CN109078644B - Graphene-loaded Bi-BiOCl-TiO2Photocatalyst and preparation method thereof - Google Patents
Graphene-loaded Bi-BiOCl-TiO2Photocatalyst and preparation method thereof Download PDFInfo
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [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 2
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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- B01J35/39—
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- B01J35/50—
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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
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
Graphene-loaded Bi-BiOCl-TiO2A photocatalyst and a preparation method thereof, belonging to the field of photocatalysis. The graphene-loaded Bi-BiOCl-TiO2The preparation method of the photocatalyst comprises the following steps: mixing a mixture of bismuth nitrate, polyethylene glycol and tetra-n-butyl titanate and a mixture of sodium chloride and citric acid dissolved in water, and keeping the temperature of the mixture at 140-200 ℃ for 8-16 h under 2-4 MPa to obtain Bi-BiOCl-TiO2Mixing the photocatalytic particles and the graphene solution thickly, reacting for 1-5 h at the temperature of 100-150 ℃ under the pressure of 2-4 MPa, and centrifugally drying to obtain the graphene loaded Bi-BiOCl-TiO2A photocatalyst. The photocatalyst can effectively inhibit the rapid combination of pure BiOCl electron hole pairs and improve the utilization rate of visible light, so that BiOCl grows towards the (001) orientation, and the photocatalytic efficiency is greatly improved. The method has the advantages of simple preparation process, low cost, less time consumption and rapid production.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to graphene loaded Bi-BiOCl-TiO2A photocatalyst and a preparation method thereof.
Background
The semiconductor photocatalytic oxidation technology can effectively degrade various pollutants harmful to the environment and mineralize the pollutants into CO2、H2Small molecules such as O are an advanced oxidation process, and are one of the important methods for dealing with environmental pollution problems in recent years. TiO22Due to the fact thatThe photocatalyst has the advantages of high catalytic activity, strong oxidation capability, good chemical, physical and biological stability, no toxicity and the like, and is proved to be one of the most excellent semiconductor photocatalysts at present. TiO22The band gap energy of the material is 3.2eV, and the TiO can be excited only under the irradiation of ultraviolet light with the wavelength of less than 387nm2Electron-hole pairs are generated. However, in the energy spectrum of sunlight, ultraviolet light of 400nm or less is less than 5%, and visible light having a wavelength of 400 to 800nm accounts for 43%. BiOCl is a novel layered semiconductor compound, the crystal structure of which is a tetragonal PbFCl type and can also be regarded as double X along the C axis direction-Layer and [ Bi ]2O2]2+The layered structure formed by the alternate arrangement of the layers belongs to a tetragonal system. However, the photo-generated electrons and holes of BiOCl are susceptible to rapid recombination, resulting in a decrease in the efficiency of the photocatalytic reaction.
The graphene is formed by a monolayer of carbon atoms passing through sp2The carbon atoms of the hexagonal honeycomb two-dimensional crystal plane structure formed by the hybrid tracks are connected through strong sigma bonds, and the C-C bonds enable the graphene to have excellent structural rigidity and higher strength in the direction parallel to the lamella. The graphene has excellent properties such as high electron mobility, high specific surface area, high strength, higher Young modulus and the like. The excellent performances enable the graphene to have wide application prospects in the fields of nano electronic devices, gas sensors, energy storage, composite materials and the like. Graphene, as an excellent electron conductor, can chemically complex with photocatalytic particles. When the photocatalytic particles are excited by light to generate electrons and holes, the graphene can rapidly conduct away the electrons, so that the recombination of the holes and the electrons is blocked, the generation of photoproduction holes is promoted, and the visible light photocatalytic capability is improved.
Disclosure of Invention
The invention solves the key problem of providing the graphene loaded Bi-BiOCl-TiO2A photocatalyst and a preparation method thereof. The graphene-loaded Bi-BiOCl-TiO2The photocatalyst can effectively inhibit the rapid combination of pure BiOCl electron hole pairs and improve the utilization rate of visible light, so that BiOCl grows towards (001) orientation, and compared with the photocatalysis performance of pure BiOCl, the graphene-loaded Bi-BiOCl-TiO2Photocatalytic efficiency obtaining pole of photocatalystThe maximum improvement can reach 99.1 percent.
In order to achieve the purpose, the invention adopts the following scheme:
the invention relates to graphene loaded Bi-BiOCl-TiO2The preparation method of the photocatalyst comprises the following steps:
step 1: preparing a reaction solution
(1) Weighing raw materials according to a ratio, dissolving bismuth nitrate, polyethylene glycol and tetrabutyl titanate in deionized water, and uniformly stirring to obtain a mixture A; wherein, according to the solid-liquid ratio of each component, the ratio of bismuth nitrate: polyethylene glycol: tetra-n-butyl titanate: deionized water (0.9-1) g: (0.1-0.2) g: (1-2) mL: (25-30) mL;
(2) weighing raw materials according to a ratio, dissolving sodium chloride and citric acid in deionized water, and uniformly stirring to obtain a mixture B; wherein, according to the solid-liquid ratio of each component, the ratio of sodium chloride: citric acid: deionized water (110-112) mg: (490-500) mg: (25-30) mL;
(3) mixing the mixture A and the mixture B to obtain a reaction solution; wherein, in the mixture A, Ti4+: cl in the mixture B-＝1:1；
Step 2: preparation of Bi-BiOCl-TiO2Photocatalytic particles
(1) Placing the reaction solution in a high-pressure reaction kettle, and preserving the temperature for 8-16 h at the temperature of 140-200 ℃ under the pressure of 2-4 MPa to obtain the Bi-BiOCl-TiO2A photocatalytic particle mixture;
(2) adding Bi-BiOCl-TiO2Centrifuging the photocatalytic particle mixture, washing a centrifuged solid product for several times, and drying to obtain Bi-BiOCl-TiO2Photocatalytic particles;
and step 3: dispersed graphene solution
(1) Dissolving graphene in a mixed solution of deionized water and absolute ethyl alcohol, and performing ultrasonic dispersion uniformly to obtain a graphene solution with the mass concentration of 0.2-0.4 mg/mL;
(2) mixing graphene solution and Bi-BiOCl-TiO2Mixing the photocatalytic particles, and uniformly stirring to obtain graphene and Bi-BiOCl-TiO2A mixed solution of photocatalytic particles; wherein the content of the first and second substances,according to the mass ratio, graphene: Bi-BiOCl-TiO2Photocatalytic particles ═ 1: (100-20);
and 4, step 4: preparation of graphene loaded Bi-BiOCl-TiO2Photocatalyst and process for producing the same
(1) Mixing graphene and Bi-BiOCl-TiO2Placing the mixed solution of the photocatalytic particles in a high-pressure reaction kettle, and reacting for 1-5 h at the temperature of 100-150 ℃ under the pressure of 2-4 MPa to obtain the graphene-containing loaded Bi-BiOCl-TiO2A photocatalyst mixture;
(2) loading Bi-BiOCl-TiO to graphene-containing2Centrifuging the photocatalyst mixture, and loading the centrifuged graphene with Bi-BiOCl-TiO2Cleaning and drying the photocatalyst to obtain the graphene loaded Bi-BiOCl-TiO2A photocatalyst.
In the step 1(1), the polyethylene glycol is preferably polyethylene glycol 800.
In the step 2(1), in a high-pressure reaction kettle, under the acidic and hydrothermal conditions, part of polyethylene glycol is decomposed to obtain ethylene glycol, and Bi is added3+Reducing the metal Bi into metal Bi.
In the step 2(2), the drying is carried out at a temperature of 60-90 ℃.
Preferably, in the step 3(1), in the mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of deionized water: and (1) absolute ethyl alcohol (1-2) and (1).
In the step 3(1), the ultrasonic dispersion is carried out, and the ultrasonic frequency is 30-50 KHz.
In the step 4(2), the drying is carried out at a temperature of 60-90 ℃.
The invention relates to graphene loaded Bi-BiOCl-TiO2The photocatalyst is prepared by the preparation method.
The invention relates to graphene loaded Bi-BiOCl-TiO2Photocatalyst comprising graphene and Bi-BiOCl-TiO2Photocatalytic particles of Bi-BiOCl-TiO2The photocatalytic nanosheets are distributed inside and on the surface of the graphene.
The graphene loaded Bi-BiOCl-TiO2The photocatalyst can promote the growth of BiOCl along (001) orientation and has high degreeExposure (001) is more favorable for the formation of oxygen vacancies, which enhances photocatalytic performance.
The graphene loaded Bi-BiOCl-TiO2The highest photocatalytic efficiency of the photocatalyst within 50min reaches 99.1%.
The graphene-loaded Bi-BiOCl-TiO2 photocatalyst and the preparation method thereof have the beneficial effects that: this text changes graphene with Bi-BiOCl-TiO2Mass ratio of Bi-BiOCl-TiO2The mass ratio of the graphene to the graphene is respectively 1000:10, 800:10, 600:10, 400:10 and 200:10, which are respectively marked as BBTR100, BBTR80, BBTR60, BBTR40 and BBTR20, and the method effectively leads the graphene and Bi-BiOCl-TiO to be mixed2Combined together, in an experiment of degrading methyl orange by photocatalysis, the degradation rate is as high as 99.1% after 50 min; the preparation process is simple, the cost is low, the time consumption is low, and the rapid production can be realized.
Drawings
FIG. 1 shows that in example 1 of the present invention, graphene is loaded with Bi-BiOCl-TiO2XRD patterns of photocatalyst and its intermediate products;
FIG. 2 shows that in example 1 of the present invention, graphene is loaded with Bi-BiOCl-TiO2A raman spectrum of the photocatalyst and intermediates thereof;
FIG. 3 shows that example 1 of the present invention includes graphene loaded with Bi-BiOCl-TiO2SEM picture of photocatalyst-BBTR-20.
FIG. 4 shows that different proportions of the graphene loaded Bi-BiOCl-TiO of the invention2Degradation rate of the photocatalyst and its intermediates.
FIG. 5 shows that the prepared graphene supported Bi-BiOCl-TiO of the invention2A process flow diagram for a photocatalyst.
In the above figure, Bi/BiOCl/TiO2Representing graphene loaded Bi-BiOCl-TiO2Photocatalyst, Bi/BiOCl stands for the Bi-BiOCl photocatalyst product of comparative example 1, BBTR-20 stands for Bi-BiOCl-TiO2Graphene loaded Bi-BiOCl-TiO with the mass ratio of 200:10 to graphene2Photocatalyst BBT stands for graphene loaded Bi-BiOCl-TiO2A photocatalyst.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Graphene-loaded Bi-BiOCl-TiO2The preparation method of the photocatalyst has a process flow chart shown in figure 5, and comprises the following steps:
step 1: preparing a reaction solution
(1) Weighing raw materials according to a ratio, dissolving 0.93g of bismuth nitrate, 0.2g of polyethylene glycol 800 and 2mL of tetrabutyl titanate in 30mL of deionized water, magnetically stirring for 30min, and uniformly stirring to obtain a mixture A;
(2) weighing raw materials according to a ratio, dissolving 0.112g of sodium chloride and 500mg of citric acid in 30mL of deionized water, and uniformly stirring by magnetic force to obtain a mixture B;
(3) mixing the mixture A and the mixture B to obtain a reaction solution; wherein, in the mixture A, Ti4+: cl in the mixture B-＝1:1；
Step 2: preparation of Bi-BiOCl-TiO2Photocatalytic particles
(1) Placing the reaction solution in a high-pressure reaction kettle, and keeping the temperature at 160 ℃ for 12h under 3MPa to obtain the Bi-BiOCl-TiO2A photocatalytic particle mixture;
(2) adding Bi-BiOCl-TiO2Centrifuging the photocatalytic particle mixture, washing the centrifuged solid product for several times, and drying at 80 ℃ to obtain Bi-BiOCl-TiO2Photocatalytic particles;
and step 3: dispersed graphene solution
(1) Dissolving 10mg of graphene in a mixed solution of 20mL of deionized water and 10mL of absolute ethyl alcohol, performing ultrasonic dispersion for 30min at an ultrasonic frequency of 40KHz, and uniformly dispersing to obtain a graphene solution with a mass concentration of 0.33 mg/mL;
(2) mixing the obtained graphene solution with 200mg of Bi-BiOCl-TiO2Mixing the photocatalytic particles, magnetically stirring for 2 hours, and uniformly mixing to obtain graphene and Bi-BiOCl-TiO2A mixed solution of photocatalytic particles; wherein, according to the mass ratio, the graphene: Bi-BiOCl-TiO2Photocatalytic particles ═ 1: 20;
and 4, step 4: preparation of graphene loaded Bi-BiOCl-TiO2Photocatalyst and process for producing the same
(1) Mixing graphene and Bi-BiOCl-TiO2Placing the mixed solution of the photocatalytic particles in a high-pressure reaction kettle, and reacting at 120 ℃ for 3h under 3MPa to obtain the graphene-containing loaded Bi-BiOCl-TiO2A photocatalyst mixture;
(2) loading Bi-BiOCl-TiO to graphene-containing2Centrifuging the photocatalyst mixture, and loading the centrifuged graphene with Bi-BiOCl-TiO2The photocatalyst is washed for a plurality of times by deionized water and absolute ethyl alcohol and dried at 80 ℃ to obtain the graphene loaded Bi-BiOCl-TiO2A photocatalyst.
The graphene-supported Bi-BiOCl-TiO prepared in the example2Photocatalyst comprising graphene and Bi-BiOCl-TiO2Photocatalytic particles of Bi-BiOCl-TiO2The photocatalytic nanosheets are distributed inside and on the surface of the graphene.
In this example, the graphene supported Bi-BiOCl-TiO2SEM picture of photocatalyst BBTR-20, see FIG. 3, and FIG. 3 shows Bi-BiOCl-TiO2Well grown on the RGO surface.
Example 2
Graphene-loaded Bi-BiOCl-TiO2The preparation method comprises the following steps:
step 1, preparing a reaction solution
(1) Dissolving 1g of bismuth nitrate, 0.1g of polyethylene glycol 800 and 1mL of tetrabutyl titanate in a 25mL deionized water beaker 1, and magnetically stirring for 30-40 min to obtain a mixture A;
(2) dissolving 110mg of sodium chloride and 490mg of citric acid in a 25ml deionized water beaker 2, and mechanically stirring uniformly to obtain a mixture B;
(3) pouring the mixture B solution in the beaker 2 into the mixture A in the beaker 1, and stirring uniformly to fully react to obtain a reaction solution.
(1) Pouring the reaction solution into a high-pressure reaction kettle, and preserving the heat for 16 hours at the temperature of 140 ℃ under the pressure of 4MPa to obtain the Bi-BiOCl-TiO-containing material2A photocatalytic particle mixture;
(2) adding Bi-BiOCl-TiO2Centrifuging the photocatalytic particle mixture, washing the centrifuged solid product with deionized water and absolute ethanol to obtain Bi-BiOCl-TiO2Drying for several times at 90 ℃ to obtain Bi-BiOCl-TiO2Photocatalytic particles.
Step 3, dispersing the graphene solution
(1) Dissolving 10mg of graphene in 20mL of deionized water and 20mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 30-40 min, and uniformly dispersing to obtain a graphene solution with the mass concentration of 0.25 mg/mL;
(2) 200mgBi-BiOCl-TiO2Mixing with graphene solution, magnetically stirring for 2h, and uniformly stirring to obtain graphene and Bi-BiOCl-TiO2A mixed solution of photocatalytic particles; wherein, according to the mass ratio, the graphene: Bi-BiOCl-TiO2Photocatalytic particles ═ 1: 20;
step 4, preparing the graphene loaded Bi-BiOCl-TiO2Photocatalyst and process for producing the same
(1) Mixing graphene and Bi-BiOCl-TiO2Pouring the mixed solution of the photocatalytic particles into a high-pressure reaction kettle, and respectively heating at 100 ℃ for 5h to obtain the graphene-containing loaded Bi-BiOCl-TiO2A photocatalyst mixture.
(2) Loading Bi-BiOCl-TiO to graphene-containing2Centrifuging the photocatalyst mixture, and loading the centrifuged graphene with Bi-BiOCl-TiO2The photocatalyst is washed for a plurality of times by deionized water and absolute ethyl alcohol and dried at the temperature of 90 ℃ to obtain the graphene-loaded Bi-BiOCl-TiO2A photocatalyst.
Step 5, photocatalytic experiment
The prepared photocatalyst (30mg) was dispersed in 50ml of an aqueous methyl orange solution having a concentration of 20mg/L, and the suspension was magnetically stirred in the dark for 30 minutes before light irradiation to achieve adsorption/desorption equilibrium between the photocatalyst and methyl orange. Then, 4ml of the suspension was taken every 10 minutes during irradiation and centrifuged. The solution centrifuged at the wavelength of maximum absorption was recorded.
Example 3
Graphene-loaded Bi-BiOCl-TiO2The preparation method comprises the following steps:
step 1, preparing a reaction solution
(1) Dissolving 0.93g of bismuth nitrate, 0.2g of polyethylene glycol 400 and 2ml of tetra-n-butyl titanate in a 30ml of deionized water beaker 1, and mechanically stirring for 30min to obtain a mixture A;
(2) dissolving 0.112g of sodium chloride and 500mg of citric acid in a 30ml deionized water beaker 2, and magnetically stirring for 30min to obtain a mixture B;
(3) the mixture B solution in beaker 2 was poured into the mixture A in beaker 1 and magnetically stirred for 30min to obtain a reaction solution.
(1) Pouring the reaction solution into a high-pressure reaction kettle, and preserving the heat for 12 hours at the temperature of 160 ℃ under the pressure of 2MPa to obtain the Bi-BiOCl-TiO2A photocatalytic particle mixture;
(2) adding Bi-BiOCl-TiO2Centrifuging the photocatalytic particle mixture, washing the centrifuged solid product with deionized water and absolute ethanol to obtain Bi-BiOCl-TiO2Drying for several times at 80 ℃ to obtain Bi-BiOCl-TiO2Photocatalytic particles.
Step 3, dispersing the graphene solution
(1) Dissolving 10mg of graphene in 15mL of deionized water and 10mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 30min, and uniformly dispersing to obtain a graphene solution with the mass concentration of 0.4 mg/mL;
(2) 200mgBi-BiOCl-TiO2Mixing with graphene solution, magnetically stirring for 2h, and magnetically stirring for 2h to obtain graphene and Bi-BiOCl-TiO2A mixed solution of photocatalytic particles; wherein, according to the mass ratio, the graphene: Bi-BiOCl-TiO2Photocatalytic particles ═ 1: 20.
step 4, preparing the graphene loaded Bi-BiOCl-TiO2Photocatalyst and process for producing the same
(1) Mixing graphene and Bi-BiOCl-TiO2Pouring the mixed solution of the photocatalytic particles into a high-pressure reaction kettle, and respectively heating at 120 ℃ for 3h to obtain the graphene-containing loaded Bi-BiOCl-TiO2A photocatalyst mixture.
(2) Loading Bi-BiOCl-TiO to graphene-containing2Centrifuging the photocatalyst mixture, and loading the centrifuged graphene with Bi-BiOCl-TiO2The photocatalyst is washed for a plurality of times by deionized water and absolute ethyl alcohol and dried at the temperature of 80 ℃ to obtain the graphene-loaded Bi-BiOCl-TiO2A photocatalyst.
Example 4
Graphene-loaded Bi-BiOCl-TiO2The preparation method of the photocatalyst is the same as that of example 1, except that the weight ratio of graphene: Bi-BiOCl-TiO2＝1000:10。
The graphene-supported Bi-BiOCl-TiO prepared in the example2The photocatalyst is BBTR 100.
Example 5
Graphene-loaded Bi-BiOCl-TiO2The preparation method of the photocatalyst is the same as that of example 1, except that the weight ratio of graphene: Bi-BiOCl-TiO2＝800:10。
The graphene-supported Bi-BiOCl-TiO prepared in the example2The photocatalyst is BBTR 80.
Example 6
Graphene-loaded Bi-BiOCl-TiO2The preparation method of the photocatalyst is the same as that of example 1, except that the weight ratio of graphene: Bi-BiOCl-TiO2＝600:10。
The graphene-supported Bi-BiOCl-TiO prepared in the example2The photocatalyst is BBTR 60.
Example 7
Graphene-loaded Bi-BiOCl-TiO2The preparation method of the photocatalyst is the same as that of example 1, except that the weight ratio of graphene: Bi-BiOCl-TiO2＝400:10。
The graphene-supported Bi-BiOCl-TiO prepared in the example2The photocatalyst is BBTR 40.
Comparative example 1
A preparation method of Bi-BiOCl photocatalytic particles comprises the following steps:
step 1: preparing a reaction solution
(1) Weighing raw materials according to a ratio, dissolving 0.93g of bismuth nitrate and 0.2g of polyethylene glycol 800 in 30mL of deionized water, magnetically stirring for 30min, and uniformly stirring to obtain a mixture A;
(2) weighing raw materials according to a ratio, dissolving 0.112g of sodium chloride and 500mg of citric acid in 30mL of deionized water, and uniformly stirring by magnetic force to obtain a mixture B;
(3) mixing the mixture A and the mixture B to obtain a reaction solution; wherein, in the mixture A, Ti4+: cl in the mixture B-＝1:1；
Step 2: preparation of Bi-BiOCl photocatalytic particles
(1) Placing the reaction solution in a high-pressure reaction kettle, and keeping the temperature at 160 ℃ for 12h under 3MPa to obtain a mixture containing Bi-BiOCl photocatalytic particles;
(2) centrifuging the mixture containing the Bi-BiOCl photocatalytic particles, washing a centrifuged solid product for several times, and drying at 80 ℃ to obtain the Bi-BiOCl photocatalytic particles.
The graphene prepared in example 1 is loaded with Bi-BiOCl-TiO2XRD analysis was performed on the photocatalyst and the product of the comparative example, and the pattern after the analysis is shown in FIG. 1, from which FIG. 1, it can be derived that: no impurities were detected in all samples, indicating that the product was of high purity and crystallized well. Notably, with Bi/BiOCl and Bi/BiOCl/TiO2In contrast, BBTR-20 has the highest (001) peak. The results indicate that BiOCl should promote growth in the (001) orientation. The high exposure (001) is more favorable for the formation of oxygen vacancies, which enhances photocatalytic performance.
The graphene prepared in example 1 is loaded with Bi-BiOCl-TiO2The Raman spectrum of the photocatalyst and the intermediate product of the comparative example is shown in figure 2, and the Raman spectrum is at 90cm-1A weaker band is observed, due to the first-order scattering A of Bi1gMode(s). BiOCl has two typical characteristic peaks respectively located at 153.2cm-1(AlgInternal Bi — Cl stretching mode) and 202.4cm-1(EgInternal Bi — Cl stretching vibration). At 399.1 (B)1g)，510.2(A1g+B1g) And 629.1cm-1(Eg) Is TiO2Characteristic peak of (2).
The graphene loaded Bi-BiOCl-TiO prepared in example 1 and examples 4-7 according to different proportions2Photocatalyst and comparative productThe degradation rate of BBTR-20 is shown in FIG. 4, and it can be seen visually and clearly from FIG. 4 that it exhibits the highest photocatalytic performance. Graphene-loaded Bi-BiOCl-TiO2The highest photocatalytic efficiency of the photocatalyst within 50min reaches 99.1%.
Claims (6)
1. Graphene-loaded Bi-BiOCl-TiO2The preparation method of the photocatalyst is characterized by comprising the following steps:
step 1: preparing a reaction solution
(1) Weighing raw materials according to a ratio, dissolving bismuth nitrate, polyethylene glycol and tetrabutyl titanate in deionized water, and uniformly stirring to obtain a mixture A; wherein, according to the solid-liquid ratio of each component, the ratio of bismuth nitrate: polyethylene glycol: tetra-n-butyl titanate: deionized water = (0.9-1) g: (0.1-0.2) g: (1-2) mL: (25-30) mL;
(2) weighing raw materials according to a ratio, dissolving sodium chloride and citric acid in deionized water, and uniformly stirring to obtain a mixture B; wherein, according to the solid-liquid ratio of each component, the ratio of sodium chloride: citric acid: deionized water = (110-112) mg: (490-500) mg: (25-30) mL;
(3) mixing the mixture A and the mixture B to obtain a reaction solution; wherein, in the mixture A, Ti4+: cl in the mixture B-=1:1；
Step 2: preparation of Bi-BiOCl-TiO2Photocatalytic particles
(1) Placing the reaction solution in a high-pressure reaction kettle, and preserving the temperature at 140-200 ℃ for 8-16 h under 2-4 MPa to obtain the Bi-BiOCl-TiO-containing material2A photocatalytic particle mixture;
(2) adding the Bi-BiOCl-TiO2Centrifuging the photocatalytic particle mixture, washing a centrifuged solid product for several times, and drying to obtain Bi-BiOCl-TiO2Photocatalytic particles;
and step 3: dispersed graphene solution
(1) Dissolving graphene in a mixed solution of deionized water and absolute ethyl alcohol, and performing ultrasonic dispersion uniformly to obtain a graphene solution with the mass concentration of 0.2-0.4 mg/mL;
(2) mixing the graphene solution and the Bi-BiOCl-TiO2Mixing the photocatalytic particles, and uniformly stirring to obtain graphene and Bi-BiOCl-TiO2A mixed solution of photocatalytic particles; wherein, according to the mass ratio, the graphene: Bi-BiOCl-TiO2Photocatalytic particles = 1: (100-20);
and 4, step 4: preparation of graphene loaded Bi-BiOCl-TiO2Photocatalyst and process for producing the same
(1) Mixing the graphene and Bi-BiOCl-TiO2Placing the mixed solution of the photocatalytic particles in a high-pressure reaction kettle, and reacting for 1-5 h at the temperature of 100-150 ℃ under the pressure of 2-4 MPa to obtain the graphene-containing loaded Bi-BiOCl-TiO2A photocatalyst mixture;
(2) loading Bi-BiOCl-TiO on the graphene-containing material2Centrifuging the photocatalyst mixture, and loading the centrifuged graphene with Bi-BiOCl-TiO2Cleaning and drying the photocatalyst to obtain the graphene loaded Bi-BiOCl-TiO2A photocatalyst;
the graphene loaded Bi-BiOCl-TiO2The photocatalyst comprises graphene and Bi-BiOCl-TiO2Photocatalytic particles of Bi-BiOCl-TiO2The photocatalytic nanosheets are distributed in the graphene and on the surface of the graphene, and BiOCl grows along the (001) orientation.
2. The graphene-supported Bi-BiOCl-TiO of claim 12The preparation method of the photocatalyst is characterized in that in the step 1(1), the polyethylene glycol is polyethylene glycol 800.
3. The graphene-supported Bi-BiOCl-TiO of claim 12The preparation method of the photocatalyst is characterized in that in the step 2(2), the drying is carried out at the drying temperature of 60-90 ℃.
4. The graphene-supported Bi-BiOCl-TiO of claim 12The preparation method of the photocatalyst is characterized in that in the step 3(1), in the mixed solution of deionized water and absolute ethyl alcohol, the volume ratio of deionized water: absolute ethyl alcohol = (1-2): 1.
5. Graphene according to claim 1Bi-BiOCl-TiO load2The preparation method of the photocatalyst is characterized in that in the step 3(1), the ultrasonic dispersion is carried out, and the ultrasonic frequency is 30-50 KHz.
6. The graphene-supported Bi-BiOCl-TiO of claim 12The preparation method of the photocatalyst is characterized in that in the step 4(2), the drying is carried out at the drying temperature of 60-90 ℃.
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