Heterometallic doped alkyltin metal oxysulfide cluster crystalline material and preparation method and application thereof

Abstract

The present invention discloses a heterometallic doped alkyltin metal oxysulfide cluster crystalline material and a preparation method and application thereof. The molecular formula of the heterometallic doped alkyltin metal oxysulfide cluster crystalline material is (RSn): 12 M4N 16 8S 20 , wherein: R is an alkyl group with 1-10 carbon atoms, and M is one of In, Ga, Mn, and Bi; the heterometallic doped alkyl tin metal oxysulfide cluster crystalline material is a tetragonal crystal system; the heterometallic doped alkyl tin metal oxysulfide cluster crystalline material is an organic-inorganic hybrid compound; the heterometallic doped alkyl tin metal oxysulfide cluster crystalline material is a ring structure; the heterometallic doped alkyl tin metal oxysulfide cluster crystalline material is a symmetrical structure; the preparation method has simple process requirements, low requirements on raw material purity, easy to obtain raw materials and low price, and is convenient for large-scale production. The yield prepared by the synthesis method can reach more than 40%; the heterometallic doped alkyl tin metal oxysulfide cluster crystalline material can be used in organic catalysis, electrocatalytic carbon dioxide reduction, photoresist and other fields.

Description

Technical Field

[0001] The invention relates to the technical field of crystal material preparation, in particular to a heterometallic doped alkyltin metal oxysulfide cluster crystalline material and a preparation method and application thereof. Background Art

[0002] Crystalline metal chalcogenides are widely used in photoelectrocatalysis, photoluminescence, nonlinear optics, ion exchange, etc. due to their diverse structures and precisely adjustable components. Structurally, chalcogenides are different from oxides. The coordination modes of sulfur atoms are diverse, and they can be di-, tri-, or tetra-coordinated. When coordinated with metal atoms, di- and tri-coordinated are mostly used. After the chalcogen atoms are coordinated with the metal, their SMS bond angle is usually between 109°-116°, which is smaller than the corresponding OMO bond angle of 140°-145° in the oxide. Therefore, chalcogen atoms and metal atoms tend to form clusters. It is also worth noting that the smaller bond angle and longer bond length between metal atoms and chalcogen elements make the Tn-type supertetrahedral clusters and their derivative clusters dominant in metal chalcogen clusters, while chalcogen clusters based on non-supertetrahedral clusters as building units are rarely reported. Clusters are the most important basic building blocks of cluster-based crystalline materials. Different types, sizes, components and assembly methods play a decisive role in the structure and function. Therefore, in order to enrich the structure and properties of cluster-based materials, it is necessary to explore new synthesis methods to synthesize new non-supertetrahedral sulfide cluster-based materials with novel structures and excellent performance. Summary of the invention

[0003] In order to achieve the above-mentioned object, the present invention provides a heterometallic doped alkyltin metal oxysulfide cluster crystalline material and a preparation method and application thereof.

[0004] To achieve the above object, the present invention adopts the following technical solutions:

[0005] A heterometallic doped alkyltin metal oxysulfide cluster crystalline substance, the molecular formula of which is (RSn) 12 M 4 N 16 O 8 S 20 , wherein: R is an alkyl group with 1-10 carbon atoms, M is one of In, Ga, Mn, and Bi; the heterometallic doped alkyl tin metal oxysulfide cluster crystalline material is a tetragonal crystal system; the heterometallic doped alkyl tin metal oxysulfide cluster crystalline material is an organic-inorganic hybrid compound; the heterometallic doped alkyl tin metal oxysulfide cluster crystalline material is a ring structure; the heterometallic doped alkyl tin metal oxysulfide cluster crystalline material is a symmetrical structure.

[0006] A method for preparing a heterometallic doped alkyltin metal oxysulfide cluster crystalline material, the specific preparation process is as follows:

[0007] S1, uniformly mixing an organic tin metal salt, an inorganic metal salt and a sulfur source in a molar ratio of 1:(0.1-1.5):(1-10) in a mixed solvent of an organic amine and a polyol amine, and performing a thermal reaction in the mixed solvent;

[0008] S2, separating the mixture after the thermal reaction to obtain a solid product;

[0009] S3. The separated solid product is washed with alcohol and dried at room temperature to obtain a pure phase heterometallic doped alkyl tin metal oxysulfide cluster crystalline material.

[0010] Preferably, in step S1, the organic tin metal salt, the inorganic metal salt, the sulfur source and the mixed solvent are mixed, placed in a glass bottle or a polytetrafluoroethylene reactor, stirred and reacted at a constant temperature, and then naturally cooled to room temperature.

[0011] Preferably, the reaction temperature of the thermal reaction in step S1 is 30-140° C., and the reaction time is 72-360 h.

[0012] Preferably, the organic tin metal salt is one of methyltin, ethyltin, propyltin, butyltin, tert-butyltin, pentyltin, hexyltin, and octyltin; the inorganic metal salt is one or more of the nitrate, acetate, halide, sulfate, and glutaric acid salt of the required metal M; and the sulfur source is one or more of elemental sulfur powder, inorganic sulfide, and organic sulfide.

[0013] Preferably, elemental selenium or selenium dioxide is also added to the sulfur source.

[0014] Preferably, the organic amine is a mixture of one of N,N-dimethylformamide, N,N-diethylformamide, N-methylformamide, N,N-dimethylacetamide and one of acetonitrile, benzyl cyanide, glutaronitrile, pivaloyl acetonitrile; the polyol amine is one of N-(2-hydroxyethyl)ethylenediamine and diethanolamine; the addition ratio of the organic amide, polyol amine and organic nitrile amine is 1:(1-2):(2.5-3.5).

[0015] Preferably, the alcohol used to wash the solid product in step S3 is one or more of methanol, ethanol, propanol and isopropanol.

[0016] Preferably, an auxiliary agent is further added to the mixed solvent in step S1, and the auxiliary agent is one or more of zinc trifluoromethanesulfonate, copper trifluoromethanesulfonate, nickel trifluoromethanesulfonate, calcium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, tin trifluoromethanesulfonate, bismuth trifluoromethanesulfonate, cerium trifluoromethanesulfonate, and lithium trifluoromethanesulfonate.

[0017] The invention discloses an application of a heterometallic doped alkyltin metal oxysulfide cluster crystalline material, wherein the heterometallic doped alkyltin metal oxysulfide cluster crystalline material is applied in the fields of organic catalysis, electrocatalytic carbon dioxide reduction and photoresist.

[0018] After adopting the above technical solution, the present invention has the following beneficial effects: a new type of material, namely, an organic-inorganic hybrid heterometallic doped organic tin metal sulfide cluster, can be obtained by adopting the present invention. The heterometallic doped alkyl tin metal oxysulfide cluster crystalline material prepared by the present invention is a symmetrical ring structure with a size of about At the same time, the preparation method has simple process requirements, low requirements for raw material purity, easy and cheap raw materials, convenient for large-scale production, and simple and easy post-processing, and only needs to be separated by simple alcohol washing and indoor drying to obtain a pure phase crystalline product. The method has less pollution during the synthesis process and meets the requirements of green environmental protection. In addition, the heterometallic doped organic tin metal sulfur cluster prepared by the synthesis method is a ring structure, and the yield can reach more than 40%. The heterometallic doped alkyl tin metal oxygen sulfur cluster crystalline can be used in organic catalysis, electrocatalytic carbon dioxide reduction, photoresist and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 Schematic diagram of the crystal structure of the crystalline product prepared in Example 1;

[0020] Figure 2 is the X-ray powder diffraction pattern of the crystalline product prepared in Example 1, wherein the lower line is the theoretical value and the upper line is the experimental value;

[0021] Figure 3 is the infrared spectrum of the crystalline product prepared in Example 1;

[0022] Figure 4 This is the X-ray energy dispersive spectrum (EDS) of the crystalline product prepared in Example 1. DETAILED DESCRIPTION

[0023] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0024] See also Figures 1 to 4 shown.

[0025] Example 1: Preparation of heterometallic doped alkyltin metal oxysulfide cluster crystals

[0026] Thiourea (120.3 mg, 1.58 mmol), zinc trifluoromethanesulfonate (46.2 mg, 0.12 mmol), indium tri(2,4-pentanedione) (41.2 mg, 0.1 mmol) were weighed, and butyltin trichloride (45 uL, 0.27 mmol), N,N-dimethylformamide (DMF 0.5 mL, 6.46 mmol), acetonitrile (1 mL, 19.17 mmol) and N-(2-hydroxyethyl)ethylenediamine (1 mL, 9.89 mmol) were added in sequence, mixed evenly at room temperature, and then sealed in a 20 mL glass bottle, and then placed in a 65 ° C oven for 7 days, taken out and naturally cooled to room temperature, the solid product was separated, and the solid product was washed with ethanol to obtain a heterometallic doped alkyltin metal oxygen sulfur cluster crystalline material, whose molecular formula is C 80 H 180 In 4 N 16 O 8 S 20 Sn 12 The heterometallic doped alkyl tin metal oxysulfide cluster crystalline material is a colorless polyhedral crystal 0D-Ring-Sn12In4.

[0027] According to tests, the yield of the heterometallic doped alkyltin metal oxysulfide cluster crystalline material prepared in Example 1 can reach 40%.

[0028] The crystal parameters of the heterometallic doped alkyltin metal oxysulfide cluster crystalline material prepared in Example 1 are shown in Table 1.

[0029] Table 1

[0030]

[0031] Example 2: Preparation of heterometallic doped alkyltin metal oxysulfide cluster crystals

[0032] Thiourea (120.3 mg, 1.58 mmol), zinc trifluoromethanesulfonate (46.2 mg, 0.12 mmol), and gallium tri(2,4-pentanedione) (37.2 mg, 0.1 mmol) were weighed, and butyltin trichloride (45 uL, 0.27 mmol), N,N-dimethylformamide (DMF 0.5 mL, 6.46 mmol), acetonitrile (1 mL, 19.17 mmol) and N-(2-hydroxyethyl)ethylenediamine (1 mL, 9.89 mmol) were added in sequence, mixed evenly at room temperature, and then sealed in a 20 mL glass bottle, and then placed in a 65 ° C oven for reaction for 7 days, taken out and naturally cooled to room temperature, the solid product was separated, and the solid product was washed with ethanol to obtain a heterometallic doped alkyl tin metal oxysulfide cluster crystalline material, which is a colorless polyhedral crystal 0D-Ring-Sn12Ga4.

[0033] After testing, the yield of the heterometallic doped alkyltin metal oxysulfide cluster crystalline product prepared in Example 2 exceeds 40%. The structure of the crystalline product prepared in Example 2 is the same as that of the product in Example 1. From a macroscopic point of view, the crystalline product of Example 2 is also a colorless block crystal.

[0034] Single crystal X-ray analysis confirms that the heterometallic doped alkyltin metal oxysulfide cluster prepared in the present invention has a ring structure.

[0035] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A method for preparing a heterometallic doped alkyltin metal oxysulfide cluster crystalline material, characterized in that: The specific preparation process is: S1, uniformly mixing an organic tin metal salt, an inorganic metal salt and a sulfur source in a molar ratio of 1:(0.1-1.5):(1-10) in a mixed solvent of an organic amine and a polyol amine, and performing a thermal reaction in the mixed solvent; An auxiliary agent is further added to the mixed solvent in step S1, and the auxiliary agent is one or more of zinc trifluoromethanesulfonate, copper trifluoromethanesulfonate, nickel trifluoromethanesulfonate, calcium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, tin trifluoromethanesulfonate, bismuth trifluoromethanesulfonate, cerium trifluoromethanesulfonate, and lithium trifluoromethanesulfonate; S2, separating the mixture after the thermal reaction to obtain a solid product; S3, washing the separated solid product with alcohol, and drying it at room temperature to obtain a pure phase heterometallic doped alkyltin metal oxysulfide cluster crystalline material; The heterometallic doped alkyltin metal oxysulfide cluster crystalline material is a tetragonal system; the heterometallic doped alkyltin metal oxysulfide cluster crystalline material is an organic-inorganic hybrid compound; The heterometallic doped alkyltin metal oxysulfide cluster crystalline material is a ring structure; the heterometallic doped alkyltin metal oxysulfide cluster crystalline material is a symmetrical structure; the molecular formula of the heterometallic doped alkyltin metal oxysulfide cluster crystalline material is C 80 H 180 In4N 16 8S 20 Sn 12 .

2. The method for preparing a heterometallic doped alkyltin metal oxysulfide cluster crystalline material according to claim 1, characterized in that: In step S1, the organic tin metal salt, the inorganic metal salt, the sulfur source and the mixed solvent are mixed, placed in a glass bottle or a polytetrafluoroethylene reactor, stirred and reacted at a constant temperature, and then naturally cooled to room temperature.

3. The method for preparing a heterometallic doped alkyltin metal oxysulfide cluster crystalline material according to claim 1, characterized in that: The reaction temperature of the thermal reaction in step S1 is 30-140° C., and the reaction time is 72-360 hours.

4. The method for preparing a heterometallic doped alkyltin metal oxysulfide cluster crystalline material according to claim 1, characterized in that: The organic tin metal salt is one of methyltin, ethyltin, propyltin, butyltin, tert-butyltin, pentyltin, hexyltin, and octyltin; the inorganic metal salt is one or more of nitrate, acetate, halide, sulfate, and glutaric acid salt of the required metal M; and the sulfur source is one or more of elemental sulfur powder, inorganic sulfide, and organic sulfide.

5. The method for preparing a heterometallic doped alkyltin metal oxysulfide cluster crystalline material according to claim 4, characterized in that: The sulfur source is also added with elemental selenium or selenium dioxide.

6. The method for preparing a heterometallic doped alkyltin metal oxysulfide cluster crystalline material according to claim 1, characterized in that: In step S3, the alcohol used to wash the solid product is one or more of methanol, ethanol, propanol, and isopropanol.

7. An application of the heterometallic doped alkyltin metal oxysulfide cluster crystalline material as claimed in claim 1, characterized in that: The heterometallic doped alkyltin metal oxysulfide cluster crystalline material is applied in the fields of organic catalysis, electrocatalytic carbon dioxide reduction and photoresist.

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