Fe-doped amorphous SnS2 piezoelectric material as well as preparation method and application thereof
The preparation of Fe-doped amorphous SnS2 piezoelectric material through room temperature precipitation method solves the problems of low catalytic efficiency and high energy consumption in the preparation process of existing SnS2 piezoelectric materials, and achieves an efficient and environmentally friendly catalytic degradation effect.
Patent Information
- Application Number
- CN202411496977.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-24
- Publication Date
- 2025-02-07
AI Technical Summary
The existing SnS2 piezoelectric materials have low efficiency in catalytic degradation of organic pollutants, and the hydrothermal preparation process consumes high energy and takes a long time, which poses a risk of environmental pollution.
The room temperature precipitation method is used to prepare Fe-doped amorphous SnS2 piezoelectric material. By mixing and dissolving the tin source and iron source, adding a solution of sulfur source dropwise and stirring, the solid precipitate is collected and washed and dried to obtain Fe-doped non-ferrous. Crystal SnS2 piezoelectric material.
A simple and environmentally friendly piezoelectric catalytic material preparation was achieved, with significantly improved catalytic performance. The degradation efficiency of 5% Fe-doped amorphous SnS2 on carbamazepine reached 86.3%, which is far higher than that of amorphous SnS2 and crystal SnS2.
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Figure CN119386898A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of piezoelectric material preparation, and in particular to an Fe-doped amorphous SnS2 piezoelectric material and a preparation method and application thereof. Background Art
[0002] Tin disulfide (SnS2) is a transition metal disulfide with a two-dimensional layered structure. Compared with other two-dimensional piezoelectric materials, SnS2 is theoretically predicted to have a higher piezoelectric coefficient. Currently, SnS2 piezoelectric materials have been widely studied and applied in energy conversion and environmental governance. SnS2 piezoelectric materials can deform under the action of vibration energy (such as ultrasound and stirring), forming a built-in electric field, and then generating piezoelectric charges on the surface of the material. The piezoelectric charges will be further converted into active species such as superoxide radicals and hydroxyl radicals. These highly active free radicals can efficiently degrade organic pollutants.
[0003] However, the piezoelectric catalytic degradation efficiency of organic pollutants by pure SnS2 is low, and most of the reported SnS2-based piezoelectric materials have adopted the hydrothermal method in the preparation process. Since the hydrothermal method is limited by high temperature and high pressure reaction conditions, the preparation process of SnS2-based materials has high energy consumption, long time and low efficiency. In addition, the hydrothermal method for preparing SnS2 usually uses organic reagents such as thiourea and thioacetamide. Hydrogen sulfide gas is released during the reaction, which poses a risk of environmental pollution. Summary of the invention
[0004] [Technical issues]
[0005] The technical problem to be solved by the present invention is to provide a simple and environmentally friendly method for preparing Fe-doped amorphous SnS2 piezoelectric material with improved catalytic performance of the obtained piezoelectric catalytic material.
[0006] [Technical solution]
[0007] In order to solve the above technical problems, the present invention provides the following technical solutions:
[0008] In a first aspect, the present invention provides a method for preparing an Fe-doped amorphous SnS2 piezoelectric material, the method comprising the following steps:
[0009] S1, mixing and dissolving a tin source and an iron source to obtain a solution A;
[0010] S2, adding the sulfur source-containing solution B dropwise to the solution A described in S1, stirring, solid-liquid separation, and collecting the solid precipitate;
[0011] S3, washing the solid precipitate in S2, and drying it to obtain Fe-doped amorphous SnS2 piezoelectric material.
[0012] In one embodiment, the tin source includes one or more of tin tetrachloride or tin tetrachloride pentahydrate.
[0013] In one embodiment, the iron source comprises an inorganic salt of iron. Optionally but not limiting, the inorganic salt of iron comprises one or more of ferric nitrate, ferric chloride or ferric sulfate.
[0014] In one embodiment, the sulfur source includes one or more of sodium sulfide, potassium sulfide or ammonium sulfide.
[0015] In one embodiment, the molar ratio of the iron element in the iron source to the tin element in the tin source is 1:10 to 100. Optionally but not limiting, the molar ratio of the iron element in the iron source to the tin element in the tin source is 3 to 5:100.
[0016] In one embodiment, the molar ratio of the tin element in the tin source to the sulfur element in the sulfur source is 1:1 to 1:2.
[0017] In one embodiment, the stirring conditions are not limited, and only need to allow the solution A and the solution B to fully react. Optionally, the stirring time is 30 minutes.
[0018] In a second aspect, the present invention also provides Fe-doped amorphous SnS2 piezoelectric material prepared by the method described in the first aspect.
[0019] In a third aspect, the present invention further provides the use of the method described in the first aspect or the Fe-doped amorphous SnS2 piezoelectric material described in the second aspect in a piezoelectric catalytic reaction.
[0020] In one embodiment, the piezoelectric catalytic reaction includes degradation of organic pollutants.
[0021] In one embodiment, the organic contaminant comprises carbamazepine.
[0022] It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described below (such as embodiments) can be combined with each other to form a new or preferred technical solution. Due to space limitations, they will not be described one by one here.
[0023] Compared with the prior art, the present invention has the following beneficial effects:
[0024] (1) The preparation method of the Fe-doped amorphous SnS2 piezoelectric material provided by the present invention is simple, involving only a room temperature precipitation method, without harsh conditions of high temperature and high pressure, and does not involve organic reagents such as thiourea and thioacetamide. The reaction is more environmentally friendly and more suitable for large-scale production.
[0025] (2) The Fe-doped amorphous SnS2 piezoelectric material prepared by the present invention shows excellent degradation performance in the degradation of carbamazepine, and its degradation efficiency for carbamazepine is much higher than that of amorphous SnS2 and crystalline SnS2, and the degradation efficiency of 5% Fe-doped amorphous SnS2 is the highest, reaching 86.3% in 40 minutes. BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Figure 1 X-ray diffraction patterns (XRD) of amorphous SnS2, 5% Fe-doped amorphous SnS2 and crystalline SnS2.
[0027] Figure 2 The piezoelectric catalytic degradation curves of carbamazepine of crystalline SnS2, amorphous SnS2, 3% Fe-doped amorphous SnS2 and 5% Fe-doped amorphous SnS2. DETAILED DESCRIPTION
[0028] The present invention is further described in detail below in conjunction with specific embodiments, and the examples provided are only for illustrating the present invention, rather than for limiting the scope of the present invention. The examples provided below can be used as a guide for further improvements by those of ordinary skill in the art, and do not constitute a limitation of the present invention in any way.
[0029] The experimental methods in the following examples, unless otherwise specified, are all conventional methods, and are performed according to the techniques or conditions described in the literature in the field or according to the product instructions. The materials and reagents used in the following examples, unless otherwise specified, can all be obtained from commercial channels.
[0030] Example:
[0031] Example 1
[0032] 5mmol of tin tetrachloride pentahydrate and 0.25mmol of ferric nitrate nonahydrate were mixed and dissolved in 30ml of deionized water to obtain solution A, and 8mmol of sodium sulfide nonahydrate was dissolved in 30ml of deionized water to obtain solution B. Solution B was slowly added to solution A under stirring conditions, and stirring was continued for 30min after the addition was completed. The obtained mixed solution was centrifuged for solid-liquid separation, the precipitate was collected, and washed three times with deionized water and ethanol respectively; then the obtained solid was dried at 60°C for 12 hours, and the sample was ground after drying to finally obtain Fe-doped amorphous SnS2 piezoelectric material (amorphous 5% Fe-SnS2).
[0033] Example 2
[0034] 5mmol of tin tetrachloride pentahydrate and 0.15mmol of ferric nitrate nonahydrate were mixed and dissolved in 30ml of deionized water to obtain solution A, and 8mmol of sodium sulfide nonahydrate was dissolved in 30ml of deionized water to obtain solution B. Solution B was slowly added to solution A under stirring conditions, and stirring was continued for 30min after the addition was completed. The obtained mixed solution was centrifuged for solid-liquid separation, the precipitate was collected, and washed three times with deionized water and ethanol respectively; then the obtained solid was dried at 60°C for 12 hours, and the sample was ground after drying to finally obtain Fe-doped amorphous SnS2 piezoelectric material (amorphous 3% Fe-SnS2).
[0035] Example 3
[0036] 5mmol of tin tetrachloride pentahydrate and 0.25mmol of ferric nitrate nonahydrate were mixed and dissolved in 30ml of deionized water to obtain solution A, and 10mmol of sodium sulfide nonahydrate was dissolved in 30ml of deionized water to obtain solution B. Solution B was slowly added to solution A under stirring conditions, and stirring was continued for 30min after the addition was completed. The obtained mixed solution was centrifuged for solid-liquid separation, the precipitate was collected, and washed three times with deionized water and ethanol respectively; then the obtained solid was dried at 60°C for 12 hours, and the sample was ground after drying to finally obtain Fe-doped amorphous SnS2 piezoelectric material.
[0037] Example 4
[0038] 5mmol of tin tetrachloride pentahydrate and 0.25mmol of ferric nitrate nonahydrate were mixed and dissolved in 30ml of deionized water to obtain solution A, and 8mmol of potassium sulfide nonahydrate was dissolved in 30ml of deionized water to obtain solution B. Solution B was slowly added to solution A under stirring conditions, and stirring was continued for 30min after the addition was completed. The obtained mixed solution was centrifuged for solid-liquid separation, the precipitate was collected, and washed three times with deionized water and ethanol respectively; then the obtained solid was dried at 60°C for 12 hours, and the sample was ground after drying to finally obtain Fe-doped amorphous SnS2 piezoelectric material.
[0039] Comparative Example 1
[0040] Crystalline SnS2 prepared by hydrothermal method, preparation method: tin tetrachloride pentahydrate and thiourea are hydrothermally reacted at 180°C for 24 hours. Specifically, 5mmol tin tetrachloride pentahydrate and 50mmol thiourea are mixed and dissolved in 60ml deionized water, and the mixed solution is placed in a 100ml reactor and hydrothermally reacted at 180°C for 24 hours, cooled naturally, centrifuged for solid-liquid separation and washed, and then the obtained solid is dried at 60°C for 12 hours to finally obtain a crystalline SnS2 piezoelectric material.
[0041] Comparative Example 2
[0042] Preparation of amorphous SnS2:
[0043] The specific experimental method is as in Example 1, except that no iron source is added. The solid finally obtained is dried at 60° C. for 12 hours, and the sample is ground after drying to finally obtain an amorphous SnS2 piezoelectric material.
[0044] Example 5
[0045] The piezoelectric materials prepared in Example 1 and Comparative Examples 1 and 2 were subjected to structural detection by X-ray diffraction detection.
[0046] Experimental results: XRD Figure 1 As shown in the figure (SnS2-PDF#23-0677 is the standard XRD spectrum of crystalline SnS2), compared with the sharp XRD peak of crystalline SnS2, the XRD of the material prepared by precipitation method shows a steamed bun peak, which is a typical amorphous feature. In addition, the XRD peak of 5% Fe-doped amorphous SnS2 has no obvious change compared with the XRD peak of amorphous SnS2, and no Fe-related peak appears, indicating that Fe is doped into the amorphous SnS2 material.
[0047] Example 6
[0048] In this example, the Fe-doped amorphous SnS2 piezoelectric material prepared in Example 1 and Example 2 is used as a catalyst, and the crystalline SnS2 prepared in Comparative Example 1 and the amorphous SnS2 prepared in Comparative Example 2 are used as controls to verify its ability to catalyze the degradation of organic pollutants.
[0049] A 100 ml reaction bottle containing a mixed solution of catalyst and organic pollutants was placed in an ultrasonic cleaner with an ultrasonic frequency of 40 kHz. The cavitation effect of the ultrasonic wave can induce the deformation of the piezoelectric material. During the piezoelectric catalytic degradation process, the ultrasonic cleaner was connected to circulating cooling water to keep the temperature of the solution at around 25°C.
[0050] The specific experimental steps are as follows: 50 mg of catalyst was weighed and added into 50 mL of carbamazepine solution with a concentration of 5 ppm. Before the ultrasonically triggered piezoelectric catalysis, the mixed solution was stirred for 20 min in the dark to achieve adsorption equilibrium.
[0051] Degradation ability test method: Samples (1 ml) were taken regularly during the adsorption and catalytic degradation experiments and filtered with a 0.22 μm filter membrane to remove the catalyst. The obtained samples were analyzed for organic pollutant concentrations by high performance liquid chromatography. The pollutant degradation efficiency was defined as (C0-C t ) / C0, where C0 and C t are the initial concentration of organic pollutants and the residual concentration of pollutants at time t respectively.
[0052] The degradation curves of the catalysts prepared in Examples 1 and 2 for carbamazepine pollutants are as follows: Figure 2 As shown, it can be seen that the amorphous SnS2 and Fe-doped amorphous SnS2 prepared by the present invention have better piezoelectric catalytic degradation performance for carbamazepine than the crystalline SnS2 prepared by the hydrothermal method. At 40 min, the degradation efficiencies of 5% Fe-doped amorphous SnS2, 3% Fe-doped amorphous SnS2, amorphous SnS2 and crystalline SnS2 are 86.3%, 80.5%, 76.9% and 25.7%, respectively.
[0053] Although the present invention has been disclosed as above in the form of a preferred embodiment, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the definition of the claims.
Claims
1. A method for preparing Fe-doped amorphous SnS2 piezoelectric material, characterized in that: The following steps are involved: S1, mixing and dissolving a tin source and an iron source to obtain a solution A; S2, adding the sulfur source-containing solution B dropwise to the solution A described in S1, stirring, solid-liquid separation, and collecting the solid precipitate; S3, washing the solid precipitate in S2, and drying it to obtain Fe-doped amorphous SnS2 piezoelectric material.
2. The method according to claim 1, characterized in that: The tin source includes one or more of tin tetrachloride or tin tetrachloride pentahydrate.
3. The method according to claim 1, characterized in that The iron source includes inorganic salts of iron.
4. The method according to claim 3, characterized in that The inorganic iron salt includes one or more of ferric nitrate, ferric chloride or ferric sulfate.
5. The method according to claim 1, characterized in that The sulfur source includes one or more of sodium sulfide, potassium sulfide or ammonium sulfide.
6. The method according to claim 1, characterized in that The molar ratio of the iron element in the iron source to the tin element in the tin source is 1:10-100.
7. The method according to claim 1, characterized in that The molar ratio of the tin element in the tin source to the sulfur element in the sulfur source is 1:1 to 1:
2.
8. Fe-doped amorphous SnS2 piezoelectric material prepared by the method according to any one of claims 1 to 7.
9. Use of the method according to any one of claims 1 to 7 or the Fe-doped amorphous SnS2 piezoelectric material according to claim 8 in piezoelectric catalytic reactions.
10. The use according to claim 9, characterized in that: The piezoelectric catalytic reaction includes degradation of organic pollutants.