption is characterized in that: the specific reaction conditions are as follows: GO/TiO 2 The composite material and MB are evenly mixed and then are placed in a cuvette, the cuvette is placed in an ultraviolet spectrophotometer, and the GO/TiO is reflected by the change of absorbance 2 Adsorption capacity of composite materials for MB.
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