CN115196669B - Zinc sulfide-tin sulfide-molybdenum disulfide multielement composite semiconductor material and preparation method and application thereof - Google Patents

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

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CN115196669B
CN115196669B CN202210628855.3A CN202210628855A CN115196669B CN 115196669 B CN115196669 B CN 115196669B CN 202210628855 A CN202210628855 A CN 202210628855A CN 115196669 B CN115196669 B CN 115196669B
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zinc
sulfide
molybdenum disulfide
semiconductor material
tin
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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 multielement composite semiconductor material, which 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 microstructure of the composite material is that molybdenum disulfide is lamellar, tin sulfide and zinc sulfide are nano particles, and the nano particles are uniformly loaded on the surface of a molybdenum disulfide lamellar. The preparation method comprises the following steps: step 1, zinc stannate Zn 2 SnO 4 Is prepared by the steps of (1); and 2, preparing the zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material. As the application of degrading methylene blue, when the methylene blue with the photocatalytic degradation concentration of 10 mg/L is degraded, 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 rhodamine B with the photocatalytic degradation concentration of 10 mg/L is used for degrading the rhodamine B, the degradation rate of the rhodamine B reaches 99.5% within 100 minutes.

Description

Zinc sulfide-tin sulfide-molybdenum disulfide multielement 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
Along with the rapid development of global industry and continuous deterioration of ecological environment, the research and development of materials for efficiently degrading organic dye in industrial wastewater by utilizing solar energy has become a hot spot of current research; half-way up to now, various photocatalysts for water pollution remediation, such as metal oxides, metal sulfides, layered bimetallic oxides, etc., have been developed through 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 occurs in CdS. Photocatalysts with high stability, relatively great productivity and good photocatalytic activity are still being sought. Finding a new high-efficiency photocatalyst from the experimental and theoretical point of view remains a difficult task.
For the photocatalyst, the main idea of 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 because of their unique photoelectric properties and visible light absorption properties, and have been used for carbon dioxide abatement and wastewater treatment. MoS (MoS) 2 The catalyst has a unique two-dimensional (2D) layered structure, has active sites at the edges, is easy to disperse and has great attention, but has poor catalytic performance due to the problems of low mobility of photo-generated carriers and the like caused by photo-corrosion and rapid recombination of photo-generated electron holes. To improve MoS 2 Various methods such as binary/ternary layered heterojunction formation, doping, dipping, and surface modification are used to hinder the recombination of its active charge carriers.
Aiming at the problem of low carrier mobility, a semiconductor with a band gap tuning function is combined with MoS 2 And the composite material shortens the band gap of the material and improves the sunlight utilization rate.
For example, document 1 (Enhanced Sunlight-Driven Photocatalytic and Antibacterial Activities of Flower-Like ZnO@MoS) 2 Nanocomposite (doi: 10.1007/s 11051-019-4710-3), srikanta Karmakar et al realized MoS by sulfidation using sodium molybdate as the molybdenum source and thioacetamide as the sulfur source 2 Preparation of nanomaterials, moS in 2 h 2 The photocatalytic degradation rate of the methylene blue reaches 40 percent. The technology has the technical problems that the degradation rate is too low to meet the application requirement。
In order to improve the degradation rate, a photo-generated electron-hole rapid recombination technology can be adopted, and photon absorption and electron-hole pair consumption are realized through forming a multi-component heterostructure with different effects, so that rapid recombination of photo-generated carriers is inhibited. The band gap energy is adjusted to match with the semiconductor material with proper band position, so that the photo-generated electrons can be conducted away in time to inhibit MoS 2 Electron-hole pair recombination effects of (c). 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 one of the effective modes for improving the photocatalytic efficiency at present.
For example, document 2 (Inorganic-organic nanohybrid of MoS) 2 -PANI for advanced photocatalytic application (doi: 10.1007/s 40089-019-0267-5), shreya Saha et al by simple synthesis of two-dimensional MoS 2 The 3D structure is formed by the nano-sheet and one-dimensional conductive polymer Polyaniline (PANI), and the technical effect that the photocatalytic degradation rate of 2 h to methylene blue reaches 30% is obtained. The technical problem of the technology is that the pure MoS 2 The degradation rate of the methylene blue can reach 40 percent, and the degradation rate is reduced to 30 percent after the one-dimensional conductive polymer polyaniline is compounded. According to the research of the inventor, the reason is that polyaniline is used as one-dimensional conductive polymer, and only MoS can be changed in the technical scheme 2 Is a micro-morphology of (2) and improves MoS 2 Poor electron conductivity and nanosheets agglomeration, but does not possess a role in MoS itself 2 Photocatalytic properties, and thus degradation properties, are reduced.
In order to solve the above problems, it is known from common knowledge in the art that ZnS photocatalysts have the characteristics of high piezoelectric coefficient, good photoactivity and the like, and can increase the migration velocity of photo-generated charge carriers of materials; snS is often introduced into a photocatalytic system as a photosensitizer, so that most of visible light can be absorbed, and the light absorption range of the material is improved.
At present, no successful ZnS-SnS-MoS preparation exists yet 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 existing 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 degradation performance is realized by improving the transmission speed of photo-generated electrons and holes;
2. the zinc stannate nano material and the molybdenum disulfide solution are subjected to hydrothermal recombination, and the method can solve the problem of rapid recombination of photo-generated electron holes of the molybdenum disulfide material;
in order to achieve the aim of the invention, the invention adopts the following technical scheme:
a zinc sulfide-tin sulfide-molybdenum disulfide multielement 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 preparing the zinc stannate through a second hydrothermal reaction by taking thioacetamide as a sulfur source and ammonium molybdate as a molybdenum source;
the microstructure of the multi-element composite semiconductor material is that molybdenum disulfide is lamellar, tin sulfide and zinc sulfide are nano particles, and the nano particles 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 Weighing L-tryptophan, zinc acetate and tin tetrachloride pentahydrate according to a certain mass ratio, then adding water into the L-tryptophan, the zinc acetate and the tin tetrachloride pentahydrate to mix to obtain a solution A, finally, carrying out a first hydrothermal reaction on the solution A under a certain condition, and washing and drying the obtained product to obtain zinc stannate;
in the step 1, the mass ratio of the L-tryptophan, the zinc acetate and the tin tetrachloride pentahydrate is 5:2:1, a step of;
in the step 1, the condition of obtaining the solution A by mixing is that L-tryptophan is heated in water bath at 60 ℃ until the L-tryptophan is dissolved, then zinc acetate and tin tetrachloride pentahydrate are added, the mixture is stirred for 10 min, then 5 ml of NaOH with the concentration of 7 mol/L is slowly dripped to adjust the pH value of the solution to be 10, and the mixture is continuously stirred for 30 min to obtain the solution A;
in the step 1, the first hydrothermal reaction condition is that the reaction temperature is 200 ℃ and the reaction time is 24 h;
in the step 1, the drying condition is that the drying temperature is 60 ℃ and the drying time is 6 h.
And 2, preparing a zinc sulfide-tin sulfide-molybdenum disulfide multielement composite semiconductor material, weighing thioacetamide, ammonium molybdate and zinc stannate obtained in the step 1 according to a certain mass ratio, then adding water into the thioacetamide, ammonium molybdate and zinc stannate to mix to obtain a reaction solution B, performing a second hydrothermal reaction, and washing, centrifuging and drying the obtained precipitate to obtain the zinc sulfide-tin sulfide-molybdenum disulfide multielement composite semiconductor material.
In the step 2, the mass ratio of thioacetamide, ammonium molybdate and zinc stannate is 140:110: (11-17);
in the step 2, the condition of mixing to obtain a reaction solution B is that thioacetamide and ammonium molybdate are added into 60 ml deionized water and are subjected to ultrasonic treatment for 30 min, and then zinc stannate is added and are subjected to ultrasonic treatment for 30 min to obtain the reaction solution B;
in the step 2, the condition of the second hydrothermal reaction is that the reaction temperature is 200 ℃ and the reaction time is 24 h.
Application of zinc sulfide-tin sulfide-molybdenum disulfide multielement composite semiconductor material as degradation methylene blue, when methylene blue with the photocatalytic degradation concentration of 10 mg/L is degraded, 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 multielement composite semiconductor material as the degradation rhodamine B, when the rhodamine B with the photocatalytic degradation concentration of 10 mg/L is degraded, the degradation rate of the rhodamine B reaches 99.5 percent within 100 minutes.
The technical effect of the invention is detected by experiments, and the specific contents are as follows:
XRD detection shows that: znS-SnS-MoS 2 The three-phase has good crystallization type and successful compounding.
The TEM detection shows that: moS (MoS) 2 Exhibiting lamellar morphology, znS-SnS-MoS 2 Presentation of ZnS-SnS nanoparticle Supported on MoS 2 Microstructure on lamina.
The XPS detection shows that: znS-SnS-MoS 2 Characteristic peaks of Sn 3d, zn 2p, mo 3d and S2 p exist, and there are no other impurities.
As a result of experimental examination of TEM, XRD, XPS, it was found that ZnS-SnS-MoS of the present invention 2 For the prior art, the following advantages are achieved:
1. ZnS-SnS-MoS prepared by the invention 2 The adopted multicomponent composite has the photocatalytic degradation rate of 98.7 percent to methylene blue in 1 h, and the preparation MoS of the prior document 1 2 The photocatalytic degradation rate of the PANI composite material 2 h to methylene blue reaches 30%, and the ZnS-SnS nano particles to MoS 2 The photocatalytic degradation performance is improved more obviously, compared with MoS prepared in the prior document 1 2 PANI has a faster photocatalytic degradation rate.
2. ZnS-SnS-MoS prepared by the invention 2 Ammonium molybdate was selected as a molybdenum source, and compared with the molybdenum source of the prior document 2, sodium molybdate was used as a ZnS-SnS-MoS of the molybdenum source 2 Has better photocatalytic degradation performance.
Drawings
FIG. 1 shows ZnS-SnS-MoS prepared in example 1, example 2, example 3 and comparative example 5 of the present invention 2 MoS prepared in comparative example 4 2 An X-ray diffraction pattern of (2) and a PDF card;
FIG. 2 is ZnS-SnS-MoS prepared in example 1 2 And the MoS prepared in comparative example 4 2 XPS profile of (a);
FIG. 3 is ZnS-SnS-MoS obtained in example 1 of the present invention 2 Transmission electron microscopy images;
FIG. 4 shows ZnS-SnS-MoS obtained in example 1 of the present invention 2 Is a high definition transmission electron microscopy image;
FIG. 5 shows ZnS-SnS-MoS obtained in example 1 of the present invention 2 Is an EDS map of (2);
FIG. 6 shows ZnS-SnS-MoS prepared in example 1, example 2, example 3 and comparative example 5 of the present invention 2 MoS prepared in comparative example 4 2 Corresponding degradation patterns when the methylene blue dye wastewater is degraded by photocatalysis;
FIG. 7 shows ZnS-SnS-MoS prepared in example 1, example 2, example 3 and comparative example 5 of the present invention 2 MoS prepared in comparative example 4 2 Corresponding degradation dynamics mechanical drawing when the methylene blue dye wastewater is degraded by photocatalysis;
FIG. 8 is ZnS-SnS-MoS prepared in example 1 of the present invention 2 A degradation map corresponding to the photocatalytic degradation of rhodamine B dye;
FIG. 9 is ZnS-SnS-MoS prepared in example 1 and comparative example 1, comparative example 2 of the present invention 2 Corresponding degradation patterns when the methylene blue dye wastewater is degraded by photocatalysis;
FIG. 10 shows ZSM-type porous membrane prepared in comparative example 3 of the present inventionsDegradation patterns corresponding to the degradation of methylene blue dye wastewater by ZSM-15 prepared in example 1;
FIG. 11 is an X-ray diffraction pattern and Zn of ZSM-s prepared in example 4 and ZSM-15 prepared in example 1 of the present invention 2 SnO 4 PDF card of (c).
FIG. 12 MoS prepared in comparative example 4 of the present invention 2 Transmission electron microscopy of the photocatalyst;
description of the embodiments
The present invention will now be described in further detail by way of examples, and not by way of limitation, 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 multi-element composite semiconductor material is called ZnS-SnS-MoS for short 2 。
Examples
MoS (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 100:15 comprises the following steps:
step 1, zinc stannate Zn 2 SnO 4 Weighing 0.4 g L-tryptophan, 0.2214 g zinc acetate and 0.263 g penta-water stannic chloride, heating the L-tryptophan in a water bath at 60 ℃ until the L-tryptophan is dissolved, adding the zinc acetate and the penta-water stannic chloride, stirring for 10 min, slowly dripping 5 ml of 7 mol/L NaOH to regulate the pH value of the solution to be 10, continuously stirring for 30 min to obtain a solution A, washing the obtained product with absolute ethyl alcohol for 3 times under the condition that the reaction temperature is 200 ℃ and the reaction time is 24 h, and drying the obtained product under the condition that the drying temperature is 60 ℃ and the drying time is 6 h to obtain zinc stannate, namely Zn for short 2 SnO 4 ；
And 2, preparing a zinc sulfide-tin sulfide-molybdenum disulfide multielement composite semiconductor material, weighing 0.2214 g thioacetamide, 0.263 g ammonium molybdate and 0.024 g zinc stannate obtained in the step 1, adding thioacetamide and ammonium molybdate into 60 ml deionized water, performing ultrasonic treatment for 30 min, adding zinc stannate and performing ultrasonic treatment for 30 min to obtain a reaction solution B, performing a second hydrothermal reaction on the reaction solution B under the condition that the reaction temperature is 200 ℃ and the reaction time is 24 h, and washing, centrifuging and drying the obtained precipitate to obtain the zinc sulfide-tin sulfide-molybdenum disulfide multielement composite semiconductor material with the mass ratio of 100:15, namely ZSM-15.
XRD testing was performed to demonstrate the composition of ZSM-15. The test results are shown in FIG. 1, ZSM-15 contains characteristic peaks of tin sulfide, zinc sulfide and molybdenum disulfide together, and no other impurity products are present.
To further demonstrate the composition of ZSM-15, XPS tests were performed. The test results are shown in FIG. 2, ZSM-15 contains characteristic peaks of Sn 3d, zn 2p, mo 3d and S2 p at the same time, and no other impurity products exist.
To demonstrate the microscopic morphology of ZSM-15, TEM and EDS tests were performed. The test results are shown in fig. 3, 4 and 5, and EDS results show that Sn, zn, mo, S elements exist on the surface of ZSM-15, and the microstructure of ZSM-15 is shown by combining TEM, namely tin sulfide and zinc sulfide nano particles are loaded on the surface of a molybdenum disulfide lamellar sheet.
ZnS-SnS-MoS 2 The specific method for testing the photocatalytic degradation performance of the catalyst comprises the following steps: preparing methylene blue dye solution 50 ml with concentration of 10 mg/L, weighing ZnS-SnS-MoS 0.01 g 2 And (3) adding the mixture into the prepared methylene blue solution, performing dark treatment for 30 min under a stirring state, and then opening a xenon lamp to simulate sunlight for a degradation experiment to test the photocatalytic degradation performance of the mixture.
The results of the photocatalytic degradation performance test of ZSM-15 are shown in FIG. 6 and Table 1, and the degradation rate of ZSM-15 to dye is 98.7%; to more intuitively demonstrate the performance of the catalyst, the degradation rate of ZSM-15 was calculated and the result is shown in FIG. 7, where the degradation rate of ZSM-15 is 0.0994 min -1 。
TABLE 1 initial materials and ZSM-xPerformance table of (2)
In order to prove the universality of the photocatalytic degradation effect of ZSM-15, the photocatalytic degradation performance test is carried out on rhodamine B, and particularly, the degradation rate of rhodamine B is particularly indicated as 'degradation rate of rhodamine B', and if the degradation rate is not indicated, the degradation rate is the degradation rate of methylene blue. As shown in FIG. 8, the ZSM-15 has a degradation rate of 99.5% for rhodamine B within 100 minutes. Therefore, ZSM-15 is versatile for photocatalytic degradation of a variety of contaminants.
To demonstrate the effect of a molybdenum source on the composite material, according to the controlled variable method, comparative example 1 was provided in which sodium molybdate was used as the molybdenum source ZnS-SnS-MoS prepared by substituting sodium molybdate for ammonium molybdate 2 。
Comparative example 1
ZnS-SnS-MoS with sodium molybdate as molybdenum source 2 The procedure not specifically described was the same as in example 1 except that: the step 2 uses sodium molybdate instead of ammonium molybdate, and the resulting material is named ZSM-mn.
As shown in FIG. 9, the ZSM-mn photocatalytic degradation test results show that the photocatalytic degradation rate is 86.8% at a methylene blue concentration of 10 mg/L, which is lower than the 98.7% photocatalytic degradation rate of ZSM-15 obtained in example 1, in 60 minutes.
As is evident from a comparison of example 1 and comparative example 1, ammonium molybdate is superior to sodium molybdate as a molybdenum source, and at the same time, it has been demonstrated that ammonium molybdate and sodium molybdate cannot be simply replaced by molybdenum salts in a unified manner.
To demonstrate the effect of a sulfur source on the composite, comparative example 2 was provided according to the controlled variable method, wherein the sulfur source prepared by substituting sodium sulfide for thioacetamide was ZnS-SnS-MoS of sodium sulfide 2 。
Comparative example 2
ZnS-SnS-MoS with sodium sulfide as sulfur source 2 The procedure not specifically described was the same as in example 1 except that: the step 2 uses sodium sulfide instead of thioacetamide and the resulting material is named ZSM-ns.
As shown in FIG. 9, the photocatalytic degradation test result of ZSM-ns shows that the photocatalytic degradation rate is 64.7% in 60 min at the methylene blue concentration of 10 mg/L, which is far lower than the 98.7% photocatalytic degradation rate of ZSM-15 obtained in example 1.
As is evident from a comparison of example 1 and comparative example 2, thioacetamide was superior to sodium sulfide as a sulfur source, and at the same time, it was confirmed that, in a unified manner, thioacetamide and sodium sulfide could not be simply replaced.
Furthermore, by combining comparative example 1 and comparative example 2, the following conclusion can also be drawn in comparison with example 1: according to analysis, sodium molybdate and sodium sulfide are sodium salts, and ammonium molybdate and thioacetamide adopted by the invention are nitrogen-containing compounds with ammonium or amine, and the difference directly determines the performance of a final material.
To demonstrate the effect of the preparation process on the composite material, comparative example 3 was provided, using stirring during the zinc stannate addition operation of step 2Preparing ZnS-SnS-MoS obtained by stirring instead of ultrasonic 2 。
Comparative example 3
ZnS-SnS-MoS obtained by stirring 2 The procedure not specifically described was the same as in example 1 except that: in said step 2, stirring was used instead of sonication, and the resulting product was designated ZSM-s.
XRD testing was performed to demonstrate the composition of ZSM-s. As shown in FIG. 10, ZSM-s contains both Zn and 2 SnO 4 and MoS 2 Is a characteristic peak of (2). As compared with the XRD test results of example 1, there is a substantial difference in the components obtained by ultrasonic and stirring—ultrasonic successfully produced ZnS, snS. As known from common knowledge in the art, zn 2 SnO 4 Does not have photocatalytic performance. Therefore, the preparation process, ultrasonic, has obvious influence on the components of the composite material, and further has obvious influence on the photocatalytic performance of the composite material.
The result of the photocatalytic degradation test of ZSM-s is shown in FIG. 11, and the photocatalytic degradation rate is 94.3% when the concentration of methylene blue is 10 mg/L. The experimental result proves that the photocatalytic performance of the ultrasonic composite material has remarkable influence.
To demonstrate the effect of ZnS and SnS loading on the composite, comparative example 4 was provided, without Zn addition 2 SnO 4 MoS of (F) 2 。
Comparative example 4
MoS (MoS) 2 The procedure not specifically described was the same as in example 1 except that: the step 1 is not carried out, and meanwhile, the Zn obtained in the step 1 is not added in the step 2 2 SnO 4 The material obtained was named MoS 2 。
To demonstrate the effect of ZnS-SnS on the microtopography, on MoS 2 TEM testing was performed. The test results are shown in FIG. 12, and the obtained MoS 2 Is of a lamellar structure. As can be seen from comparison with example 1, ZSM-15 MoS 2 ZnS-SnS particles are attached to the surface.
MoS 2 The results of the photocatalytic degradation test of (2) are shown in FIG. 6 and Table 1, in60 Photocatalytic degradation is carried out within min, and the degradation rate is 42.5% when the concentration of methylene blue is 10 mg/L; to more intuitively demonstrate the performance of the catalyst, the catalyst was used in 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 . Experimental results show that under the same degradation condition, the degradation rate of the ZSM-15 composite material is obviously higher than that of MoS 2 The degradation rate of the material is improved by 11.7 times. The TEM test results show that the significant improvement of the degradation performance is derived from MoS 2 After hydrothermal compounding, znS-SnS particles are adhered to the surface of the composite material, namely, the degradation performance can be effectively improved by loading ZnS and SnS.
To demonstrate the mass percent of zinc sulfide-tin sulfide to molybdenum disulfide versus ZnS-SnS-MoS 2 Influence of degradation Properties, examples 2, 3 and comparative example 5 were provided to prepare MoS 2 And Zn 2 SnO 4 ZnS-SnS-MoS with mass ratios of 100:11, 100:13 and 100:17 respectively 2 。
Comparative example 5
MoS (MoS) 2 And Zn 2 SnO 4 ZnS-SnS-MoS with the mass ratio of 100:11 2 The procedure not specifically described was the same as in example 1 except that: in the step 3, zn is added 2 SnO 4 The mass of (C) was 0.0176 and g, and the obtained product was designated 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% in 60 min at a methylene blue concentration of 10 mg/L.
Examples
MoS (MoS) 2 And Zn 2 SnO 4 ZnS-SnS-MoS with the mass ratio of 100:13 2 The procedure not specifically described was the same as in example 1 except that: in the step 3, zn is added 2 SnO 4 The product obtained was named ZSM-13, having a mass of 0.0208 g.
The results of the photocatalytic degradation test of ZSM-13 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.
Examples
MoS (MoS) 2 And Zn 2 SnO 4 ZnS-SnS-MoS with the mass ratio of 100:17 2 The procedure not specifically described was the same as in example 1 except that: in the step 3, zn is added 2 SnO 4 The mass of (C) was 0.0272 and 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% in 60 min at a methylene blue concentration of 10 mg/L.
As is clear from examples 1, 2, 3 and 5, ZSM-15 of example 1 has the best effect of removing methylene blue, and the degradation efficiency is 98.7% and the degradation rate is 0.0994 min -1 . The result shows that ZnS-SnS-MoS with the mass ratio of 100:15 2 Has the best photocatalytic degradation performance.
By way of the examples and comparative examples provided by the present invention, the following conclusions can be drawn:
1. the material performance of the invention is obviously improved, the reason is that a plurality of groups of light splitting catalysts are adopted to realize the improvement of the separation efficiency of electrons and holes in a semiconductor, 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, so that the composite material is irreplaceable;
3. the dispersion method of the raw materials plays a key role in synthesizing the product.
Therefore, the obtained semiconductor material can fully exert the photocatalysis performance only by the process technology provided by the invention.

Claims (6)

1. 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 tin tetrachloride pentahydrate according to a certain mass ratio, and then adding water to mix the L-tryptophan, the zinc acetate and the tin tetrachloride pentahydrateMixing to obtain a solution A, and finally, carrying out a first hydrothermal reaction on the solution A under a certain condition, washing and drying the obtained product to obtain zinc stannate;
in the step 1, the mass ratio of the L-tryptophan, the zinc acetate and the tin tetrachloride pentahydrate is 5:2:1, a step of;
in the step 1, the first hydrothermal reaction condition is that the reaction temperature is 200 ℃ and the reaction time is 24 h;
step 2, preparing a zinc sulfide-tin sulfide-molybdenum disulfide multielement composite semiconductor material, weighing thioacetamide, ammonium molybdate and zinc stannate obtained in the step 1 according to a certain mass ratio, then adding water into the thioacetamide, ammonium molybdate and zinc stannate to mix to obtain a reaction solution B, performing a second hydrothermal reaction, and washing, centrifuging and drying the obtained precipitate to obtain the zinc sulfide-tin sulfide-molybdenum disulfide multielement composite semiconductor material;
in the step 2, the mass ratio of thioacetamide, ammonium molybdate and zinc stannate is 140:110: (11-17);
in the step 2, the condition of the second hydrothermal reaction is that the reaction temperature is 200 ℃ and the reaction time is 24 h.
2. The method of manufacturing according to claim 1, characterized in that: in the step 1, the condition of obtaining the solution A by mixing is that L-tryptophan is heated in a water bath at 60 ℃ until the L-tryptophan is dissolved, then zinc acetate and tin tetrachloride pentahydrate are added, the mixture is stirred for 10 min, then 5 ml of 7 mol/L NaOH is slowly dripped to adjust the pH value of the solution to be 10, and the mixture is continuously stirred for 30 min to obtain the solution A.
3. The method of manufacturing according to claim 1, characterized in that: in the step 2, the condition of mixing to obtain the reaction solution B is that thioacetamide and ammonium molybdate are added into 60 ml deionized water and are subjected to ultrasonic treatment for 30 min, and then zinc stannate is added and are subjected to ultrasonic treatment for 30 min, so that the reaction solution B is obtained.
4. A zinc sulfide-tin sulfide-molybdenum disulfide multi-element composite semiconductor material prepared by the preparation method according to any one of claims 1 to 3, characterized in that: preparing zinc stannate by taking L-tryptophan, zinc acetate and tin tetrachloride pentahydrate as raw materials through a first hydrothermal reaction, and preparing the zinc stannate by taking thioacetamide as a sulfur source and ammonium molybdate as a molybdenum source through a second hydrothermal reaction;
the microstructure of the multi-element composite semiconductor material is that molybdenum disulfide is lamellar, tin sulfide and zinc sulfide are nano particles and are uniformly loaded on the surface of a molybdenum disulfide lamellar.
5. The zinc sulfide-tin sulfide-molybdenum disulfide multi-component composite semiconductor material according to claim 4, wherein: when the photocatalytic degradation concentration of the methylene blue 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 。
6. The zinc sulfide-tin sulfide-molybdenum disulfide multi-component composite semiconductor material according to claim 4, wherein: when rhodamine B with the photocatalytic degradation concentration of 10 mg/L is degraded, the degradation rate of the rhodamine B reaches 99.5 percent within 100 minutes.
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