Layered transition metal sulfide with photoelectric response and preparation method and application thereof
The synthesis of Cs2Ag2Mn2S4 via a mild solvothermal method solves the synthesis problem of Ag/Mn dual transition metal quaternary sulfides, and prepares a pure phase single crystal with significant photoelectric response. This overcomes the energy consumption and impurity phase problems of high-temperature methods, and realizes the application of highly stable and efficient optoelectronic materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-04-22
- Publication Date
- 2026-06-16
AI Technical Summary
Existing technologies make it difficult to form an ordered multi-element crystal framework of Ag2S and MnS in conventional hydrothermal/solventothermal systems. Traditional high-temperature solid-state methods consume a lot of energy and the products are prone to impurities. Mild liquid-phase synthesis routes for Ag/Mn dual transition metal quaternary sulfides are scarce, resulting in a scarcity of Ag-Mn-based quaternary sulfide materials and poor structural controllability.
Cs2Ag2Mn2S4 was synthesized using a mild solvothermal method. By using excess sulfur powder as a mineralizing agent, a solvothermal reaction was carried out at 180℃ to form a two-dimensional [Ag2Mn2S4]2- anion layer and a layered structure filled with Cs+, thus avoiding the formation of Ag2S impurity phases and preparing pure phase single crystals.
A pure-phase single-crystal synthesis of Ag/Mn dual transition metal quaternary sulfides was achieved, exhibiting significant photoelectric response performance and high stability, making it suitable for photoelectric detection, photocatalysis, and solar cell applications.
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Figure CN122212256A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of inorganic functional materials technology, specifically relating to a layered transition metal sulfide with photoelectric response, its preparation method, and its application. Background Technology
[0002] Multi-metal sulfides possess unique electronic, crystal, and photoelectric properties, making them valuable for applications in photocatalysis, ion exchange, nonlinear optics, photodetectors, and solar cells. Among them, quaternary sulfides containing two transition metals such as Ag and Mn can significantly modulate the bandgap and enhance carrier migration and photoelectric response due to dp orbital hybridization effects, making them an important research direction for next-generation optoelectronic functional materials.
[0003] However, existing technologies have the following obvious drawbacks: 1) Ag2S and MnS have extremely low solubility and are very easy to precipitate directly in conventional hydrothermal / solvothermal systems, making it difficult to form an ordered multi-element crystal framework; 2) Traditional high-temperature solid-state methods and flux methods have high reaction temperatures (>600℃), high energy consumption, and the products are prone to impurities and have poor structural controllability; 3) Mild liquid-phase synthesis routes for Ag / Mn dual transition metal quaternary sulfides are rarely reported, and the controllable preparation of layered structures is extremely difficult; 4) Ag-Mn-based quaternary sulfide materials that combine pure phase, regular layered structure, and stable photoelectric response are scarce.
[0004] Therefore, developing a mild, simple, and pure-phase method for preparing dual-transition metal quaternary sulfides to obtain novel optoelectronic materials with well-defined structures and stable performance is of great scientific significance and application prospects. Summary of the Invention
[0005] The purpose of this invention is to provide a layered transition metal sulfide with photoelectric response. This sulfide has a novel structure, is air-stable, and exhibits significant photoelectric response. This invention also provides a method for preparing and applying the layered transition metal sulfide with photoelectric response.
[0006] The chemical formula of the photoelectric responsive layered transition metal sulfide described in this invention is Cs2Ag2Mn2S4. This sulfide is a layered crystal structure with an orthorhombic crystal system and Cmma space group.
[0007] The crystal structure is an infinitely extended two-dimensional [Ag₂Mn₂S₄] 2- Anion layer and Cs filling the interlayer + composition.
[0008] The anion layer is assembled by connecting AgS4 helical chains and MnS4 helical chains on common edges.
[0009] The method for preparing the photoelectric responsive layered transition metal sulfide of the present invention includes the following steps: (1) Weigh out Cs2CO3, AgNO3, MnSO4·H2O and excess sulfur powder according to the ratio; (2) Add solvent, stir evenly, transfer to heat-resistant glass tube and seal; (3) Place the sealed system in a stainless steel reactor for a solvothermal reaction; (4) After the reaction is complete, the mixture is allowed to cool naturally to room temperature, washed, and dried to obtain orange-red square single crystal Cs2Ag2Mn2S4.
[0010] The solvent in step (2) is 1,3-propanediamine.
[0011] The temperature of the solvothermal reaction in step (3) is 180℃.
[0012] The solvothermal reaction in step (3) takes 7 days.
[0013] In step (4), the washing is done with anhydrous ethanol.
[0014] The application of the photoelectric responsive layered transition metal sulfides described in this invention is in optoelectronic functional materials.
[0015] Photoelectric functional materials include photoelectric detection materials, photocatalytic materials, solar cell absorber layers, and photoelectric conversion devices.
[0016] This invention provides a quaternary mixed transition metal sulfide with the chemical formula Cs₂Ag₂Mn₂S₄, belonging to the orthorhombic crystal system. Cmma Space group, crystallographic parameters are: a=5.9507(7)Å, b=14.0328(16)Å, c=5.9775(7)Å; α=β=γ=90°, Z=2.
[0017] Key structural features: One-dimensional chains are formed by connecting AgS4 tetrahedra and MnS4 tetrahedra respectively; The two chains are further assembled to form a two-dimensional, infinitely extending [Ag2Mn2S4] 2- Anion layer; Cs + As balanced cations, they are orderly filled in the interlayer to form a typical layered structure; Ag + With Mn 2+ It exhibits an ordered distribution, a highly regular crystal structure, and excellent thermal and air stability.
[0018] This invention achieves, for the first time, a mild solvothermal synthesis in an Ag / Mn dual transition metal quaternary sulfide system; excess sulfur powder acts as a mineralizing agent, generating polysulfide ions in situ, significantly increasing the Ag content. + It has high solubility and inhibits the formation of Ag2S impurity phase; the reaction temperature is low (180℃), no high-temperature calcination is required, the process is green and has good repeatability; the product is a pure phase single crystal with high crystallinity, no impurities, and regular morphology.
[0019] The compound Cs2Ag2Mn2S4 of this invention exhibits significant and stable photoelectric response properties: It generates a rapid and repeatable photocurrent response under simulated sunlight irradiation; it exhibits high efficiency in the generation and separation of photogenerated electron-hole pairs; and it maintains structural stability over long-term placement in air, making it suitable for device applications. It can be widely used in: photodetectors, photocatalytic materials, solar cell absorber layers, photoelectric conversion devices, etc.
[0020] The beneficial effects of this invention are as follows: 1) Pioneering synthesis route: For the first time, a mild solvothermal method was used to prepare pure phase layered single crystals in Ag / Mn dual transition metal quaternary sulfides, breaking through the limitations of high-temperature methods.
[0021] 2) Unique mineralization mechanism: Excess sulfur powder is used as a mineralizing agent to solve the key problems of Ag / Mn sulfides being difficult to dissolve and easy to precipitate.
[0022] 3) Novel and unique structure: It has a brand-new two-dimensional layered structure, providing a new structural model for chalcogenide optoelectronic materials.
[0023] 4) Outstanding photoelectric properties: It has a stable photoelectric response and is a new type of inorganic photoelectric functional material with great potential.
[0024] 5) Simple and green process: mild conditions, universal equipment, simple post-processing, no toxic by-products, suitable for batch preparation in the laboratory. Attached Figure Description
[0025] Figure 1 This is a photograph of a Cs2Ag2Mn2S4 crystal.
[0026] Figure 2 The image shows the SEM morphology of Cs2Ag2Mn2S4.
[0027] Figure 3 The image shows the energy spectrum analysis of Cs2Ag2Mn2S4.
[0028] Figure 4 This is a schematic diagram of the anion layer of Cs₂Ag₂Mn₂S₄, where (a) represents [Ag₂Mn₂S₄]. n 2n- (b) shows the anion layer and its crystal structure.
[0029] Figure 5 Experimental and simulated XRD spectra of Cs2Ag2Mn2S4.
[0030] Figure 6 The image shows the photoelectric response (it) curve of Cs2Ag2Mn2S4. Detailed Implementation
[0031] The present invention will be further described below with reference to embodiments.
[0032] Example 1 Preparation of Cs2Ag2Mn2S4 Accurately weigh: Cs2CO3: 0.05 mmol (16.7 mg) S powder: 0.66 mmol (21.0 mg) AgNO3: 0.02 mmol (3.1 mg) MnSO4·H2O: 0.02mmol (3.9mg); After mixing the above raw materials thoroughly, the mixture was transferred to a Pyrex glass tube, and 1.25 mL of 1,3-propanediamine was added. The tube was then sealed and placed in a stainless steel reactor, where it was heated at a constant temperature of 180°C for 7 days. After naturally cooling to room temperature, the mixture was washed 3-5 times with anhydrous ethanol and dried at room temperature to obtain orange-red square single crystals of Cs₂Ag₂Mn₂S₄.
[0033] Characterized by SEM, EDS, and X-ray single-crystal diffraction, the product was a pure-phase Cs₂Ag₂Mn₂S₄, orthorhombic crystal system, Cmma space group, without impurities. The detection results are shown in [Figure number missing]. Figure 1-6 .
Claims
1. A layered transition metal sulfide with photoelectric response, characterized in that... Its chemical formula is Cs2Ag2Mn2S4. This sulfide is a layered crystal with an orthorhombic crystal system and Cmma space group.
2. The layered transition metal sulfide with photoelectric response according to claim 1, characterized in that... Its crystal structure consists of an infinitely extended two-dimensional [Ag₂Mn₂S₄] crystal. 2- Anion layer and Cs filling the interlayer + composition.
3. The layered transition metal sulfide with photoelectric response according to claim 2, characterized in that... The anion layer is assembled by connecting AgS4 helical chains and MnS4 helical chains on common edges.
4. A method for preparing a layered transition metal sulfide with photoelectric response as described in any one of claims 1-3, characterized in that... Includes the following steps: (1) Weigh out Cs2CO3, AgNO3, MnSO4·H2O and excess sulfur powder according to the ratio; (2) Add solvent, stir evenly, transfer to heat-resistant glass tube and seal; (3) Place the sealed system in a stainless steel reactor for a solvothermal reaction; (4) After the reaction is complete, the mixture is allowed to cool naturally to room temperature, washed, and dried to obtain orange-red square single crystal Cs2Ag2Mn2S4.
5. The method for preparing a layered transition metal sulfide with photoelectric response according to claim 4, characterized in that... The solvent in step (2) is 1,3-propanediamine.
6. The method for preparing a layered transition metal sulfide with photoelectric response according to claim 4, characterized in that... The temperature of the solvothermal reaction in step (3) is 180℃.
7. The method for preparing a layered transition metal sulfide with photoelectric response according to claim 4, characterized in that... The solvothermal reaction in step (3) takes 7 days.
8. The method for preparing a layered transition metal sulfide with photoelectric response according to claim 4, characterized in that... In step (4), the washing is done with anhydrous ethanol.
9. An application of the layered transition metal sulfide with photoelectric response as described in any one of claims 1-3, characterized in that... Applications in optoelectronic functional materials.
10. The method for preparing a layered transition metal sulfide with photoelectric response according to claim 9, characterized in that... Photoelectric functional materials include photoelectric detection materials, photocatalytic materials, solar cell absorber layers, and photoelectric conversion devices.