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CN110624532B - TiO 22-BiVO4-graphene ternary composite photocatalytic material and preparation method thereof - Google Patents

TiO 22-BiVO4-graphene ternary composite photocatalytic material and preparation method thereof Download PDF

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CN110624532B
CN110624532B CN201910887702.9A CN201910887702A CN110624532B CN 110624532 B CN110624532 B CN 110624532B CN 201910887702 A CN201910887702 A CN 201910887702A CN 110624532 B CN110624532 B CN 110624532B
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韦江雄
陈列列
余其俊
祝雯
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South China University of Technology SCUT
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Abstract

The invention relates to a TiO compound2‑BiVO4-graphene ternary composite materials and methods of making the same. The TiO is2‑BiVO4Square micron-sized BiVO in-graphene ternary composite material4Deposit petal-shaped nano TiO on the surface2TiO formed by the two2‑BiVO4The composite material is uniformly deposited on the surface of the graphene. The TiO is2‑BiVO4The-graphene ternary composite material has a large specific surface area, and the BiVO is remarkably improved4With TiO2The photocatalytic activity and the utilization rate of visible light can be used for degrading organic pollutants, and the application prospect is wide.

Description

TiO 22-BiVO4-graphene ternary composite photocatalytic material and preparation method thereof
Technical Field
The invention belongs to the field of inorganic nano photocatalytic materials, and particularly relates to TiO2-BiVO4-graphene ternary composite photocatalytic material and a preparation method thereof.
Background
With the development of global economy, water pollution is worsened continuously, the content of organic matters in sewage is high, toxicity is high, human life and body health are seriously affected, and sustainable development of society is seriously affected, so that sewage purification becomes a hot problem of global attention. The traditional methods for treating sewage mostly adopt physical adsorption methods, activated carbon adsorption and the like, which reduce the pollution of the wastewater to a certain extent, but because the efficiency is too low and secondary pollution is easy to generate, the method is difficult to be widely applied. The semiconductor catalysis technology is a new environment-friendly technology reflected in eye curtains of various scientists, and researches show that the semiconductor catalysis technology is low in energy consumption, high in catalysis efficiency, strong in oxidizability and wide in application range. Compared with the traditional environment purification treatment method, the semiconductor photocatalysis technology has mild reaction conditions, simpler operation and no secondary pollution to the environment, and utilizes sunlight as photocatalysis energy, and the photocatalyst can be continuously recycled. The characteristics of low preparation cost, energy conservation and environmental friendliness of the photocatalytic technology enable the photocatalytic technology to have a huge application prospect in the aspect of solving the environmental problems.
BiVO4As a semiconductor with visible light response activity, visible light with the wavelength of 420nm or more is used as an excitation light source to carry out photocatalytic degradation on organic matters. But BiVO4The generated electrons and holes are easy to be recombined, the photocatalytic activity is greatly weakened, and the problems can be solved by carrying out heterogeneous recombination with the wide-bandgap semiconductor nano particles. Such as BiVO4/TiO2The compound semiconductor not only broadens TiO2The response in the visible light region also suppresses recombination of electrons and holes to some extent. But BiVO4/TiO2The composite semiconductor has small specific surface area and poor adsorption capacity. The specific surface area of the compound semiconductor can be increased by introducing the graphene, so that the adsorption capacity of the compound semiconductor is enhanced, and the formed ternary composite photocatalytic material has the advantages that: TiO 22-BiVO4Graphene (see CN 105944711A). The photocatalytic activity of the photocatalyst is far higher than that of BiVO4、TiO2、BiVO4/TiO2Due to the excellent conductivity, the photo-generated electrons can be conducted to the surface of the material more quickly, photo-generated electron-hole pairs are effectively separated, and the recombination rate of the photo-generated electron-hole pairs is reduced, so that the graphene has good application prospect in the field of photocatalysis due to the outstanding performance and the easy processability of the graphene.
However, the existing three-component composite photocatalytic material still has two problems to be solved in the aspect of degrading organic pollutants. First, the catalytic activity of a single catalyst in nature is not high, such as: BiVO4With TiO2
The two have a common disadvantage that recombination of holes and electrons is easy to occur, and even if a compound semiconductor is formed by the two, the improvement of the photocatalytic activity is limited. Secondly, the service life of the photocatalyst is limited because organic pollutants occupy active sites in the catalytic degradation process of the catalyst, so that BiVO is generated4With TiO2Activity is greatly reduced after multiple uses.
Disclosure of Invention
The invention aims to provide TiO2-BiVO4-graphene ternary composite photocatalytic material and a preparation method thereof. TiO 22-BiVO4The-graphene ternary composite material is prepared by synthesizing a multi-time hydrothermal reaction method through bismuth nitrate pentahydrate, ammonium metavanadate and TiO2And dispersing and dissolving the graphene oxide in a solvent, stirring, carrying out hydrothermal treatment, washing and drying. The ternary composite material with controllable morphology and particle size is synthesized and prepared by utilizing the advantage of controllable conditions of a hydrothermal method.
The object of the present invention is achieved by at least one of the following technical means.
TiO 22-BiVO4-graphene ternary composite photocatalytic material, square micron-sized BiVO4Surface ofDeposit petal-shaped nano TiO2TiO formed by the two2-BiVO4The composite material is uniformly deposited on the surface of the graphene.
The preparation method of the ternary composite photocatalytic material comprises the following steps:
(1) adding butyl titanate into glacial acetic acid until the solution is milky, and stirring to obtain the synthetic TiO2Carrying out hydrothermal reaction on the precursor solution of the particles, washing, drying and calcining to obtain petal-shaped TiO2；
(2) Dissolving bismuth nitrate pentahydrate in a nitric acid solution to obtain a solution A; dissolving ammonium metavanadate in a sodium hydroxide solution to obtain a solution B; slowly dripping the solution B into the solution A, and magnetically stirring to obtain the synthetic BiVO4A precursor liquid of the particles;
(3) adding TiO into the mixture2Adding the mixture and CTAB solution into the step (2) for synthesizing BiVO4Uniformly stirring and mixing the precursor solution of the particles, carrying out hydrothermal reaction, and then washing and drying to obtain BiVO4/TiO2Composite particles;
(4) dissolving graphene oxide in an absolute ethyl alcohol solution, and performing ultrasonic dispersion to obtain a graphene oxide suspension; BiVO obtained in the step (3)4/TiO2Adding the composite particles into the graphene oxide suspension, stirring, carrying out hydrothermal reaction, then washing to be neutral, and drying to obtain the TiO2-BiVO4-a graphene ternary composite photocatalytic material.
Further, in the step (1), the temperature of the hydrothermal reaction is 140-200 ℃, the time is 5-10 h, and preferably the reaction is carried out for 6h at 180 ℃; the calcining temperature is 500-800 ℃, the time is 1-2 h, and the calcining time is preferably 2h at 600 ℃.
Further, in the step (1), after washing, drying in a vacuum drying oven for 12 hours.
Further, in the step (2), the concentration of the nitric acid solution is 1mol/L to 3mol/L, the concentration of the sodium hydroxide solution is 1mol/L to 3mol/L, and the concentrations of the nitric acid solution and the sodium hydroxide solution are preferably 2 mol/L.
Further, in the step (2), the molar ratio of bismuth nitrate to ammonium metavanadate is 1: 0.5-1: 2, preferably 1: 1.
further, in the step (3), the temperature of the hydrothermal reaction is 140 ℃ to 200 ℃ and the time is 5h to 20h, preferably 6 h.
Further, in the step (3), after washing, vacuum drying is carried out for 10-12 h.
Further, in the step (3), BiVO4/TiO2BiVO in composite particle4：TiO2The mass ratio is 0.25-4: 1.
further, in the step (3), the concentration of the CTAB solution is 5-15 g/L.
Further, in the step (4), the hydrothermal reaction temperature is 100 ℃ to 120 ℃, the time is 1h to 6h, and the hydrothermal reaction temperature is preferably 110 ℃.
Further, in the step (4), the mass fraction of the graphene oxide suspension is 1-10%.
The invention has the advantages that:
1. nano TiO synthesized by using butyl titanate as precursor2The shape of the film is petal-shaped, and when visible light irradiates on petal-shaped TiO2In the process, incident light can be reflected for multiple times, so that the contact between visible light and the photocatalyst is increased, more visible light is absorbed, and the photocatalytic activity of the ternary composite catalyst is further enhanced.
2. The bismuth vanadate with controllable morphology and particle size is prepared by a method of combining multiple times of hydrothermal processes, and a certain amount of surfactant is added into the solution, so that the nano-scale titanium dioxide is deposited on the surface of the polygonal bismuth vanadate, and the problems that the nano-scale titanium dioxide is easy to agglomerate and uneven in deposition are solved.
3. By means of multiple hydrothermal processes, TiO2-BiVO4The composite catalyst is uniformly deposited on graphene, a hydrothermal method has reducibility, and graphene oxide is reduced into flaky graphene. Prepared TiO2-BiVO4The-graphene ternary composite material has a large specific surface area, and can remarkably improve BiVO4With TiO2Is photo-catalysisThe compound has chemical activity and the utilization rate of visible light, can be used for degrading organic pollutants, has the degradation removal rate of 99 percent within 2h to 100ml of 10g/L rhodamine B, can be almost completely degraded, and has wide application prospect in the aspect of environmental protection.
Drawings
In FIG. 1, a is TiO prepared in step (2) of example 12B is the TiO prepared in step (3) of example 12-BiVO4C is TiO prepared in step (4) of example 12-BiVO4SEM images of graphene;
FIG. 2 shows TiO prepared in example 1 of the present invention2-BiVO4-graphene X-ray diffraction patterns;
FIG. 3 shows TiO prepared in example 1 of the present invention2-BiVO4A removal rate schematic diagram of degrading 100ml of 10mg/L rhodamine B by the graphene ternary composite catalyst under the excitation of visible light.
Detailed description of the preferred embodiment
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
TiO 22-BiVO4A method for preparing a graphene ternary composite material, comprising the steps of:
example 1
(1) Respectively weighing bismuth nitrate pentahydrate and ammonium metavanadate according to the molar ratio of 1:1, respectively dissolving the bismuth nitrate pentahydrate and the ammonium metavanadate in 30ml of 2mol/L nitric acid solution and 30ml of 2mol/L sodium hydroxide solution to form A, B solution, slowly adding the solution B into the solution A under the condition of continuous stirring, and carrying out magnetic stirring for 0.5h after dropwise adding to form the precursor solution for synthesizing the bismuth vanadate.
(2) Measuring 75ml of glacial acetic acid in a beaker, slowly dropwise adding 1ml of butyl titanate into the beaker until the solution is milky, and magnetically stirring for 1 hour to obtain the synthetic TiO2And (3) putting the precursor solution of the particles into a 100ml reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 6 hours. Washing with anhydrous ethanol and deionized water for several times, drying in a vacuum drying oven for 12h, and calcining at 600 deg.C for 2h to obtain petal-shaped and nano-grade TiO2(a in FIG. 1)For the TiO prepared in this step2SEM of (5), TiO in FIG. 22Is prepared by this step).
(3) Preparing 1L of CTAB solution of 10g/L according to BiVO4：TiO22.5914 g of TiO are weighed out in a mass ratio of 0.252And measuring 20ml of 10g/L CTAB solution, adding the CTAB solution into the precursor solution of the bismuth vanadate formed in the step (1), and magnetically stirring for 1h to mix uniformly. The hydrothermal reaction temperature is 180 ℃, and the hydrothermal reaction time is 10 h. Washing with anhydrous ethanol and deionized water for multiple times, and drying in a vacuum drying oven at 60 deg.C for 12h to obtain BiVO4/TiO2Composite particles (b in FIG. 1 is BiVO prepared in this step4/TiO2SEM of composite particles).
(4) Weighing 5% of graphene oxide by mass fraction in 75ml of absolute ethyl alcohol, ultrasonically dissolving for 1h to form a graphene oxide suspension, and mixing the synthesized TiO with the suspension2-BiVO4The composite material is added into a graphene oxide suspension, magnetic stirring is carried out for 1h, the uniformly stirred solution is placed into a reaction kettle with a polytetrafluoroethylene lining, hydrothermal is carried out for 5h at 110 ℃, and after the reaction is completed, deionized water is used for washing for multiple times until the solution is neutral. Putting into a vacuum drying oven for vacuum drying at 60 ℃ for 12 h. To obtain TiO2-BiVO4Graphene ternary composite material (c in fig. 1 is TiO prepared in this step2-BiVO4SEM of graphene ternary composites).
As can be seen from a in FIG. 1, the calcined TiO2The petal-shaped structure is more beneficial to the absorption of visible light; from b in FIG. 1, it can be seen that BiVO is in the micron range4The surface is deposited with petal-shaped and nano-grade TiO2(ii) a As can be seen from c in FIG. 1, the TiO formed by the two2-BiVO4The composite material is uniformly deposited on the surface of the graphene; as can be seen from FIG. 2, it was confirmed by XRD that monoclinic scheelite-type BiVO was synthesized in this example4With anatase type TiO2。
Example 2
(1) Respectively weighing bismuth nitrate pentahydrate and ammonium metavanadate according to the molar ratio of 1:1, respectively dissolving the bismuth nitrate pentahydrate and the ammonium metavanadate in 30ml of 2mol/L nitric acid solution and 30ml of 2mol/L sodium hydroxide solution to form A, B solution, slowly adding the solution B into the solution A under the condition of continuous stirring, and carrying out magnetic stirring for 0.5h after dropwise adding to form the precursor solution for synthesizing the bismuth vanadate.
(2) Measuring 75ml of glacial acetic acid in a beaker, slowly dropwise adding 1ml of butyl titanate into the beaker until the solution is milky, and magnetically stirring for 1 hour to obtain the synthetic TiO2The precursor solution of the particles is put into a 100ml reaction kettle and undergoes hydrothermal reaction for 6 hours at 140 ℃. Washing with anhydrous ethanol and deionized water for several times, drying in a vacuum drying oven for 12h, and calcining at 500 deg.C for 2h to obtain petal-shaped and nano-grade TiO2。
(3) Preparing 1L of CTAB solution of 10g/L according to BiVO4：TiO20.9718 g of TiO were weighed out in a mass ratio of 0.672And measuring 20ml of 10g/L CTAB solution, adding the CTAB solution into the precursor solution of the bismuth vanadate formed in the step (1), and magnetically stirring for 1h to mix uniformly. The hydrothermal reaction temperature is 140 ℃, and the hydrothermal reaction time is 5 h. Washing with anhydrous ethanol and deionized water for multiple times, and drying in a vacuum drying oven at 60 deg.C for 12h to obtain BiVO4/TiO2Composite particles.
(4) Weighing 1% of graphene oxide by mass fraction in 75ml of absolute ethyl alcohol, ultrasonically dissolving for 1h to form a graphene oxide suspension, and mixing the synthesized TiO with the suspension2-BiVO4The composite material is added into a graphene oxide suspension, magnetic stirring is carried out for 1h, the uniformly stirred solution is placed into a reaction kettle with a polytetrafluoroethylene lining, hydrothermal is carried out for 1h at 110 ℃, and after the reaction is completed, deionized water is used for washing for multiple times until the solution is neutral. Putting into a vacuum drying oven for vacuum drying at 60 ℃ for 12 h. To obtain TiO2-BiVO4-a graphene ternary composite.
Example 3
(1) Respectively weighing bismuth nitrate pentahydrate and ammonium metavanadate according to the molar ratio of 1:1, respectively dissolving the bismuth nitrate pentahydrate and the ammonium metavanadate in 30ml of 2mol/L nitric acid solution and 30ml of 2mol/L sodium hydroxide solution to form A, B solution, slowly adding the solution B into the solution A under the condition of continuous stirring, and carrying out magnetic stirring for 0.5h after dropwise adding to form the precursor solution for synthesizing the bismuth vanadate.
(2) Measuring 75ml of glacial acetic acid in a beaker, slowly dropwise adding 1ml of butyl titanate into the beaker until the solution is milky, and magnetically stirring for 1 hour to obtain the synthetic TiO2The precursor solution of the particles is put into a 100ml reaction kettle and undergoes hydrothermal reaction for 6 hours at 160 ℃. Washing with anhydrous ethanol and deionized water for several times, drying in a vacuum drying oven for 12h, and calcining at 700 deg.C for 2h to obtain petal-shaped and nano-grade TiO2。
(3) Preparing 1L of CTAB solution of 10g/L according to BiVO4：TiO2Weighing 0.4318 g of TiO in a mass ratio of 1.52And measuring 20ml of 10g/L CTAB solution, adding the CTAB solution into the precursor solution of the bismuth vanadate formed in the step (1), and magnetically stirring for 1h to mix uniformly. The hydrothermal reaction temperature is 160 ℃, and the hydrothermal reaction time is 15 h. Washing with anhydrous ethanol and deionized water for multiple times, and drying in a vacuum drying oven at 60 deg.C for 12h to obtain BiVO4/TiO2Composite particles.
(4) Weighing graphene oxide with the mass fraction of 1% in 75ml of absolute ethyl alcohol, ultrasonically dissolving for 1h to form a graphene oxide suspension, and mixing the synthesized TiO2-BiVO4The composite material is added into a graphene oxide suspension, magnetic stirring is carried out for 1h, the uniformly stirred solution is placed into a reaction kettle with a polytetrafluoroethylene lining, hydrothermal is carried out for 1h at 110 ℃, and after the reaction is completed, deionized water is used for washing for multiple times until the solution is neutral. Putting into a vacuum drying oven for vacuum drying at 60 ℃ for 12 h. To obtain TiO2-BiVO4-a graphene ternary composite.
Example 4
(1) Respectively weighing bismuth nitrate pentahydrate and ammonium metavanadate according to the molar ratio of 1:1, respectively dissolving the bismuth nitrate pentahydrate and the ammonium metavanadate in 30ml of 2mol/L nitric acid solution and 30ml of 2mol/L sodium hydroxide solution to form A, B solution, slowly adding the solution B into the solution A under the condition of continuous stirring, and carrying out magnetic stirring for 0.5h after dropwise adding to form the precursor solution for synthesizing the bismuth vanadate.
(2) Measuring 75ml of glacial acetic acid in a beaker, slowly dropwise adding 1ml of butyl titanate into the beaker until the solution is milky, and magnetically stirring for 1 hour to obtain the synthetic TiO2The precursor solution of the particles is put into a 100ml reaction kettle and undergoes hydrothermal reaction for 6 hours at 200 ℃. Washing with anhydrous ethanol and deionized water for several times, drying in a vacuum drying oven for 12h, and calcining at 800 deg.C for 2h to obtain petal-shaped and nano-grade TiO2。
(3) Preparing 1L of CTAB solution of 10g/L according to BiVO4：TiO20.16196TiO is weighed according to the mass ratio of 42And measuring 20ml of 10g/L CTAB solution, adding the CTAB solution into the precursor solution of the bismuth vanadate formed in the step (1), and magnetically stirring for 1h to mix uniformly. The hydrothermal reaction temperature is 200 ℃, and the hydrothermal reaction time is 20 h. Washing with anhydrous ethanol and deionized water for multiple times, and drying in a vacuum drying oven at 60 deg.C for 12h to obtain BiVO4/TiO2Composite particles.
(4) Weighing graphene oxide with the mass fraction of 10% in 75ml of absolute ethyl alcohol, ultrasonically dissolving for 1h to form a graphene oxide suspension, and mixing the synthesized TiO2-BiVO4The composite material is added into the suspension of graphene oxide, magnetic stirring is carried out for 10 hours, the uniformly stirred solution is placed into a reaction kettle with a polytetrafluoroethylene lining, hydrothermal is carried out for 10 hours at 110 ℃, and after the reaction is completed, deionized water is used for washing for multiple times until the solution is neutral. Putting into a vacuum drying oven for vacuum drying at 60 ℃ for 12 h. To obtain TiO2-BiVO4-a graphene ternary composite.
Example 5
10mg/L rhodamine B is prepared for standby, 100ml of 10mg/L rhodamine B solution is measured and put into a beaker which can be filled with circulating cooling water, and 0.1g of BiVO synthesized in the embodiment 1 is added4-TiO2And (3) magnetically stirring the graphene ternary composite material in the dark for 1 hour to achieve adsorption and desorption balance, adding a cut-off filter plate with the particle size of below 420nm into a xenon lamp serving as a light source, introducing circulating cooling water, degrading the graphene ternary composite material for 3 hours under visible light, taking a sample every 0.5 hour, and detecting the concentration change of the graphene ternary composite material under an ultraviolet visible spectrophotometer. As can be seen from FIG. 3, TiO has been hydrothermally synthesized several times2-BiVO4After the graphene ternary composite material is illuminated for 3 hours, the degradation removal rate of 100ml of 10mg/L rhodamine B reaches 99%, and almost complete degradation can be realized.
Example 6
Respectively weighing bismuth nitrate pentahydrate and ammonium metavanadate according to the molar ratio of 1:1, respectively dissolving the bismuth nitrate pentahydrate and the ammonium metavanadate in 30ml of 2mol/L nitric acid solution and 30ml of 2mol/L sodium hydroxide solution to form A, B solution, slowly adding the solution B into the solution A under the condition of continuous stirring, and carrying out magnetic stirring for 0.5h after dropwise adding to form the precursor solution for synthesizing the bismuth vanadate. Putting the mixture into a 100ml reaction kettle, carrying out hydrothermal treatment at 180 ℃ for 10h, washing the mixture for multiple times by using absolute ethyl alcohol and deionized water, and drying the washed mixture in a vacuum drying oven at 60 ℃ for 12h to obtain BiVO4Particles. BiVO in FIGS. 2-34Particles were prepared as in this example.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention is described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or some technical features of the present invention may be equally replaced. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. TiO 22-BiVO4-graphene ternary composite photocatalytic material, characterized by a square micron-sized BiVO4Deposit petal-shaped nano TiO on the surface2TiO formed by the two2-BiVO4The composite material is uniformly deposited on the surface of the graphene;
the preparation method of the ternary composite photocatalytic material comprises the following steps:
(1) adding butyl titanate into glacial acetic acid until the solution is milky, and stirring to obtain the synthetic TiO2Carrying out hydrothermal reaction on the precursor solution of the particles, and then washing, drying and calcining to obtain petal-shaped TiO2(ii) a The temperature of the hydrothermal reaction is 140-200 ℃, and the time is 5-10 h;
(2) dissolving bismuth nitrate pentahydrate in a nitric acid solution to obtain a solution A; dissolving ammonium metavanadate in a sodium hydroxide solution to obtain a solution B; slowly dropping the solution B into the solution A, andmagnetically stirring to obtain synthetic BiVO4A precursor liquid of the particles;
(3) adding TiO into the mixture2Adding the mixture and CTAB solution into the step (2) for synthesizing BiVO4Uniformly stirring and mixing the precursor solution of the particles, carrying out hydrothermal reaction, and then washing and drying to obtain BiVO4/TiO2Composite particles; the temperature of the hydrothermal reaction is 140-200 ℃, and the time is 5-20 h;
(4) dissolving graphene oxide in an absolute ethyl alcohol solution, and performing ultrasonic dispersion to obtain a graphene oxide suspension; BiVO obtained in the step (3)4/TiO2Adding the composite particles into the graphene oxide suspension, stirring, carrying out hydrothermal reaction, then washing to be neutral, and drying to obtain the TiO2-BiVO4-a graphene ternary composite photocatalytic material; the hydrothermal reaction temperature is 100-120 ℃ and the time is 1-6 h.
2. The preparation method of the three-component composite photocatalytic material as recited in claim 1, comprising the steps of:
(1) adding butyl titanate into glacial acetic acid until the solution is milky, and stirring to obtain the synthetic TiO2Carrying out hydrothermal reaction on the precursor solution of the particles, and then washing, drying and calcining to obtain petal-shaped TiO2(ii) a The temperature of the hydrothermal reaction is 140-200 ℃, and the time is 5-10 h;
(2) dissolving bismuth nitrate pentahydrate in a nitric acid solution to obtain a solution A; dissolving ammonium metavanadate in a sodium hydroxide solution to obtain a solution B; slowly dripping the solution B into the solution A, and magnetically stirring to obtain the synthetic BiVO4A precursor liquid of the particles;
(3) adding TiO into the mixture2Adding the mixture and CTAB solution into the step (2) for synthesizing BiVO4Uniformly stirring and mixing the precursor solution of the particles, carrying out hydrothermal reaction, and then washing and drying to obtain BiVO4/TiO2Composite particles; the temperature of the hydrothermal reaction is 140-200 ℃, and the time is 5-20 h;
(4) dissolving graphene oxide in absolute ethyl alcohol solutionPerforming ultrasonic dispersion to obtain a graphene oxide suspension; BiVO obtained in the step (3)4/TiO2Adding the composite particles into the graphene oxide suspension, stirring, carrying out hydrothermal reaction, then washing to be neutral, and drying to obtain the TiO2-BiVO4-a graphene ternary composite photocatalytic material; the hydrothermal reaction temperature is 100-120 ℃ and the time is 1-6 h.
3. The preparation method according to claim 2, wherein in the step (1), the calcining temperature is 500-800 ℃ and the time is 1-2 h.
4. The method according to claim 2, wherein in the step (2), the concentration of the nitric acid solution is 1 to 3mol/L, and the concentration of the sodium hydroxide solution is 1 to 3 mol/L.
5. The preparation method according to claim 2, wherein in the step (2), the molar ratio of bismuth nitrate to ammonium metavanadate is 1: 0.5-1: 2.
6. The production method according to claim 2, wherein in the step (3), BiVO4/TiO2BiVO in composite particle4：TiO2The mass ratio is 0.25-4: 1.
7. The method according to claim 2, wherein in the step (3), the concentration of the CTAB solution is 5g/L to 15 g/L.
8. The preparation method according to claim 2, wherein in the step (4), the mass fraction of the graphene oxide suspension is 1-10%.
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