CN115672353A - Bi 2 S 3 /Bi 2 WO 6 Heterojunction photocatalytic material and preparation method and application thereof - Google Patents
Bi 2 S 3 /Bi 2 WO 6 Heterojunction photocatalytic material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Bi 2 S 3 /Bi 2 WO 6 A heterojunction photocatalytic material and a preparation method and application thereof belong to the technical field of photocatalysis, and specifically comprise the following steps: (1) Bi 2 WO 6 Preparing; (2) Bi 2 S 3 /Bi 2 WO 6 And (3) preparing the heterojunction photocatalytic material. Also discloses Bi prepared by the preparation method 2 S 3 /Bi 2 WO 6 Heterojunction photocatalytic materials and the use of such Bi are also disclosed 2 S 3 /Bi 2 WO 6 Application of the heterojunction photocatalytic material in photocatalytic reduction of Cr (VI) containing wastewater. The preparation method disclosed by the invention is convenient to popularize, short in synthesis time and excellent in effect, and the prepared Bi 2 S 3 /Bi 2 WO 6 The heterojunction catalyst has wide application prospect in the aspect of actual purification of Cr (VI) -containing water environment.
Description
Technical Field
The invention relates to the field of photocatalysis, in particular to Bi 2 S 3 /Bi 2 WO 6 A heterojunction photocatalytic material, a preparation method and application thereof.
Background
In recent years, rapid development of industrialization causes serious environmental pollution, and particularly industrial wastewater containing heavy metal Cr (VI) has great harm. Cr (VI) comes from industries such as leather, printing and dyeing, metallurgy, electroplating and the like, not only has high water solubility and strong carcinogenic effect, but also is easy to permeate into human bodies through channels such as digestion, respiratory tract, skin and the like so as to seriously affect the health of people, and the reduction of Cr (VI) into nontoxic Cr (III) is an effective method for effectively reducing the harm of Cr (VI). In many methods, the photocatalytic semiconductor technology utilizes sunlight as an energy source, has the characteristics of energy conservation, environmental protection, high efficiency and the like, is a green chemical treatment technology, and has wide prospects in the aspects of environmental cleanness and energy conversion.
Bi 2 WO 6 Is prepared from (WO) 4 ) 2- Layer and (Bi) 2 O 2 ) 2+ The layers alternately form perovskite type oxide, the band gap is about 2.7eV, and the perovskite type oxide has visible light response capability, and has the advantages of good light stability, adjustable structure and performance and the like. However, bi alone 2 WO 6 The system has the problem that electron-hole pairs are easy to recombine, so that the generated active substances are less in quantity, and Bi is hindered 2 WO 6 The method is applied to the actual water pollution treatment. In the prior art, bi is added 2 WO 6 The construction of a heterojunction photocatalyst with another semiconductor is an effective method for improving the visible light catalytic activity thereof. Reported in the literature that Hu et al converts CuAlO 2 And Bi 2 WO 6 Grinding for 6h to obtain CuAlO 2 /Bi 2 WO 6 Heterojunction, and the reduction efficiency of Cr (VI) is 98.8% under visible light illumination for 150 min; lu et al prepared by solvothermal method at 220 ℃ to obtain CoO/Bi 2 WO 6 The reduction efficiency of Cr (VI) of the heterojunction under visible light for 90 min is 57.5%, and the degradation efficiency of tetracycline is 90.7%.
Although Bi is as described above 2 WO 6 The catalytic activity of the base composite photocatalyst is improved to a certain extent, but the preparation of the material is complex, the synthesis time is long, the reduction activity of Cr (VI) in a solution is general, and even the pH value is regulated by acid to improve the reduction efficiency of Cr (VI), and the problems are not favorable for large-scale production and application.
Therefore, how to provide a material which is simple to prepare and has strong reduction activity for Cr (VI) in wastewater is a technical problem that needs to be solved by those skilled in the art.
Disclosure of Invention
The object of the present invention is to provide a Bi 2 S 3 /Bi 2 WO 6 A heterojunction photocatalytic material, a preparation method and an application thereof are provided to solve the problems of the prior art.
In order to achieve the purpose, the invention provides the following scheme:
bi 2 S 3 /Bi 2 WO 6 The preparation method of the heterojunction photocatalytic material specifically comprises the following steps:
(1) Mixing acetic acid solution of pentahydrate bismuth nitrate and aqueous solution of sodium tungstate dihydrate, heating by microwave, cooling, washing and drying to obtain Bi 2 WO 6 ；
(2) The Bi is added 2 WO 6 Mixing the aqueous solution and thioacetamide solution, heating by microwave, cooling, washing and drying to obtain the Bi 2 S 3 /Bi 2 WO 6 A heterojunction photocatalytic material.
Advantageous effects: among the different types of heterojunctions, the Z-type heterojunction, in particular, is a relatively efficient photocatalyst, and compared with the II-type heterojunction, the Z-type heterojunction has a higher energy level for electrons and a lower energy level for holes, thereby having a stronger redox capability. The invention adopts a microwave hydrothermal method to prepare Bi 2 S 3 /Bi 2 WO 6 Heterojunction photocatalytic material, bi selected for 2 WO 6 And Bi 2 S 3 In the band structure, bi 2 S 3 The material has better visible light absorption capability and excellent physicochemical characteristics due to the narrower band gap structure (1.7 eV), and Bi 2 WO 6 Has large specific surface area, and the formation of the Z-type heterojunction effectively reserves the strong oxidation-reduction capability of electrons and holes and can promote the electrons in Bi 2 S 3 The accumulation of the surface increases the electronegativity of the surface, which is beneficial to realizing the adsorption of Cr (VI), therefore, the Bi provided by the invention 2 S 3 /Bi 2 WO 6 The Z-type heterojunction photocatalytic material has higher capability of photocatalytic reduction of Cr (VI).
Preferably, the molar ratio of the bismuth nitrate pentahydrate to the sodium tungstate dihydrate in the step (1) is (1-3): 1;
the concentration of the acetic acid solution of the bismuth nitrate pentahydrate is 0.5-0.6 mol.L -1 ；
The concentration of the aqueous solution of sodium tungstate dihydrate is 0.05 mol.L -1 。
Has the advantages that: the molar ratio of bismuth nitrate pentahydrate to sodium tungstate dihydrate in the present invention is based on the formation of Bi 2 WO 6 The required raw material mole ratio is determined; addition of a proper amount of acetic acid can promote spherical Bi 2 WO 6 The product formation is more regular.
Preferably, the microwave heating temperature in the step (1) is 145-170 ℃, and the heating time is 90-110 min.
Has the beneficial effects that: the photocatalyst synthesized by the microwave-assisted hydrothermal method has the advantages of being green, simple and convenient, easy to regulate and control, capable of promoting efficient reaction, lower in cost and capable of realizing batch production.
Preferably, the thioacetamide is reacted with Bi in step (2) 2 WO 6 The mass ratio of (2-8) to (100);
the thioacetamide solution is thioacetamide aqueous solution, and the concentration is 0.2-0.8 g. L -1 ；
The Bi 2 WO 6 The concentration of the aqueous solution of (1) is 10 g.L -1 。
Has the advantages that: the invention adds proper amount of sulfur source into Bi 2 WO 6 Surface in-situ growth of Bi 2 S 3 The two materials are tightly combined together, and the heterojunction material has stronger photoresponse performance while promoting the separation of photon-generated carriers.
Preferably, the microwave heating temperature in the step (2) is 50-65 ℃, and the microwave heating time is 5-20 min.
Has the advantages that: the sulfur source and the cation in the invention are combined in a covalent bond form and grow by nucleation, and the ionic activity can be reduced by synthesizing at a milder temperature, so that Bi is enabled 2 S 3 Is very uniform in size distribution. In addition, the synthesis in the temperature range is extremely safe.
Bi 2 S 3 /Bi 2 WO 6 Bi prepared by preparation method of heterojunction photocatalytic material 2 S 3 /Bi 2 WO 6 A heterojunction photocatalytic material.
Has the advantages that: compared with the same type of catalyst obtained by other preparation methods, the Bi of the invention 2 S 3 /Bi 2 WO 6 The preparation method of the heterojunction photocatalyst has the advantages of lower synthesis temperature and shorter reaction time. Also, bi prepared by the present invention 2 S 3 /Bi 2 WO 6 The heterojunction photocatalyst has high visible light activity and stable chemical property, and has good reusability. Meanwhile, the Bi prepared by the invention 2 S 3 /Bi 2 WO 6 The heterojunction photocatalyst has stronger anti-interference capability and practicability, has better photo-reduction Cr (VI) activity in industrial wastewater containing Cr (VI), and can be used in sunlightPotential for scale reduction of Cr (VI).
Bi 2 S 3 /Bi 2 WO 6 Application of the heterojunction photocatalytic material in photocatalytic reduction of Cr (VI) -containing wastewater.
More preferably, the wastewater containing Cr (VI) is industrial wastewater containing Cr (VI) or simulated wastewater containing Cr (VI).
The industrial wastewater containing Cr (VI) is the actual industrial wastewater of Yunnan Luliang chemical industry Co.
More preferably, the Bi 2 S 3 /Bi 2 WO 6 The application of the heterojunction photocatalytic material in photocatalytic reduction of Cr (VI) -containing wastewater specifically comprises the following steps:
adding Bi 2 S 3 /Bi 2 WO 6 Placing in Cr (VI) -containing wastewater, stirring for 60min in a dark place, then reducing Cr (VI) into Cr (III) by illumination, centrifuging 3mL of supernate at intervals of 10min for 10min, and measuring the absorbance.
The illumination time is 0.5-2 h;
the mass concentration of Cr (VI) in the industrial wastewater containing Cr (VI) is 10-80 mg.L -1 ；
The volume of the industrial wastewater containing Cr (VI) is 50-3000 mL;
the Bi 2 S 3 /Bi 2 WO 6 The dosage of the Cr (VI) in the industrial wastewater is 0.5 to 5 g.L -1 。
The invention discloses a Bi 2 S 3 /Bi 2 WO 6 Heterojunction photocatalytic material, preparation method and application thereof, and Bi provided by the invention 2 S 3 /Bi 2 WO 6 The heterojunction composite photocatalyst can efficiently reduce Cr (VI) in water, has a great application prospect in the aspect of reducing Cr (VI) in large-scale practical industrial wastewater under sunlight, is a green, energy-saving and environment-friendly water environment treatment method, and is beneficial to promoting the application of a photocatalytic technology in water environment restoration. In addition, the preparation method of the composite photocatalyst is simple, short in synthesis time, mild in reaction condition, capable of being recycled for many times, and suitable for large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows Bi obtained in example 1 2 WO 6 And Bi 2 S 3 /Bi 2 WO 6 SEM and TEM images of the heterojunction photocatalytic material;
FIG. 2 shows Bi obtained in example 1 2 WO 6 And Bi 2 S 3 /Bi 2 WO 6 XRD pattern of the heterojunction photocatalytic material;
FIG. 3 shows Bi obtained in example 1 2 WO 6 And Bi 2 S 3 /Bi 2 WO 6 A UV-Vis diagram of the heterojunction photocatalytic material;
FIG. 4 shows Bi obtained in example 1 2 WO 6 And Bi 2 S 3 /Bi 2 WO 6 The reduction efficiency of the heterojunction photocatalytic material to Cr (VI) in water under the LED lamp;
FIG. 5 shows Bi obtained in example 1 2 S 3 /Bi 2 WO 6 The recycling effect of the heterojunction photocatalytic material in photocatalytic reduction of Cr (VI) under the LED lamp is achieved;
FIG. 6 shows Bi obtained in example 2 2 S 3 /Bi 2 WO 6 The reduction efficiency of the heterojunction photocatalytic material to Cr (VI) in actual industrial wastewater under sunlight;
FIG. 7 shows Bi obtained in example 7 for examples 1, 5, 6 and comparative example 1 2 S 3 /Bi 2 WO 6 And (3) detecting the reduction efficiency of the heterojunction photocatalytic material to Cr (VI) in water under the LED lamp.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Example 1
Bi 2 S 3 /Bi 2 WO 6 The preparation method of the heterojunction photocatalytic material comprises the following steps:
(1)Bi 2 WO 6 preparation of
Dissolving 3mmol of bismuth nitrate pentahydrate in 4mL of acetic acid, dissolving 1.5mmol of sodium tungstate dihydrate in 21mL of deionized water, then uniformly mixing the two solutions, pouring the mixture into a microwave reaction tube, heating the mixture at 160 ℃ for 100min by microwaves, taking out the reaction tube, cooling the reaction tube to room temperature, washing and drying the product to obtain Bi 2 WO 6 ；
(2)Bi 2 S 3 /Bi 2 WO 6 Preparation of
0.15g of Bi 2 WO 6 Respectively dissolving thioacetamide with the mass ratio of 6% in 20mL of deionized water, then uniformly mixing the two solutions, pouring the mixture into a 100mL microwave reaction tube, placing the microwave reaction tube into a microwave reaction system, heating the mixture for 10min at 60 ℃, cooling the mixture to room temperature, and then washing and drying the mixture to obtain Bi 2 S 3 /Bi 2 WO 6 A heterojunction photocatalytic material.
The technical effects are as follows:
1. bi obtained in step (1) 2 WO 6 Materials and Bi obtained in step (2) 2 S 3 /Bi 2 WO 6 SEM and TEM characteristics of the heterojunction photocatalytic material are shown in figure 1:
wherein (a) is Bi 2 WO 6 Scanning electron microscope images of; (b) Bi 2 S 3 /Bi 2 WO 6 Scanning electron microscope images of; (c) Bi 2 WO 6 Transmission electron microscopy images of; (d) Bi 2 S 3 /Bi 2 WO 6 Transmission electron micrograph (D).
The synthesized Bi can be seen from the portion (a) in FIG. 1 2 WO 6 Is a microsphere structure formed by self-assembling a plurality of flaky nano sheets, and the diameter of the microsphere structure is about 3 mu m; as can be seen from part (b) of FIG. 1, a large amount of Bi 2 S 3 Nanoparticles immobilized on Bi 2 WO 6 The surface and the original microsphere structure are not obviously changed, and a large number of nano particles are loaded on the nano sheet.
2. For Bi obtained in step (1) of example 1 2 WO 6 Material and Bi prepared in step (2) 2 S 3 /Bi 2 WO 6 The materials are respectively subjected to XRD characterization, and the test results are shown in figure 2:
it can be seen that Bi 2 WO 6 The characteristic peaks of the (113), (200), (220) and (313) crystal faces are obvious, bi 2 S 3 /Bi 2 WO 6 In the material Bi 2 WO 6 Sharp characteristic peak, indicating Bi 2 S 3 /Bi 2 WO 6 Bi in heterojunction photocatalytic material structure 2 WO 6 The crystal form is not destroyed. In addition, bi was not found 2 S 3 Phase-related distinct diffraction peaks, indicating the synthesized Bi 2 S 3 /Bi 2 WO 6 Bi produced in the sample 2 S 3 Is in a low crystalline or amorphous state.
3. For Bi obtained in step (1) of example 1 2 WO 6 Material and Bi prepared in step (2) 2 S 3 /Bi 2 WO 6 The heterojunction photocatalytic materials are respectively subjected to UV-Vis characterization, and the test results are shown in FIG. 3:
as can be seen, bi obtained in the step (2) of example 1 2 S 3 /Bi 2 WO 6 With the Bi prepared in the step (1) 2 WO 6 In contrast, bi prepared 2 S 3 /Bi 2 WO 6 The material has obvious blue shift in the absorption wavelength region, which shows that Bi 2 S 3 /Bi 2 WO 6 The heterojunction light absorption range is wider, probably because:since Bi 2 S 3 Has smaller band gap and larger absorption coefficient, and enhances Bi 2 S 3 /Bi 2 WO 6 Light absorption properties of the heterostructure.
Example 2
Bi obtained in the step (1) of example 1 2 WO 6 Material and Bi obtained in step (2) 2 S 3 /Bi 2 WO 6 The study on the photocatalytic performance of the heterojunction photocatalytic material specifically comprises the following steps:
at 3 g.L -1 Adding Bi in an amount 2 WO 6 Material and Bi 2 S 3 /Bi 2 WO 6 The heterojunction photocatalytic material is respectively added into two identical 50mL solutions prepared in a laboratory, the concentration of the two solutions is 50 mg.L -1 Stirring the mixture in a water solution of Cr (VI) for 60min in a dark place to ensure that the mixture is in adsorption and desorption equilibrium, and then placing the mixture in a water solution with the power of 450mW/cm 2 The LED lamp is used for simulating illumination, carrying out photocatalytic photoreaction, and centrifuging 3mL of supernate for 10min at certain intervals.
The absorbance of the supernatant after centrifugation was measured by diphenylcarbonyldihydrazide spectrophotometry, and the measurement results are shown in FIG. 4, where Bi is shown 2 S 3 /Bi 2 WO 6 The photocatalytic reduction efficiency of the photocatalyst on Cr (VI) for 30 minutes under the irradiation of the LED reaches 100 percent, and the method is the same as that of Bi prepared in the step (1) of the example 1 2 WO 6 Compared with the material, the Bi prepared in the step (2) 2 S 3 /Bi 2 WO 6 The photocatalytic efficiency of the material is obviously improved.
Example 3
Bi obtained in example 1 2 S 3 /Bi 2 WO 6 The material is subjected to cyclic utilization performance research, and the cyclic utilization performance research comprises the following steps:
the catalyst after the reaction in example 2 was recovered, washed with deionized water, dried for future use, and the above process was repeated with the recovered catalyst, with the recycling effect as shown in fig. 5. After 5 times of recycling, bi 2 S 3 /Bi 2 WO 6 Cr (VI) can be reduced with high efficiency, which shows that the Cr (VI) has excellent stability.
Example 4
Bi 2 S 3 /Bi 2 WO 6 Application of Bi prepared in example 1 in photocatalytic reduction of Cr (VI) in industrial wastewater containing Cr (VI) 2 S 3 /Bi 2 WO 6 The heterojunction photocatalytic material is evaluated by the efficiency of reducing Cr (VI) in actual industrial wastewater under visible light, and comprises the following steps:
at 3 g.L -1 The Bi content in (b) is 50mL, 1L, and 3L of the actual industrial waste liquid containing Cr (VI) ions, respectively 2 S 3 /Bi 2 WO 6 After the heterojunction photocatalytic material is subjected to light-shielding stirring for 60min, the heterojunction photocatalytic material is subjected to adsorption and desorption balance, and then the heterojunction photocatalytic material is placed under the sunlight for photocatalytic photoreaction. 3mL of the supernatant was centrifuged for 10min at 10min intervals. The supernatant after centrifugation was tested for absorbance using diphenylcarbodihydrazide spectrophotometry.
The test results are shown in fig. 6, and it can be seen that the photocatalyst has a Cr (VI) photocatalytic reduction efficiency of 100% in 40 minutes under sunlight irradiation, and still has a good photocatalytic activity in 3L of actual industrial Cr (VI) -containing wastewater.
Example 5
Bi 2 S 3 /Bi 2 WO 6 The preparation method of the heterojunction photocatalytic material comprises the following steps:
(1)Bi 2 WO 6 preparation of (2)
Dissolving 3mmol of bismuth nitrate pentahydrate in 4mL of acetic acid, dissolving 1.5mmol of sodium tungstate dihydrate in 21mL of deionized water, then uniformly mixing the two solutions, pouring the mixture into a microwave reaction tube, heating the mixture at 160 ℃ for 100min by microwaves, taking out the reaction tube, cooling the reaction tube to room temperature, washing and drying the product to obtain Bi 2 WO 6 ；
(2)Bi 2 S 3 /Bi 2 WO 6 Preparation of
0.15g of Bi 2 WO 6 Respectively dissolving thioacetamide with the mass ratio of 2% in 20mL of deionized water, then uniformly mixing the two solutions, pouring the mixture into a 100mL microwave reaction tube, placing the microwave reaction tube into a microwave reaction system, and heating the microwave reaction system at 60 ℃ by using microwavesAfter 10min, cooling to room temperature, and then washing and drying to obtain Bi 2 S 3 /Bi 2 WO 6 A heterojunction photocatalytic material.
Example 6
Bi 2 S 3 /Bi 2 WO 6 The preparation method of the heterojunction photocatalytic material comprises the following steps:
(1)Bi 2 WO 6 preparation of
Dissolving 3mmol of bismuth nitrate pentahydrate in 4mL of acetic acid, dissolving 1.5mmol of sodium tungstate dihydrate in 21mL of deionized water, uniformly mixing the two solutions, pouring the mixture into a microwave reaction tube, heating the mixture at 160 ℃ for 100min by microwaves, taking out the reaction tube, cooling the reaction tube to room temperature, washing and drying the product to obtain Bi 2 WO 6 ；
(2)Bi 2 S 3 /Bi 2 WO 6 Preparation of
0.15g of Bi 2 WO 6 Respectively dissolving thioacetamide with the mass ratio of 8% in 20mL of deionized water, then uniformly mixing the two solutions, pouring the mixture into a 100mL microwave reaction tube, placing the microwave reaction tube into a microwave reaction system, heating the mixture for 10min at 60 ℃, cooling the mixture to room temperature, and then washing and drying the mixture to obtain Bi 2 S 3 /Bi 2 WO 6 A heterojunction photocatalytic material.
Comparative example 1
Bi 2 S 3 /Bi 2 WO 6 The preparation method of the heterojunction photocatalytic material is different from the preparation method of the heterojunction photocatalytic material in that:
(1)Bi 2 WO 6 preparation of
Dissolving 3mmol of bismuth nitrate pentahydrate in 4mL of acetic acid, dissolving 1.5mmol of sodium tungstate dihydrate in 21mL of deionized water, transferring the two mixed solutions to a 100mL polytetrafluoroethylene reaction kettle for hydrothermal reaction under the reaction condition of 160 ℃ for 16h, cooling to room temperature, washing and drying the product to obtain Bi 2 WO 6 ；
(2)Bi 2 S 3 /Bi 2 WO 6 Preparation of
0.15g of Bi 2 WO 6 Respectively dissolving thioacetamide with the mass ratio of 6 percent in 20ml of deionized water, then uniformly mixing the two solutions, and carrying out hydrothermal reaction on the obtained mixed solution at the temperature of 60 ℃ for 2 hours to obtain Bi 2 S 3 /Bi 2 WO 6 A heterojunction photocatalytic material.
Example 7
Bi obtained in the step (2) of example 1 2 S 3 /Bi 2 WO 6 A heterojunction photocatalytic material, denoted as BWS-6; EXAMPLE 5 Bi obtained in step (2) 2 S 3 /Bi 2 WO 6 A heterojunction photocatalytic material, denoted as BWS-2; EXAMPLE 6 Bi obtained in step (2) 2 S 3 /Bi 2 WO 6 A heterojunction photocatalytic material, denoted as BWS-8; comparative example 1 Bi obtained in step (2) 2 S 3 /Bi 2 WO 6 A heterojunction photocatalytic material, named as BWSH-6, is used for carrying out photocatalytic performance research, and specifically comprises the following steps:
at 3 g.L -1 Adding Bi in an amount 2 S 3 /Bi 2 WO 6 The heterojunction photocatalytic material is respectively added into two identical 50mL solutions prepared in a laboratory, the concentration of the two solutions is 50 mg.L -1 Stirring the mixture in a water solution of Cr (VI) for 60min in a dark place to ensure that the mixture is in adsorption and desorption equilibrium, and then placing the mixture in a water solution with the power of 450mW/cm 2 The photocatalytic photoreaction is carried out under the LED lamp, 3mL of supernatant is taken at certain time intervals and centrifuged for 10min.
The absorbance of the centrifuged supernatant was measured by diphenylcarbonyldihydrazide spectrophotometry, and the results are shown in fig. 7, and it can be seen that, after being irradiated for 30min by the LED lamp, the reduction rates of BWSH-6 photocatalyst reduced Cr (VI) prepared by the conventional hydrothermal method in comparative example 1 were only 59.33%, and the reduction rates of BWS-2, BWS-6 and BWS-8 catalyst reduced Cr (VI) were 80.58%, 100.00% and 99.89%, respectively, indicating that BWS-6 has better activity of photo-reduced Cr (VI). Bi is only present in small amounts in BWS-2 samples 2 S 3 Less Bi 2 S 3 In Bi 2 WO 6 The active sites generated on the surface are few, which is not beneficial to the photogeneration of charges, and the photocatalytic efficiency is reduced. Bi with a high BWS-8 content 2 S 3 Covered with the original Bi 2 WO 6 The pore structure and the specific surface area of the material prevent light from reaching Bi 2 WO 6 The surface, the photoresponse ability of the heterojunction is reduced.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (7)
1. Bi 2 S 3 /Bi 2 WO 6 The preparation method of the heterojunction photocatalytic material is characterized by comprising the following steps:
(1) Mixing acetic acid solution of pentahydrate bismuth nitrate and aqueous solution of sodium tungstate dihydrate, heating by microwave, cooling, washing and drying to obtain Bi 2 WO 6 ；
(2) The Bi is added 2 WO 6 Mixing the aqueous solution and thioacetamide solution, heating by microwave, cooling, washing and drying to obtain the Bi 2 S 3 /Bi 2 WO 6 A heterojunction photocatalytic material.
2. The Bi of claim 1 2 S 3 /Bi 2 WO 6 The preparation method of the heterojunction photocatalytic material is characterized in that the molar ratio of bismuth nitrate pentahydrate to sodium tungstate dihydrate in the step (1) is (1-3) to 1;
the concentration of the acetic acid solution of the bismuth nitrate pentahydrate is 0.5-0.6 mol.L -1 ；
The concentration of the aqueous solution of sodium tungstate dihydrate is 0.05 mol.L -1 。
3. The Bi of claim 1 2 S 3 /Bi 2 WO 6 The preparation method of the heterojunction photocatalytic material is characterized in that the microwave heating temperature in the step (1) is 145-170 ℃, and the heating time is90～110min。
4. The Bi of claim 1 2 S 3 /Bi 2 WO 6 The preparation method of the heterojunction photocatalytic material is characterized in that the thioacetamide and the Bi in the step (2) 2 WO 6 The mass ratio of (2-8) to (100);
the thioacetamide solution is a thioacetamide aqueous solution, and the concentration of the thioacetamide solution is 0.2-0.8 g.L -1 ；
The Bi 2 WO 6 The concentration of the aqueous solution of (1) is 10 g.L -1 。
5. The Bi of claim 1 2 S 3 /Bi 2 WO 6 The preparation method of the heterojunction photocatalytic material is characterized in that the microwave heating temperature in the step (2) is 50-65 ℃, and the microwave heating time is 5-20 min.
6. The Bi of any one of claims 1 to 5 2 S 3 /Bi 2 WO 6 Bi prepared by preparation method of heterojunction photocatalytic material 2 S 3 /Bi 2 WO 6 A heterojunction photocatalytic material.
7. The Bi of claim 6 2 S 3 /Bi 2 WO 6 Application of the heterojunction photocatalytic material in photocatalytic reduction of Cr (VI) -containing wastewater.
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