CN115196669A - Zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material and preparation method and application thereof - Google Patents

Zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material and preparation method and application thereof Download PDF

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CN115196669A
CN115196669A CN202210628855.3A CN202210628855A CN115196669A CN 115196669 A CN115196669 A CN 115196669A CN 202210628855 A CN202210628855 A CN 202210628855A CN 115196669 A CN115196669 A CN 115196669A
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zinc
sulfide
molybdenum disulfide
semiconductor material
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徐芬
王颖晶
孙立贤
李亚莹
王瑜
周天昊
杨瑜锴
劳剑浩
邹勇进
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Guilin University of Electronic Technology
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Abstract

The invention discloses a zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material, which is prepared by taking L-tryptophan, zinc acetate and stannic chloride pentahydrate as raw materials through a first hydrothermal reaction to prepare zinc stannate, and then taking thioacetamide as a sulfur source and ammonium molybdate as a molybdenum source through a second hydrothermal reaction; the microscopic morphology is that molybdenum disulfide is in lamellar knot, and tin sulfide and zinc sulfide are nanoparticles and are uniformly loaded on the surface of the molybdenum disulfide lamellar. The preparation method comprises the following steps: step 1, zinc stannate Zn 2 SnO 4 Preparing; and 2, preparing the zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material. As an application of degrading methylene blue, when the concentration of the methylene blue is degraded by photocatalysis to 10 mg/L, the degradation rate of the methylene blue reaches 90.6-98.7% within 60 min, and the degradation rate is 0.0366-0.0994 min ‑1 . When the method is used for degrading rhodamine B, the degradation rate of the rhodamine B reaches 99.5 percent within 100 min when the concentration of the rhodamine B is degraded by photocatalysis to 10 mg/L.

Description

Zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of environmental material preparation, and particularly relates to a zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material, and a preparation method and application thereof.
Background
With the rapid development of global industry and the continuous deterioration of ecological environment, the research and development of materials for efficiently degrading organic dyes in industrial wastewater by using solar energy has become a hotspot of current research; semi-so far, various photocatalysts for water pollution remediation, such as metal oxides, metal sulfides, layered double oxides, and the like, have been developed through the efforts of researchers. Unfortunately, most of them are active only under uv irradiation, some of which absorb visible light in a narrow range. While other photocatalytic reaction processes that absorb visible light are less stable: for example, photo-etching can occur in CdS. Photocatalysts having high stability, relatively large productivity and good activity for photocatalytic reactions are still under search. Finding a new high efficiency photocatalyst remains a difficult task from both experimental and theoretical perspectives.
For the photocatalyst, the main idea for improving the photocatalytic performance is as follows: the light energy utilization efficiency is improved, the electron transmission speed is increased, and the recombination of photon-generated carriers is inhibited. Wherein, moS 2 Are of interest due to their unique photoelectric properties and visible light absorption, and have been used for carbon dioxide abatement and wastewater treatment. MoS 2 The catalyst has a unique two-dimensional (2D) layered structure, has active sites at the edge, is easy to disperse and attracts much attention, but has poor catalytic performance due to the problems of low photon-generated carrier mobility and the like caused by photo-corrosion and fast recombination of photon-generated electron holes. To improve MoS 2 Various methods such as formation, doping, impregnation and surface modification of binary/ternary layered heterojunctions are used to hinder recombination of active charge carriers.
Aiming at the problem of low carrier mobility, the semiconductor with the function of tuning the band gap and the MoS 2 The material band gap is shortened by compounding, and the sunlight utilization rate is improved.
For example, there is a conventional document 1 (Enhanced Sun-drive Photocalatic and Antibacterial Activities of Flower-Like ZnO @ MoS 2 Nanocomposite' doi: 10.1007/s 11051-019-4710-3), srikanta Karmakar et al realize MoS by using sodium molybdate as molybdenum source and thioacetamide as sulfur source for vulcanization 2 Preparation of nano material, moS within 2 h 2 The photocatalytic degradation rate of methylene blue reaches 40 percent. The technical problem of the technology is that the degradation rate is too low to meet the application requirementAnd (5) obtaining.
In order to improve the degradation rate, a photon-generated electron-hole rapid recombination technology can be adopted, and a multi-component heterostructure with different functions is formed to absorb photons and consume electron-hole pairs so as to inhibit the rapid recombination of photon-generated carriers. The band gap energy is adjusted to match with the semiconductor material with the appropriate energy band position, so that the photo-generated electrons can be guided away in time to inhibit MoS 2 Electron-hole pair recombination effect of (a). Compared with the traditional material, the one-dimensional nano material has higher specific surface area and higher chemical activity, and the preparation of the nano photocatalytic material is also one of the effective ways for improving the photocatalytic efficiency at present.
For example, reference 2 (Inorganic-organic Nanohrid of MoS) 2 PANI for advanced photocatalytic application (doi: 10.1007/s 40089-019-0267-5), shreya Saha et al by simple synthesis of a two-dimensional MoS 2 The nano sheets and the one-dimensional conducting polymer Polyaniline (PANI) form a 3D structure, and the technical effect that the photocatalytic degradation rate of 2 h to methylene blue reaches 30% is achieved. The technical problem of the technology is that the pure MoS 2 The degradation rate of the polyaniline can reach 40 percent, and the degradation rate is reduced to 30 percent after the polyaniline which is a one-dimensional conductive polymer is compounded. According to the research of the inventor, the reason is that the polyaniline is used as a one-dimensional conductive polymer, and only the MoS can be changed in the technical scheme 2 In a microscopic morphology, and improving MoS 2 Poor electron conductivity and the action of nanosheet agglomeration, but does not have an effect on MoS per se 2 Photocatalytic performance, and thus, degradation performance is reduced.
In order to solve the problems, the common knowledge in the field indicates that the ZnS photocatalyst has the characteristics of high piezoelectric coefficient, good optical activity and the like, and can improve the migration speed of photo-generated charge carriers of the material; the SnS is usually taken as a photosensitizer and is introduced into a photocatalytic system, so that most visible light can be absorbed, and the light absorption range of the material is improved.
At present, the successful preparation of ZnS-SnS-MoS does not exist 2 Is applied to the field of photocatalysis.
Disclosure of Invention
The invention provides a zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material and a preparation method and application thereof.
Aiming at the technical problems in the prior art, the invention adopts the following modes to solve the problems:
1. firstly, zinc stannate is used as a precursor, and is vulcanized in the synthesis process, so that a zinc sulfide and tin sulfide composite material is synthesized, and finally, the effect of improving the degradation performance is realized by improving the transmission speed of photoproduction electrons and holes;
2. the zinc stannate nano material and the molybdenum disulfide solution are subjected to hydrothermal compounding, and the method can solve the problem of rapid recombination of photoproduction electron holes of the molybdenum disulfide material;
in order to achieve the purpose of the invention, the invention adopts the technical scheme that:
a zinc sulfide-tin sulfide-molybdenum disulfide multicomponent composite semiconductor material is prepared by taking L-tryptophan, zinc acetate and stannic chloride pentahydrate as raw materials, preparing zinc stannate through a first hydrothermal reaction, and then taking thioacetamide as a sulfur source and ammonium molybdate as a molybdenum source through a second hydrothermal reaction;
the microscopic morphology of the multi-element composite semiconductor material is that molybdenum disulfide is in lamellar knot, and tin sulfide and zinc sulfide are nanoparticles and are uniformly loaded on the surface of a molybdenum disulfide lamellar.
A preparation method of a zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material comprises the following steps:
step 1, zinc stannate Zn 2 SnO 4 The preparation method comprises the steps of weighing L-tryptophan, zinc acetate and stannic chloride pentahydrate according to a certain mass ratio, then adding water to the L-tryptophan, the zinc acetate and the stannic chloride pentahydrate for mixing to obtain a solution A, finally, carrying out a first hydrothermal reaction on the solution A under a certain condition, and washing and drying an obtained product to obtain zinc stannate;
in the step 1, the mass ratio of L-tryptophan, zinc acetate and stannic chloride pentahydrate is 5:2:1;
in the step 1, the conditions for mixing to obtain the solution A are that L-tryptophan is heated in a water bath at 60 ℃ until being dissolved, then zinc acetate and stannic chloride pentahydrate are added and stirred for 10 min, then 5 ml of 7 mol/L NaOH is slowly dropped to adjust the pH =10, and stirring is continued for 30 min to obtain the solution A;
in the step 1, the conditions of the first hydrothermal reaction are that the reaction temperature is 200 ℃ and the reaction time is 24 hours;
in the step 1, the drying condition is that the drying temperature is 60 ℃ and the drying time is 6 h.
And 2, preparing the zinc sulfide-tin sulfide-molybdenum disulfide multi-component composite semiconductor material, namely weighing thioacetamide, ammonium molybdate and zinc stannate obtained in the step 1 according to a certain mass ratio, then adding water to the thioacetamide, ammonium molybdate and the zinc stannate for mixing to obtain reaction liquid B for carrying out a second hydrothermal reaction, and washing, centrifuging and drying the obtained precipitate to obtain the zinc sulfide-tin sulfide-molybdenum disulfide multi-component composite semiconductor material.
In the step 2, the mass ratio of thioacetamide to ammonium molybdate to zinc stannate is 140:110: (11-17);
in the step 2, the condition for mixing to obtain the reaction liquid B is that thioacetamide and ammonium molybdate are added into 60 ml deionized water and subjected to ultrasonic treatment for 30 min, and then zinc stannate is added and subjected to ultrasonic treatment for 30 min to obtain the reaction liquid B;
in the step 2, the conditions of the second hydrothermal reaction are that the reaction temperature is 200 ℃ and the reaction time is 24 hours.
An application of zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material as a material for degrading methylene blue is characterized in that when the methylene blue with the concentration of 10 mg/L is degraded in a photocatalysis manner, the degradation rate of the methylene blue reaches 90.6-98.7% within 60 min, and the degradation rate is 0.0366-0.0994 min -1
7. The application of the zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material as degradation rhodamine B is characterized in that when the rhodamine B with the concentration of 10 mg/L is degraded in a photocatalytic manner, the degradation rate of the rhodamine B reaches 99.5% within 100 min.
The technical effects of the invention are detected by experiments, and the specific contents are as follows:
XRD detection shows that: znS-SnS-MoS 2 The three-phase combination has good crystal form and is successfully compounded.
According to TEM detection, the following results are obtained: moS 2 In lamellar morphology, znS-SnS-MoS 2 ZnS-SnS nano particles loaded on MoS 2 Microstructure on the ply.
XPS detection shows that: znS-SnS-MoS 2 There are characteristic peaks of Sn 3d, zn 2p, mo 3d and S2 p, and no other impurities.
Therefore, the experimental detection of TEM, XRD, XPS and the like shows that the ZnS-SnS-MoS of the invention 2 Compared with the prior art, the method has the following advantages:
1. ZnS-SnS-MoS prepared by the invention 2 The adopted multi-component composition has the photocatalytic degradation rate of 98.7% to methylene blue within 1 hour, compared with the MoS prepared by the prior document 1 2 The photocatalytic degradation rate of the-PANI composite material for 2 h to methylene blue reaches 30%, and the ZnS-SnS nano particles to MoS 2 The photocatalytic degradation performance is improved more obviously than that of MoS prepared by the prior document 1 2 PANI has a faster photocatalytic degradation rate.
2. ZnS-SnS-MoS prepared by the invention 2 Ammonium molybdate is selected as the molybdenum source, and compared with the molybdenum source of the prior document 2, the molybdenum source is sodium molybdate, and the ammonium molybdate is ZnS-SnS-MoS using the molybdenum source of ZnS-SnS-MoS 2 Has better photocatalytic degradation performance.
Description of the drawings:
FIG. 1 shows ZnS-SnS-MoS prepared in examples 1, 2, 3 and 5 of the present invention 2 And MoS prepared in comparative example 4 2 The X-ray diffraction pattern and the PDF card;
FIG. 2 shows ZnS-SnS-MoS prepared in example 1 2 And MoS prepared in comparative example 4 2 XPS spectra of (1);
FIG. 3 shows ZnS-SnS-MoS prepared in example 1 of the present invention 2 A transmission electron micrograph;
FIG. 4 shows ZnS-SnS-MoS prepared in example 1 of the present invention 2 High definition transmission electron microscopy images of;
FIG. 5 shows ZnS-SnS-MoS prepared in example 1 of the present invention 2 EDS spectrum of (a);
FIG. 6 shows examples 1 and 2 of the present invention,ZnS-SnS-MoS prepared in example 3 and comparative example 5 2 And MoS prepared in comparative example 4 2 The degradation graph corresponds to the degradation graph when the methylene blue dye wastewater is degraded by photocatalysis;
FIG. 7 shows ZnS-SnS-MoS prepared in examples 1, 2, 3 and 5 of the present invention 2 And MoS prepared in comparative example 4 2 The corresponding degradation kinetics mechanical diagram when the methylene blue dye wastewater is degraded by photocatalysis;
FIG. 8 shows ZnS-SnS-MoS prepared in example 1 of the present invention 2 A corresponding degradation map when the rhodamine B dye is degraded in a photocatalysis mode;
FIG. 9 shows ZnS-SnS-MoS prepared in example 1 and comparative examples 1 and 2 according to the present invention 2 The degradation graph corresponds to the degradation graph when the methylene blue dye wastewater is degraded by photocatalysis;
FIG. 10 shows ZSM-prepared in comparative example 3 of the present inventionsDegradation graphs corresponding to those of the ZSM-15 prepared in example 1 when degrading methylene blue dye wastewater;
FIG. 11 is an X-ray diffraction pattern and Zn for ZSM-s prepared in example 4 of the present invention and ZSM-15 prepared in example 1 2 SnO 4 The PDF card of (1).
FIG. 12 MoS prepared according to comparative example 4 of the invention 2 Transmission electron microscopy of the photocatalyst.
Detailed Description
The present invention will be described in further detail by way of examples, but the present invention is not limited thereto, with reference to the accompanying drawings.
The invention is further illustrated by the following specific examples in conjunction with the accompanying drawings; wherein the zinc sulfide-tin sulfide-molybdenum disulfide multicomponent composite semiconductor material is ZnS-SnS-MoS for short 2
Example 1
MoS 2 And Zn 2 SnO 4 The preparation method of the zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material with the mass ratio of 100 comprises the following steps:
step 1, zinc stannate Zn 2 SnO 4 The preparation of (1) is carried out by weighing 0.4 g of L-tryptophan, 0.2214 g of zinc acetate and 0.263 g of tetrahydrateTin chloride, heating L-tryptophan in a water bath at 60 ℃ until the L-tryptophan is dissolved, adding zinc acetate and tin tetrachloride pentahydrate, stirring for 10 min, slowly dropping 5 ml of 7 mol/L NaOH to adjust the pH of the solution to be =10, continuously stirring for 30 min to obtain a solution A, finally carrying out a first hydrothermal reaction on the solution A at a reaction temperature of 200 ℃ for 24 h, washing the obtained product with absolute ethyl alcohol for 3 times, and drying at a drying temperature of 60 ℃ for 6 h to obtain zinc stannate, zn for short 2 SnO 4
Step 2, preparing a zinc sulfide-tin sulfide-molybdenum disulfide multi-component composite semiconductor material, namely weighing 0.2214 g of thioacetamide, 0.263 g of ammonium molybdate and 0.024 g of zinc stannate obtained in the step 1, then adding the thioacetamide and the ammonium molybdate into 60 ml of deionized water, carrying out ultrasonic treatment for 30 min, then adding the zinc stannate, carrying out ultrasonic treatment for 30 min to obtain a reaction solution B, finally carrying out a second hydrothermal reaction on the reaction solution B at the reaction temperature of 200 ℃ for 24 h, and washing, centrifuging and drying the obtained precipitate to obtain the zinc sulfide-tin sulfide-molybdenum disulfide multi-component composite semiconductor material with the mass ratio of 100, which is named as ZSM-15.
To demonstrate the composition of ZSM-15, XRD testing was performed. The test results are shown in figure 1, the ZSM-15 contains characteristic peaks of both tin sulfide, zinc sulfide and molybdenum disulfide, and no other impurity products are present.
To further demonstrate the composition of ZSM-15, XPS testing was performed. The test results are shown in fig. 2, the ZSM-15 contains characteristic peaks of Sn 3d, zn 2p, mo 3d, and S2 p together, and no other impurity products are present.
To demonstrate the microscopic morphology of ZSM-15, TEM and EDS tests were performed. The test results are shown in fig. 3, fig. 4 and fig. 5, and the EDS results indicate that Sn, zn, mo and S elements exist on the surface of the ZSM-15, and the microscopic morphology of the ZSM-15 is that tin sulfide and zinc sulfide nanoparticles are supported on the surface of the molybdenum disulfide layer, as can be seen by combining with the TEM.
ZnS-SnS-MoS 2 The photocatalytic degradation performance test method comprises the following specific steps: preparing a methylene blue dye solution with the concentration of 10 mg/L50 ml, weighing 0.01 g ZnS-SnS-MoS 2 Adding the solution into prepared methylene blue solution, carrying out dark treatment for 30 min under a stirring state, turning on a xenon lamp to simulate sunlight for carrying out a degradation experiment, and testing the photocatalytic degradation performance of the solution.
The photocatalytic degradation performance test result of the ZSM-15 is shown in figure 6 and table 1, and the degradation rate of the ZSM-15 to the dye is 98.7%; in order to more intuitively prove the performance of the catalyst, the degradation rate of the ZSM-15 is calculated, and the result is shown in FIG. 7, wherein the degradation rate of the ZSM-15 is 0.0994 min -1
TABLE 1 starting materials and ZSM-xPerformance meter (2)
Figure DEST_PATH_IMAGE001
In order to prove universality of ZSM-15 photocatalytic degradation effect, photocatalytic degradation performance test is carried out on rhodamine B, and particularly, the degradation rate of rhodamine B is particularly indicated as the degradation rate of rhodamine B, and if the degradation rate is not indicated, the degradation rate of rhodamine B is the degradation rate of methylene blue. The test result is shown in figure 8, and the degradation rate of the ZSM-15 to rhodamine B within 100 min reaches 99.5%. Therefore, ZSM-15 has universality for photocatalytic degradation of various pollutants.
To demonstrate the effect of molybdenum source on the composite, comparative example 1 was provided according to the controlled variable method, znS-SnS-MoS in which sodium molybdate was used as the molybdenum source prepared by substituting sodium molybdate for ammonium molybdate 2
Comparative example 1
ZnS-SnS-MoS with sodium molybdate as molybdenum source 2 The preparation process of (1) is the same as that of example 1 except that: in the step 2, sodium molybdate is used for replacing ammonium molybdate, and the obtained material is named as ZSM-mn.
The result of the ZSM-mn photocatalytic degradation test is shown in FIG. 9, the photocatalytic degradation rate is 86.8% within 60 min, and the concentration of methylene blue is 10 mg/L, which is lower than the 98.7% of the ZSM-15 obtained in example 1.
As can be seen from a comparison of example 1 and comparative example 1, ammonium molybdate is superior to sodium molybdate as the molybdenum source, and, at the same time, it is demonstrated that ammonium molybdate and sodium molybdate can not be simply replaced, collectively, as molybdenum salts.
To demonstrate the effect of sulfur source on the composite material, znS-SnS-MoS of comparative example 2, prepared by substituting sodium sulfide for thioacetamide with a sulfur source of sodium sulfide, was provided according to the controlled variable method 2
Comparative example 2
ZnS-SnS-MoS with sodium sulfide as sulfur source 2 The same procedure as in example 1 except that: in the step 2, sodium sulfide is used for replacing thioacetamide, and the obtained material is named ZSM-ns.
The result of the ZSM-ns photocatalytic degradation test is shown in FIG. 9, the photocatalytic degradation is carried out within 60 min, and the photocatalytic degradation rate is 64.7% when the methylene blue concentration is 10 mg/L, which is far lower than the 98.7% photocatalytic degradation rate of the ZSM-15 obtained in example 1.
It can be seen from a comparison of example 1 and comparative example 2 that thioacetamide is superior to sodium sulfide as a sulfur source and, at the same time, demonstrates that the combination of sulfide, thioacetamide and sodium sulfide cannot be simply replaced.
Furthermore, by combining comparative example 1 and comparative example 2, the following conclusions can be reached in comparison with example 1: according to the principle, the nitrogen-containing compound with ammonium or amine can be decomposed into ammonia gas to volatilize, the experimental phenomenon is that after the hydrothermal reaction is finished, obvious ammonia gas smell can appear, the gas production process plays a role in dispersing a lamellar structure and a pore-forming agent on a microscopic level, namely the effect of improving the specific surface area of the material is achieved, and finally the catalytic performance of the material is improved.
To demonstrate the effect of the preparation process on the composite material, comparative example 3 was provided, in which stirring was used instead of ultrasonication in the operation of adding zinc stannate in step 2, to prepare ZnS-SnS-MoS obtained by stirring 2
Comparative example 3
ZnS-SnS-MoS obtained by stirring 2 The same procedure as in example 1 except that: in the step 2, stirring is used for replacing ultrasonic, and the obtained product is named as ZSM-s.
To demonstrate the composition of ZSM-s, XRD testing was performed. The results are shown in FIG. 10, where ZSM-s contains Zn 2 SnO 4 And MoS 2 Characteristic peak of (2). Compared with the XRD test result of example 1, the composition obtained by ultrasonic treatment and stirring has substantial difference, namely ZnS and SnS are successfully prepared by ultrasonic treatment. According to the common knowledge in the art, zn 2 SnO 4 Does not have photocatalytic performance. Therefore, the preparation process, namely ultrasound, can prove to have obvious influence on the components of the composite material, and further have obvious influence on the photocatalytic performance of the composite material.
The results of the photocatalytic degradation test of ZSM-s are shown in FIG. 11, and the photocatalytic degradation rate is 94.3% within 60 min when the methylene blue concentration is 10 mg/L. The experimental result proves the conclusion that the photocatalytic performance of the ultrasonic composite material has obvious influence.
To demonstrate the effect of loaded ZnS and SnS on composites, comparative example 4 was provided without Zn addition 2 SnO 4 MoS of 2
Comparative example 4
MoS 2 The preparation process of (1) is the same as that of example 1 except that: step 1 is not carried out, and simultaneously, step 2 does not add Zn obtained in step 1 2 SnO 4 The obtained material is named MoS 2
To demonstrate the effect of ZnS-SnS on the micro-morphology, on MoS 2 The TEM test was performed. The results of the tests are shown in FIG. 12, and the MoS obtained 2 Is of a lamellar structure. As compared with example 1, the MoS of ZSM-15 was found 2 ZnS-SnS particles are attached to the surface.
MoS 2 The photocatalytic degradation test results are shown in fig. 6 and table 1, the photocatalytic degradation is carried out within 60 min, and the degradation rate is 42.5% when the concentration of methylene blue is 10 mg/L; for more visual demonstration of the catalystPerformance, to MoS 2 The degradation rate of (2) was calculated, and the results are shown in FIG. 7, moS 2 The degradation rate of (2) is 0.0085 min -1 . The experimental result shows that the degradation rate of the ZSM-15 composite material is obviously higher than that of MoS under the same degradation condition 2 The degradation rate of the material is improved by 11.7 times. According to the TEM test result, the remarkable improvement of the degradation performance is derived from MoS 2 After hydrothermal compounding, znS-SnS particles are attached to the surface of the composite material, namely the ZnS and SnS loaded composite material is proved to be capable of effectively improving degradation performance.
In order to prove the mass percentage ratio of zinc sulfide to tin sulfide to molybdenum disulfide of ZnS-SnS-MoS 2 Effect of degradation Properties, examples 2, 3 and comparative example 5 are provided to prepare MoS 2 And Zn 2 SnO 4 ZnS-SnS-MoS for the following materials in mass ratios of 100 2
Comparative example 5
MoS 2 And Zn 2 SnO 4 ZnS-SnS-MoS with a mass ratio of 100 2 The same procedure as in example 1 except that: in the step 3, zn is added 2 SnO 4 The mass of (b) was 0.0176 g, and the obtained product was named ZSM-11.
The results of the photocatalytic degradation test of ZSM-11 are shown in FIG. 6 and Table 1, and the photocatalytic degradation rate is 64.4% when the methylene blue concentration is 10 mg/L and the photocatalytic degradation is degraded within 60 min.
Example 2
MoS 2 And Zn 2 SnO 4 ZnS-SnS-MoS with the mass ratio of (100) 2 The same procedure as in example 1 except that: in the step 3, zn is added 2 SnO 4 The mass of (b) was 0.0208 g, and the obtained product was named ZSM-13.
The results of the ZSM-13 photocatalytic degradation test are shown in FIG. 6 and Table 1, and the photocatalytic degradation rate is 93.5% at a methylene blue concentration of 10 mg/L within 60 min.
Example 3
MoS 2 And Zn 2 SnO 4 ZnS-SnS-MoS with the mass ratio of 100 2 The same procedure as in example 1 except that: in the step 3, zn is added 2 SnO 4 Was found to have a mass of 0.0272 g, and the obtained product was named ZSM-17.
The results of the photocatalytic degradation test of ZSM-17 are shown in FIG. 6 and Table 1, and the photocatalytic degradation rate is 90.6% when the methylene blue concentration is 10 mg/L and the photocatalytic degradation is degraded within 60 min.
As can be seen from the examples 1, 2, 3 and 5, the ZSM-15 in the example 1 has the best effect of removing methylene blue, the degradation efficiency is 98.7%, and the degradation rate is 0.0994 min -1 . The result shows that the ZnS-SnS-MoS with the mass ratio of 100 2 Has the best photocatalytic degradation performance.
By means of the examples and comparative examples provided by the present invention, the following conclusions can be drawn:
1. the material performance is obviously improved because the multi-component photocatalyst is adopted, the separation efficiency of electrons and holes in a semiconductor is improved, a multi-interface heterojunction is formed, and the photocatalytic activity is improved;
2. ammonium molybdate and thioacetamide are used as molybdenum sources and sulfur sources which cannot be replaced by the composite material;
3. the dispersion method of the raw materials plays a critical role in synthesizing the product.
Therefore, the obtained semiconductor material can fully exert the photocatalytic performance only through the process technology provided by the invention.

Claims (9)

1. A zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material is characterized in that: the method is characterized in that L-tryptophan, zinc acetate and stannic chloride pentahydrate are used as raw materials, zinc stannate is prepared through a first hydrothermal reaction, thioacetamide is used as a sulfur source, ammonium molybdate is used as a molybdenum source, and the zinc stannate is prepared through a second hydrothermal reaction.
2. The production method according to claim 2, characterized in that: the microscopic morphology of the multi-element composite semiconductor material is that molybdenum disulfide is in lamellar knot, and tin sulfide and zinc sulfide are nanoparticles and are uniformly loaded on the surface of a molybdenum disulfide lamellar.
3. A preparation method of a zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material is characterized by comprising the following steps:
step 1, zinc stannate Zn 2 SnO 4 The preparation method comprises the steps of weighing L-tryptophan, zinc acetate and stannic chloride pentahydrate according to a certain mass ratio, then adding water to the L-tryptophan, the zinc acetate and the stannic chloride pentahydrate for mixing to obtain a solution A, finally, carrying out a first hydrothermal reaction on the solution A under a certain condition, and washing and drying an obtained product to obtain zinc stannate;
and 2, preparing the zinc sulfide-tin sulfide-molybdenum disulfide multi-component composite semiconductor material, namely weighing thioacetamide, ammonium molybdate and zinc stannate obtained in the step 1 according to a certain mass ratio, then adding water to the thioacetamide, ammonium molybdate and the zinc stannate for mixing to obtain reaction liquid B for carrying out a second hydrothermal reaction, and washing, centrifuging and drying the obtained precipitate to obtain the zinc sulfide-tin sulfide-molybdenum disulfide multi-component composite semiconductor material.
4. The production method according to claim 3, characterized in that: in the step 1, the mass ratio of L-tryptophan, zinc acetate and stannic chloride pentahydrate is 5:2:1; in the step 2, the mass ratio of thioacetamide to ammonium molybdate to zinc stannate is 140:110: (11-17).
5. The production method according to claim 3, characterized in that: in the step 1, the conditions of the first hydrothermal reaction are that the reaction temperature is 200 ℃ and the reaction time is 24 hours; in the step 2, the conditions of the second hydrothermal reaction are that the reaction temperature is 200 ℃ and the reaction time is 24 hours.
6. The production method according to claim 3, characterized in that: in the step 1, the conditions for mixing to obtain the solution A are that L-tryptophan is heated in a water bath at 60 ℃ until being dissolved, then zinc acetate and stannic chloride pentahydrate are added and stirred for 10 min, then 5 ml of 7 mol/L NaOH is slowly dropped to adjust the pH =10, and stirring is continued for 30 min to obtain the solution A.
7. The production method according to claim 3, characterized in that: in the step 2, the reaction liquid B is obtained by mixing under the condition that thioacetamide and ammonium molybdate are added into 60 ml of deionized water and subjected to ultrasonic treatment for 30 min, and then zinc stannate is added and subjected to ultrasonic treatment for 30 min.
8. The application of the zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material as the degradable methylene blue is characterized in that: when the concentration of the methylene blue is degraded by photocatalysis is 10 mg/L, the degradation rate of the methylene blue reaches 90.6-98.7% within 60 min, and the degradation rate is 0.0366-0.0994 min -1
9. An application of a zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material as degradation rhodamine B is characterized in that: when the concentration of rhodamine B is degraded in a photocatalytic manner to be 10 mg/L, the degradation rate of rhodamine B reaches 99.5 percent within 100 min.
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