Method for converting MnPS3 into other thiophosphates
By performing ion intercalation and replacement on MnPS3, the problem of difficult synthesis of thiophosphates was solved, and efficient and low-cost preparation of thiophosphates was achieved, especially the preparation of two-dimensional materials, which are suitable for ion transport, energy storage, sensors and other fields.
Patent Information
- Application Number
- CN202410262477.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-07
- Publication Date
- 2025-09-09
AI Technical Summary
In existing technologies, certain thiophosphates are difficult to synthesize, two-dimensional materials are difficult to prepare, the synthesis cycle is long and the equipment requirements are high, making it difficult to bring out their performance advantages.
The other thiophosphates were obtained by ion intercalation of MnPS3 using the first main group metal ions, followed by ion exchange in a replacement salt solution, and finally drying.
The efficient preparation of thiophosphates is achieved, the process flow is simplified, the cost is reduced, and it is easy to scale up to prepare two-dimensional thiophosphates without layered precursors.
Smart Images
Figure CN120607229A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of thiophosphate preparation, and particularly relates to a method for converting MnPS3 into other thiophosphates. Background Art
[0002] Due to their unique physicochemical properties, thiophosphates have broad application prospects in the fields of ion transport, energy storage, catalysis, sensors, etc. At present, this type of material is mainly prepared by chemical vapor transport. This method usually uses elemental iodine as the reaction medium and is synthesized in a dual-temperature furnace. It has the disadvantages of long synthesis cycle, high equipment requirements, post-synthesis treatment to remove iodine, and relatively limited types of thiophosphates that can be synthesized. In addition, due to strong interlayer coupling or the lack of layered precursors, the preparation of two-dimensional materials of certain thiophosphates is relatively difficult, and it is difficult to give full play to the performance advantages of two-dimensional thiophosphates in certain application scenarios. Therefore, it is of great significance to develop efficient preparation methods for thiophosphates and their two-dimensional flakes. Summary of the Invention
[0003] The purpose of the present invention is to provide a method for converting MnPS3 into other thiophosphates, so as to solve the problems in the prior art such as the difficulty in synthesizing certain thiophosphates and the difficulty in preparing two-dimensional materials of certain thiophosphates.
[0004] The technical solution of the present invention:
[0005] A method for converting MnPS3 into other thiophosphates comprises the following steps:
[0006] (1) Ion intercalation of MnPS3 using first-group metal ions;
[0007] (2) adding the ion-intercalated MnPS3 into a replacement salt solution containing one or more metal ions to perform ion replacement;
[0008] (3) After the ion exchange is completed, the replaced product is separated from the replacement salt solution and repeatedly washed;
[0009] (4) removing the residual solvent in the product by air drying, and drying the separated displacement product to obtain thiophosphate containing other metal elements.
[0010] The method for converting MnPS3 into other thiophosphates, in step (1), the intercalation solution is a sulfate solution, nitrate solution, halogen solution or oxalate solution containing a first main group metal element, and the concentration range of the intercalation solution is 0.01 mol / L -1 Until the solution is saturated, the intercalation time is 1 min to 100 h.
[0011] In the method for converting MnPS3 into other thiophosphates, in step (1), the ion-intercalated MnPS3 is in the form of a powder, a film, or a colloid containing two-dimensional sheets thereof.
[0012] The method for converting MnPS3 into other thiophosphates, in step (2), the solute in the replacement salt solution is sulfate, nitrate, halogen or oxalate of a metal ion, and the solvent is an inorganic solvent or an organic solvent.
[0013] In the method for converting MnPS3 into other thiophosphates, in step (2), the cations of the salt in the solute include but are not limited to one or more metal element ions of V, Cr, Fe, Co, Ni, Cu, Zn, Cd, and Sn.
[0014] The method for converting MnPS3 into other thiophosphates, in step (2), the concentration range of the metal ions in the replacement salt solution is 0.01 mol / L -1 Until the solution is saturated, the replacement time is 1s to 100h.
[0015] In the method for converting MnPS3 into other thiophosphates, in step (2), the molar ratio of MnPS3 to the metal ions in the replacement salt solution is 1:1 to 1:1000.
[0016] In the method for converting MnPS3 into other thiophosphates, in step (3), after the replacement is completed, the replacement product is separated from the replacement salt solution by centrifugation or filtration.
[0017] In the method for converting MnPS3 into other thiophosphates, in step (4), the drying temperature of the replacement product is 50-200°C, and the drying time is 30 minutes to 36 hours.
[0018] The design concept of the present invention:
[0019] The present invention converts MnPS3 into other thiophosphates. Prior to ion exchange, the MnPS3 is subjected to ion intercalation. The intercalated MnPS3 is then immersed in a replacement salt solution containing one or more metal ions for a predetermined period of time. After the replacement is complete, the replacement product is separated from the replacement salt solution and dried. Thus, by using a salt solution containing metal ions to perform ion exchange on MnPS3, different types of thiophosphates can be prepared.
[0020] The advantages and beneficial effects of the present invention are:
[0021] 1. The present invention uses transition metal ions to replace the Mn element in MnPS3, which is expected to solve the problems of difficulty and low efficiency in the preparation of some thiophosphates.
[0022] 2. The method of the present invention has the characteristics of simple preparation process, low cost, and easy scale-up. It is also expected to achieve the preparation of two-dimensional thiophosphates with difficult-to-strip precursors and no layered precursors. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 :(a) is the scanning electron microscope morphology of MnPS3; (b) is the energy spectrum of MnPS3, the horizontal axis Energy represents energy (keV), and the vertical axis Counts represents counts; (c) is Co 2+ Replacement product (MnPS3-Co 2+ ) of the scanning electron microscope; (d) of MnPS3-Co 2+ Energy spectrum diagram, the horizontal axis Energy represents energy (keV), and the vertical axis Counts represents counts.
[0024] Figure 2 :(a) MnPS3-Co taken by spherical aberration corrected transmission electron microscope 2+ Atomic image; (b) is the corresponding fast Fourier transform diffraction spot calibration; (c) is the high magnification of MnPS3-Co 2+ Atomic image; (d) is the corresponding Co element energy spectrum distribution diagram.
[0025] Figure 3 :Zn 2+ The replacement product of MnPS3 (MnPS3-Zn 2+ ) scanning morphology (a) and energy spectrum (b); in (b), the horizontal axis Energy represents energy (keV), and the vertical axis Counts represents counts.
[0026] Figure 4 :Sn 2+ The replacement product of MnPS3 (MnPS3-Sn 2+ ) scanning morphology (a) and energy spectrum (b); in (b), the horizontal axis Energy represents energy (keV), and the vertical axis Counts represents counts. DETAILED DESCRIPTION
[0027] In a specific implementation process, the present invention proposes a method for converting MnPS3 into other thiophosphates, comprising the following steps:
[0028] (1) Ion intercalation of MnPS3 using first-group metal ions;
[0029] (2) adding the ion-intercalated MnPS3 powder, film or two-dimensional sheet colloid into a replacement salt solution containing one or more metal ions to perform ion replacement;
[0030] (3) After the ion exchange is completed, the replaced product is separated from the replacement salt solution and repeatedly washed. The separation method can be centrifugation or filtration;
[0031] (4) removing the residual solvent in the product by air drying, and drying the separated displacement product to obtain thiophosphate containing other metal elements.
[0032] The feasibility of the present invention is further demonstrated below by examples.
[0033] Example 1
[0034] In this embodiment, 2.982 g of KCl was added to 40 mL of deionized water as an intercalation solution, and 200 mg of MnPS3 powder was added to the intercalation solution for ion intercalation. After magnetic stirring for 4 h, KCl was removed by filtration. + The intercalated MnPS3 was separated.
[0035] The concentration is 0.5 mol / L -1 Cobalt chloride aqueous solution, 50 mg of K + The intercalated MnPS3 powder was added to 5 mL of cobalt chloride aqueous solution for 15 min. 2+ The replaced MnPS3 was separated from the cobalt chloride aqueous solution, washed with deionized water several times, and then dried under 60 ° C to obtain MnPS3-Co 2+ Powder.
[0036] like Figure 1 As shown in (a), MnPS3 is a micron-sized powder with a relatively regular morphology.
[0037] like Figure 1 As shown in (b), the energy spectrum of MnPS3 shows that the sample contains three elements: Mn, P, and S, among which C and Al come from the carbon paste and the sample stage.
[0038] like Figure 1 As shown in (c), (MnPS3-Co 2+ ) morphology is basically consistent with that of MnPS3
[0039] like Figure 1 As shown in (d), (MnPS3-Co 2+ ) has an extremely low Mn content and a greatly increased Co content, indicating that Mn is replaced by Co in the sample.
[0040] like Figure 2 As shown in the transmission electron microscopy results, MnPS3-Co 2+ The crystal structure is the same as that of CoPS3, and the energy spectrum shows that the Mn in the sheet is converted into Co.
[0041] Example 2
[0042] In this embodiment, the concentration is 0.5 mol / L -1 Zinc sulfate aqueous solution, 50 mg of K + The intercalated MnPS3 powder was added to 5 mL of zinc sulfate aqueous solution for 12 h. Afterwards, Zn 2+ The replaced MnPS3 was separated from the zinc sulfate aqueous solution, washed with deionized water several times, and then dried under 60 ° C by forced air to obtain MnPS3-Zn 2+ Powder (scanning morphology and energy spectrum see Figure 3 a, 3b).
[0043] like Figure 3 As shown in (a), Zn 2+ The replacement product of MnPS3 (MnPS3-Zn 2+ ) can be seen from the scanning morphology that the sample is a micron-sized powder.
[0044] like Figure 3 As shown in (b), Zn 2+ The replacement product of MnPS3 (MnPS3-Zn 2+ ) shows that Mn is replaced by Zn.
[0045] Example 3
[0046] In this embodiment, the concentration is 0.5 mol / L -1 SnCl2·2H2O ethanol solution, 50 mg of K + The intercalated MnPS3 powder was added to 5 mL of SnCl2·2H2O ethanol solution for 12 h. Afterwards, the Sn 2+ The replaced MnPS3 was separated from the SnCl2·2H2O ethanol solution, washed with ethanol several times, and then dried under 60℃ to obtain MnPS3-Sn 2+ Powder (scanning morphology and energy spectrum see Figure 4 a, 4b).
[0047] like Figure 4 As shown in (a), Sn 2+ The replacement product of MnPS3 (MnPS3-Sn 2+ ) can be seen from the scanning morphology that the sample is a micron-sized powder.
[0048] like Figure 4 As shown in (b), Sn 2+ The replacement product of MnPS3 (MnPS3-Sn 2+ ) shows that Mn is replaced by Zn.
[0049] The implementation results show that the present invention adds MnPS3 in different states (such as powder, film, two-dimensional thin sheet colloid, etc.) obtained after intercalation of the first main group metal ions into a salt solution containing metal ions for ion replacement, and then obtains other types of thiophosphates after drying. It is expected to promote the preparation of new thiophosphates and their two-dimensional thin sheets, as well as their application in the fields of ion transport, energy storage, catalysis, sensors, etc.
Claims
1. A method for converting MnPS3 into other thiophosphates, characterized in that: The steps include: (1) Ion intercalation of MnPS3 using first-group metal ions; (2) adding the ion-intercalated MnPS3 into a replacement salt solution containing one or more metal ions to perform ion replacement; (3) After the ion exchange is completed, the replaced product is separated from the replacement salt solution and repeatedly washed; (4) removing the residual solvent in the product by air drying, and drying the separated displacement product to obtain thiophosphate containing other metal elements.
2. The method for converting MnPS3 into other thiophosphates according to claim 1, characterized in that: In step (1), the intercalation solution is a sulfate solution, nitrate solution, halogen solution or oxalate solution containing a first main group metal element, and the concentration range of the intercalation solution is 0.01 mol / L -1 Until the solution is saturated, the intercalation time is 1 min to 100 h.
3. The method for converting MnPS3 into other thiophosphates according to claim 1, characterized in that: In step (1), the ion-intercalated MnPS3 is in the form of powder, film or colloid containing two-dimensional sheets thereof.
4. The method for converting MnPS3 into other thiophosphates according to claim 1, characterized in that: In step (2), the solute in the replacement salt solution is sulfate, nitrate, halogen or oxalate of a metal ion, and the solvent is an inorganic solvent or an organic solvent.
5. The method for converting MnPS3 into other thiophosphates according to claim 4, characterized in that: In step (2), the cations of the salt in the solute include, but are not limited to, one or more of the metal element ions of V, Cr, Fe, Co, Ni, Cu, Zn, Cd, and Sn.
6. The method for converting MnPS3 into other thiophosphates according to claim 1, characterized in that: In step (2), the concentration of metal ions in the replacement salt solution is in the range of 0.01 mol / L -1 Until the solution is saturated, the replacement time is 1s to 100h.
7. The method for converting MnPS3 into other thiophosphates according to claim 1, characterized in that: In step (2), the molar ratio of MnPS3 to the metal ions in the replacement salt solution is 1:1 to 1:1000.
8. The method for converting MnPS3 into other thiophosphates according to claim 1, characterized in that: In step (3), after the replacement is completed, the replacement product is separated from the replacement salt solution by centrifugation or filtration.
9. The method for converting MnPS3 into other thiophosphates according to claim 1, characterized in that: In step (4), the drying temperature of the replacement product is 50 to 200° C., and the drying time is 30 min to 36 h.