Ternary mixed metal organotin supertetrahedral chalcogenide cluster crystalline materials for resin catalysts and methods of synthesis and use thereof

Abstract

The application provides a ternary mixed metal organotin supertetrahedral chalcogenide cluster crystal state for resin catalysts and a synthesis method and application thereof. The chalcogenide cluster compound comprises at least a core and a periphery, the core comprises metal ions, and the periphery comprises organotin; the core and the periphery form a cluster structure; and the molecular general formula of the chalcogenide cluster compound is (RSn)4M4M'2S 16 wherein R is selected from n-butyl (nBu) and / or phenyl (Ph); M is selected from In or Ga; and M' is selected from Zn, Cd, Mn and Co. The synthesis method of the application has low requirements on the purity of raw materials, simple process, and the crystal state is easy to repeat, convenient for production. The yield of the chalcogenide cluster crystal state obtained by the synthesis method of the application can reach more than 45%. The chalcogenide cluster compound of the application can be used in the fields of photoelectric catalysis and nonlinear optics.

Description

Technical Field

[0001] This invention belongs to the field of crystal material preparation technology, and relates to a ternary mixed metal organotin supertetrahedral chalcogenide cluster crystal for resin catalysts, its synthesis method and application. Background Technology

[0002] Metal chalcogenide clusters have attracted attention due to their diverse structures and rich physicochemical properties. Among them, the supertetrahedral configuration is a classic structural type of metal chalcogenide clusters. It possesses the basic building blocks of a ZnS-type cubic phase, and its structural composition is precisely known. Therefore, the crystal structure and metal element composition of the synthesized products can be controlled by adjusting the synthesis methods, thereby achieving property regulation of the target cluster. In supertetrahedral chalcogenide clusters, metal ions are typically coordinated with four chalcogenide atoms, forming a tetrahedral coordination configuration. Chalcogenide atoms are usually bonded to only two or three metal ions, i.e., typically only in di- or tri-coordinate forms. Therefore, in the structural composition of supertetrahedral chalcogenide clusters, there are more negatively charged chalcogenide atoms than positively charged metal ions, and the difference in the number of atoms increases with the size of the cluster nucleus, thus the charge difference also increases. Therefore, the nuclei of supertetrahedral chalcogenide clusters often spontaneously bridge each other by sharing end-group chalcogenide atoms to form a framework material to reduce their overall charge. Therefore, synthesizing zero-dimensional supertetrahedral chalcogenides using commonly used methods for synthesizing chalcogenide compounds presents certain challenges. Previous literature has reported synthetic strategies employing the introduction of high-valence metal ions and / or organic ligands to obtain zero-dimensional supertetrahedral chalcogenide clusters; however, research on the use of organometallic salts for the synthesis of zero-dimensional supertetrahedral chalcogenide clusters is still rare.

[0003] Therefore, it is necessary to explore an effective synthetic method to synthesize organotin zero-dimensional supertetrahedral metal chalcogenide clusters with higher core density and richer structures. Studies have shown that multi-component mixed metal organotin supertetrahedral chalcogenide clusters have good effects in catalysis, luminescent materials, and nonlinear optics. Summary of the Invention

[0004] To achieve the above objectives, this invention provides a ternary mixed-metal organotin supertetrahedral chalcogenide cluster for use in resin catalysts, its synthesis method, and its applications. The heterometallic organotin chalcogenide cluster is an isolated zero-dimensional cluster of the T3 type. The types of metal ions in the core and the peripheral organotin compounds can be controlled by adjusting the synthesis conditions. The method described in this invention is simple, efficient, and produces minimal pollution during synthesis, meeting green environmental protection requirements.

[0005] This invention provides a chalcogenide cluster compound, which includes at least a core and a periphery, wherein the core comprises a metal ion and the periphery comprises an organotin compound; the core and periphery constitute a cluster structure.

[0006] The general molecular formula of the chalcogenide cluster is (RSn)4M4M'2S 16 R is selected from n-butyl (nBu) and / or phenyl (Ph); M is selected from In or Ga; M' is selected from Zn, Cd, Mn, Co.

[0007] According to an embodiment of the present invention, the cluster structure of the chalcogenide cluster is a supertetrahedral.

[0008] Preferably, in the cluster structure of the chalcogenide cluster, organotin is located at the four apex positions of the supertetrahedron.

[0009] According to an embodiment of the present invention, the size of the cluster nucleus is 15.62-18.344 Å.

[0010] According to an embodiment of the present invention, the chalcogenide cluster compound is a pure-phase crystalline substance.

[0011] Preferably, the crystalline material is a bulk crystalline material, such as... Figure 4 , 11 Or, as shown in 16, a bulk crystalline material, or, for example, an octahedral bulk crystalline material.

[0012] Preferably, the crystal of the crystalline compound can be dark, light, or colorless, with different metal ions corresponding to different colored crystals. For example, when M is In and M' is Cd, the crystal of the crystalline compound is light yellow or light red. For example, when M is Ga and M' is Co, the crystal of the crystalline compound is green.

[0013] Preferably, the crystal size of the crystalline material is 20-200 μm.

[0014] According to an embodiment of the present invention, the crystal structure type of the chalcogenide cluster is T3 type, wherein T3 type refers to the chalcogenide cluster having isolated zero-dimensional clusters.

[0015] According to an embodiment of the present invention, the chalcogenide cluster is (nBuSn)4M4M'2S 16 Cluster compound or (PhSn)4M4M'2S 16 Clusters.

[0016] According to an exemplary embodiment of the present invention, the (nBuSn)4M4M'2S 16 The chemical formula of the cluster compound is C 16 H 36 Cd2In4Sn4S 16 .

[0017] Preferably, the (nBuSn)4M4M'2S 16 The space group of the crystalline form of the cluster compound is I41 / a, with unit cell parameters: a=b=19.5219Å, c=27.0483Å, α=90. o β is 90 o γ is 90 o V is 10308.2 Å 3 .

[0018] Preferably, the (nBuSn)4M4M'2S 16 The crystal system of the crystalline form of the cluster compound is tetragonal.

[0019] Preferably, the (nBuSn)4M4M'2S 16 The crystalline form of the cluster compound has essentially the same properties as Figure 2 The X-ray powder diffraction pattern shown.

[0020] Preferably, the (nBuSn)4M4M'2S 16 The crystalline form of the cluster compound is a bulk crystalline form, such as... Figure 4 The octahedral bulk crystalline material shown.

[0021] Preferably, when the (nBuSn)4M4M'2S 16 When M is In and M' is Cd in the cluster compound, the crystals of the crystalline compound are light yellow or light red.

[0022] According to an exemplary scheme of the present invention, (nBuSn)4M4M'2S 16 The crystal parameters of the clusters are shown in Table 1 below:

[0023] Table 1

[0024]

[0025] According to an exemplary embodiment of the present invention, the [(PhSn)4M4M'2S 16 The chemical formula of the cluster compound is C. 24 H 20 Cd2In4Sn4S 16 Or C 24 H 20 Co2Ga4Sn4S 16 .

[0026] Preferably, the (PhSn)4M4M'2S 16 The space group of the crystalline form of the cluster compound is Fd-3m, and its unit cell parameters are: a = b = c = 27.71 Å, α = 90°. o β is 90 o γ is 90 o V is 21278 Å 3 .

[0027] Preferably, the (PhSn)4M4M'2S 16 The crystal system of the crystalline form of the cluster compound is cubic.

[0028] Preferably, the (PhSn)4M4M'2S 16 The crystalline form of the cluster compound is a bulk crystalline form, such as... Figure 11 or Figure 16 The octahedral bulk crystalline material shown.

[0029] Preferably, when the (PhSn)4M4M'2S 16 When M is In and M' is Cd in the cluster compound, the crystals of the crystalline compound are light yellow in color, such as... Figure 11 As shown.

[0030] Preferably, when the (PhSn)4M4M'2S 16 When M in the cluster compound is Ga and M' is Co, the crystals of the crystalline compound are green, such as... Figure 16 As shown. According to an exemplary scheme of the present invention, the (PhSn)4M4M'2S 16 The crystal parameters of the clusters are shown in Table 2 below:

[0031] Table 2

[0032]

[0033] The present invention also provides a method for synthesizing the above-mentioned chalcogenide clusters, particularly their crystalline forms, the method comprising the following steps: mixing organotin salts, other main group metal salts, transition metal salts, and a sulfur source, and carrying out a solvothermal reaction in a mixed solvent of organic polyols and / or organic amines to obtain the chalcogenide clusters.

[0034] According to an embodiment of the present invention, the synthesis method specifically includes the following steps:

[0035] 1) Mix organotin salts, other main group metal salts, transition metal salts, and sulfur source evenly, mix them evenly in a reaction solvent, and then heat them under closed conditions to carry out a solvothermal reaction to obtain a mixture;

[0036] 2) Separate and purify the mixture obtained after the reaction in step 1) to prepare chalcogenide cluster crystals.

[0037] According to an exemplary embodiment of the present invention, step 1) specifically includes: uniformly mixing the organotin salt, other main group metal salts, transition metal salts, and sulfur source in a reaction solvent in a certain proportion, placing the mixture in a reaction vessel, heating it to a constant temperature for reaction, and then naturally cooling it to room temperature. Further, the reaction vessel can be any container known in the art, such as a glass bottle or polytetrafluoroethylene (PTFE).

[0038] According to an embodiment of the present invention, the organotin salt may be selected from at least one of methyltin, propyltin, ethyltin, butyltin, tert-butyltin, hexyltin, octyltin, phenyltin, benzyltin, methylphenyltin, ethylphenyltin, etc., preferably butyltin and phenyltin.

[0039] According to an embodiment of the present invention, the other main group metal salt may be selected from at least one of chlorides, sulfates, nitrates, acetates, etc. of other main group metals, preferably chlorides and nitrates of other main group metals.

[0040] Preferably, in the other main group metal salts, the other main group metals are selected from In and / or Ga.

[0041] According to an embodiment of the present invention, the transition metal salt may be selected from at least one of the chloride, sulfate, nitrate, and acetate salts of transition metals, preferably chloride and nitrate salts of transition metals.

[0042] Preferably, in the transition metal salt, the transition metal is selected from at least one of Zn, Cd, Mn, and Co.

[0043] For example, the nitrate is cadmium nitrate or cobalt nitrate.

[0044] For example, the chloride salt is zinc chloride or manganese chloride.

[0045] According to an embodiment of the present invention, the sulfur source may be selected from at least one of organic sulfur sources, inorganic sulfides, elemental sulfur, elemental selenium, selenium dioxide, etc.

[0046] For example, the organic sulfur source is thiourea or L-cysteine.

[0047] For example, the inorganic sulfide is sodium sulfide.

[0048] According to an embodiment of the present invention, in step 1), the molar ratio of the organotin salt, other main group metal salts, transition metal salts and sulfur source is 1:(0.2-2):(0.1-1):(1-15), preferably 1:(0.3-1):(0.2-0.5):(3-10).

[0049] According to an embodiment of the present invention, in step 1), the reaction solvent is selected from organic amines and / or organic alcohols.

[0050] Preferably, the organic amine may be selected from at least one of 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, pyrazine, 2,3-dimethylpyrazine, 4,7-diaza-1H-indazole, indole[1,2-A]pyrazine, 1,2,4-triazolo[4,3-A]pyrazine, 2,3-dimethylquinoxaline, quinoxaline, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, n-pentylamine, n-hexylamine, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N,N-diethylformamide (DEF), N,-methylformamide (NMF), etc., for example, a mixed amine solvent of one, two or more organic amines.

[0051] Preferably, the organic alcohol is selected from polyols, for example from at least one of diols containing 1-40 carbon atoms, such as at least one of ortho-diols containing 1-30 carbon atoms, 1-20 carbon atoms, 1-10 carbon atoms, or 1-6 carbon atoms.

[0052] Furthermore, the diol is selected, for example, from at least one of ethylene glycol, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, and 1,2-hexanediol, or, for example, from one, two, or a mixture of more than two of the above diols.

[0053] According to an embodiment of the present invention, in step 1), the reaction temperature of the solvothermal reaction is 40~160℃; preferably 50~140℃, such as 60℃ or 120℃. The inventors have found that if the reaction temperature is too low, the reaction time will be longer and the crystal size will be smaller.

[0054] According to an embodiment of the present invention, in step 1), the reaction time of the solvothermal reaction can be 72-360 hours, more preferably 120-300 hours, for example 168 hours or 192 hours.

[0055] As a preferred embodiment of the present invention, the solvothermal reaction can be carried out at 60°C for 192 hours or at 120°C for 168 hours.

[0056] According to an embodiment of the present invention, in step 2), the purification includes washing with a cleaning solvent and optionally drying.

[0057] Preferably, the cleaning solvent is selected from alcohol solvents and / or amine solvents.

[0058] Preferably, the present invention does not specifically limit the alcohol solvent or amine solvent, as long as it can achieve the above-mentioned cleaning.

[0059] Further, the alcohol solvent is selected, for example, from a monohydric alcohol or a dihydric alcohol. Exemplarily, the monohydric alcohol is selected from at least one of alcohols containing 1-40 carbon atoms, such as methanol, ethanol, propanol, and isopropanol. Exemplarily, the dihydric alcohol has the meaning as described above.

[0060] Furthermore, the amine solvent has the meaning as described above.

[0061] According to an embodiment of the present invention, the chalcogenide clusters prepared by the above-described synthesis method can achieve a yield of over 45%.

[0062] The present invention also provides chalcogenide clusters prepared by the above-described synthetic method.

[0063] The present invention also provides applications of the above-mentioned chalcogenide clusters, such as in photoelectrocatalysis, nonlinear optics, photoresist materials and other fields.

[0064] Preferably, the cluster compound can be used as a resin catalyst in the field of catalysis, and more preferably as a polyurethane resin catalyst.

[0065] Beneficial effects

[0066] This invention provides a novel method for synthesizing organotin chalcogenide clusters, yielding a novel material: a zero-dimensional T3-type ternary hybrid organotin supertetrahedral chalcogenide cluster crystalline material with an organic-inorganic hybrid structure, having a structural size of approximately 15.62-18.344 Å. The metal chalcogenide cluster possesses tunable metallic composition and tunable peripheral organic groups. This method is simple to synthesize, has low purity requirements for raw materials, and the raw materials are readily available and inexpensive. All raw materials can be directly purchased as chemically pure reagents, eliminating the need for further purification and facilitating large-scale production. The synthesis process generates minimal pollution, meeting green environmental protection requirements. Furthermore, the T3-type ternary hybrid organotin supertetrahedral chalcogenide cluster crystalline material prepared using this method achieves a yield of over 45%. This cluster compound can be used in fields such as photoelectrocatalysis and nonlinear optics. Attached Figure Description

[0067] Figure 1 This is a schematic diagram of the crystal structure of the crystalline product prepared in Example 1;

[0068] Figure 2 The X-ray powder diffraction pattern of the crystalline product prepared in Example 1;

[0069] Figure 3 The infrared spectrum of the crystalline product prepared in Example 1;

[0070] Figure 4 A photograph of the crystalline product prepared in Example 1;

[0071] Figure 5 The X-ray energy dispersive spectroscopy (EDS) spectrum of the crystalline product prepared in Example 1 is shown.

[0072] Figure 6 The image shows the negative ion mode EIS-MS spectrum of Example 1 in DMF;

[0073] Figure 7 The nonlinear optical properties of the crystalline product prepared in Example 1 are shown in the scatter plot, which represents the actual test line and the solid line represents the fitted line.

[0074] Figure 8 This is a schematic diagram of the crystal structure of the crystalline product prepared in Example 4;

[0075] Figure 9 X-ray powder diffraction pattern of the crystalline product prepared in Example 4;

[0076] Figure 10 The infrared spectrum of the crystalline product prepared in Example 4;

[0077] Figure 11 This is a photograph of the crystalline product prepared in Example 4.

[0078] Figure 12 The image shows the X-ray energy dispersive spectroscopy (EDS) spectrum of the crystalline product prepared in Example 4.

[0079] Figure 13 The nonlinear optical properties of the crystalline product prepared in Example 4 are shown in the scatter plot, which represents the actual test line and the solid line represents the fitted line.

[0080] Figure 14 The X-ray powder diffraction pattern of the crystalline product prepared in Example 5;

[0081] Figure 15 The infrared spectrum of the crystalline product prepared in Example 5;

[0082] Figure 16 This is a photograph of the crystalline product prepared in Example 5.

[0083] Figure 17 The image shows the X-ray energy dispersive spectroscopy (EDS) spectrum of the crystalline product prepared in Example 5.

[0084] Figure 18 The graph shows the electrocatalytic performance of the crystalline product prepared in Example 5, where each line from top to bottom represents the catalytic current density of the sample in the electrode at different rotation speeds. Detailed Implementation

[0085] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0086] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0087] The single-crystal structure analysis of this invention was performed using a Rigaku Supernova single-crystal diffractometer from Japan. The X-ray source used for the X-ray powder diffraction pattern was Cu-Kα rays.

[0088] Example 1

[0089] Weigh out sulfur powder (96 mg, 3 mmol), indium trichloride tetrahydrate (58.85 mg, 0.2 mmol), and cadmium nitrate tetrahydrate (30.85 mg, 0.1 mmol). Add 1,2-propanediol (2 ml, 27.23 mmol), n-butyltin trichloride (0.1 mL, 0.6 mmol), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN, 2 ml, 16.18 mmol), and N,N-dimethylformamide (DMF, 1 ml, 12.91 mmol) sequentially. Stir for 30 minutes. Place the mixture in an oven at 120°C for 7 days. Remove and allow to cool naturally to room temperature. Separate the solid phase and wash with alcohol or amine to obtain the target product. Figure 4 As shown, the target product of this embodiment is a pale yellow octahedral crystal with a size of approximately 80 μm and a yield of 55%; wherein the size of the cluster nucleus is approximately 18.15 Å.

[0090] Figure 1 This is a schematic diagram of the crystal structure of the crystalline material prepared in Example 1, illustrating that the crystalline material has a three-layer structure with organotin located at the four apex positions; Figure 2 The image shows the X-ray powder diffraction pattern of the crystalline compound prepared in Example 1. The theoretical value represents the simulated powder diffraction pattern, and the experimental value represents the powder diffraction pattern of the above crystal when it was actually placed in air, indicating that the cluster compound is a crystalline compound. Figure 3 The infrared spectrum of the crystalline material prepared in Example 1; Figure 5 The X-ray energy dispersive spectroscopy (EDS) spectrum of the crystalline material prepared in Example 1 is shown below. Figure 3 and Figure 5 It can be seen that the organotin sulfide cluster compound was successfully prepared; Figure 6 The image shows the negative ion mode EIS-MS spectrum of Example 1 in DMF, demonstrating that the cluster compound can maintain structural stability in DMF solution; Figure 7 The nonlinear optical properties of the crystalline compound prepared in Example 1 are shown in the scatter plot, which represents the actual test line and the solid line represents the fitted line. This indicates that the cluster compound has an obstructive effect on the passage of laser light under laser irradiation, thus reducing the energy of the laser beam.

[0091] T3-[(nBuSn)4M4M'2S prepared in Example 1 16 The molecular formula of the crystalline cluster compound is C1. 16 H 36 Cd2In4Sn4S 16 Its crystalline form is tetragonal, with space group I41 / a; its crystal parameters are shown in the table below:

[0092]

[0093] Example 2

[0094] Sulfur powder (96 mg, 3 mmol), indium trichloride tetrahydrate (58.85 mg, 0.2 mmol), and zinc chloride (13.63 mg, 0.1 mmol) were weighed and then added sequentially with ethylene glycol (1 ml, 17.93 mmol), n-butyltin trichloride (0.1 ml, 0.6 mmol), and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN, 1.75 ml, 14.16 mmol). The mixture was stirred for 30 minutes and placed in a 60°C oven for 7 days. After removal, it was allowed to cool naturally to room temperature. The solid phase was separated and washed with alcohol or amine to obtain the target product. The target product in this example was a pale yellow octahedral crystal with a crystal size of approximately 70 μm and a yield of 58%; the size of the cluster nucleus was approximately 15.84 Å.

[0095] Example 3

[0096] Sulfur powder (96 mg, 3 mmol), indium trichloride tetrahydrate (58.85 mg, 0.2 mmol), and manganese chloride (12.58 mg, 0.1 mmol) were weighed and then added sequentially with ethylene glycol (1 ml, 17.93 mmol), n-butyltin trichloride (0.1 ml, 0.6 mmol), and 1,5-diazabicyclo[4.3.0]non-5-ene (DBN, 2.5 ml, 20.22 mmol). The mixture was stirred for 30 minutes and then placed in a 60°C oven for 7 days. After removal, it was allowed to cool naturally to room temperature. The solid phase was separated and washed with alcohol or amine to obtain the target product. The target product in this example was a light red or pale yellow octahedral crystal with a crystal size of 70 μm and a yield of 50%; the size of the cluster nucleus was approximately 15.86 Å.

[0097] Tests showed that the crystal parameters and X-ray powder diffraction patterns of the target products obtained in Examples 2-3 were consistent with those in Example 1, meaning that Examples 2-3 and Example 1 were the same crystalline products.

[0098] Example 4

[0099] Weigh out sulfur powder (96 mg, 3 mmol), indium trichloride tetrahydrate (0.2 mmol, 58.85 mg), and cadmium nitrate tetrahydrate (0.1 mmol, 30.85 mg). Add 1,2-propanediol (2 ml), phenyltin trichloride (0.05 ml, 0.3 mmol), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN, 2 ml, 16.18 mmol), and N,N-dimethylformamide (DMF, 1 ml, 12.91 mmol) sequentially. Stir for 30 minutes. Place the mixture in a 120°C oven for 7 days. Remove and allow to cool naturally to room temperature. Separate the solid phase and wash with alcohol or amine to obtain the target product. Figure 11 As shown, the target product of this embodiment is a pale yellow octahedral crystal with a crystal size of approximately 100 μm and a yield of 45%; wherein the size of the cluster nucleus is approximately 15.62 Å.

[0100] Figure 8 This is a schematic diagram of the crystal structure of the crystalline material prepared in Example 4. Figure 8 It can be seen that the crystalline material has a three-layer structure, with organotin located at the four apex positions; Figure 9 The image shows the X-ray powder diffraction pattern of the crystalline compound prepared in Example 4, indicating that the cluster compound synthesized in this example is a crystalline compound. Figure 10 The infrared spectrum of the crystalline material prepared in Example 4; Figure 12 The X-ray energy dispersive spectroscopy (EDS) spectrum of the crystalline material prepared in Example 4 is shown below. Figure 10 and Figure 12 It can be seen that the organotin sulfide cluster compound was successfully prepared; Figure 13 The nonlinear optical properties of the crystalline compound prepared in Example 4 are shown in the scatter plot, which represents the actual test line and the solid line represents the fitted line. This indicates that the cluster compound has an obstructive effect on the passage of laser light under laser irradiation, thus reducing the energy of the laser beam.

[0101] T3-[(PhSn)4M4M'2S prepared in Example 4 16 The molecular formula of the crystalline cluster compound is C1. 24 H 20 Cd2In4Sn4S 16 Its crystalline form is cubic, and its space group is Fd⁻³m; its crystal parameters are shown in the table below:

[0102]

[0103] Example 5

[0104] Weigh L-cysteine ​​(243.3 mg, 2 mmol), gallium nitrate hydrate (102.3 mg, 0.2 mmol), and cobalt nitrate hexahydrate (58.2 mg, 0.1 mmol). Then, sequentially add N,N-dimethylformamide (DMF, 1 ml, 12.91 mmol), phenyltin trichloride (0.05 ml, 0.3 mmol), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN, 1 ml, 8.09 mmol), and n-propylamine (2 ml, 24.33 mmol) into a 20 ml glass bottle and stir for 30 minutes. Seal the bottle and transfer it to a 60°C oven for 7 days. Remove the bottle, allow it to cool naturally to room temperature, separate the solid phase, and wash with alcohol or amine to obtain the target product. Figure 16 As shown, the target product of this embodiment is a green octahedral crystal with a crystal size of approximately 180 μm and a yield of 48%; wherein the size of the cluster nucleus is approximately 15.6 Å.

[0105] Figure 15 The image shows the infrared spectrum of the crystalline material prepared in Example 5. Figure 17 The X-ray energy dispersive spectrum of the crystalline material prepared in Example 5 is shown below. Figure 15 and Figure 17 It can be seen that the organotin sulfide cluster compound was successfully prepared.

[0106] The molecular formula of the crystalline cluster compound prepared in Example 5 is C 24 H 20 Co2Ga4Sn4S 16 Its crystalline form is basically the same as that of the crystalline form in Example 4.

[0107] Application examples

[0108] The electrocatalytic oxygen reduction performance of the crystalline material from Example 5 was tested. Specifically, 5 mg of the crystalline material from Example 5 was dispersed in a mixed solvent of water / isopropanol with a volume ratio of 3:1. 15 μl of Nafion solution was added to prepare a working electrode. The sample mixture was dropped onto the surface of a glassy carbon electrode to form the working electrode. A platinum electrode was used as the counter electrode, and an Ag / AgCl electrode was used as the reference electrode. The test was conducted in a 0.1 M KOH electrolyte solution at a scan rate of 20 mV / s. The current density at different rotation speeds was measured to evaluate its performance.

[0109] Figure 18The graph shows the electrocatalytic oxygen reduction performance of the crystalline product prepared in Example 5. Each line from top to bottom represents the catalytic current density of the sample in the electrode at different rotational speeds (400 rpm, 625 rpm, 900 rpm, 1225 rpm, 1600 rpm, and 2025 rpm, respectively). It can be seen that the current density increases with the increase of the electrode rotation speed, indicating that increasing the electrode rotation speed helps improve the electrocatalytic oxygen reduction performance of the sample.

[0110] The exemplary embodiments of the present invention have been described above. However, the scope of protection of this application is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A chalcogen cluster compound characterized in that, The chalcogenide cluster comprises at least a core and a periphery, the core comprises metal ions, and the periphery comprises organotin; the core and the periphery form a cluster structure; The molecular general formula of the chalcogen cluster is (RSn)4M4M'2S 16 wherein R is selected from n-butyl and / or phenyl; M is selected from In or Ga; M' is selected from Zn, Cd, Mn; The cluster structure of the chalcogenide cluster is supertetrahedron; In the cluster structure of the chalcogenide cluster, the organotin is located at four apex positions of the supertetrahedron.

2. The chalcogen cluster compound of claim 1, wherein, The size of the cluster core of the cluster is 15.62-18.344 Å; The chalcogenide cluster is a pure-phase crystalline substance; The crystal structure type of the chalcogenide cluster is T3 type; The chalcogen cluster is (nBuSn)4M4M'2S 16 The chalcogen cluster is (nBuSn)4M4M'2S 16 The chalcogen cluster is (nBuSn)4M4M'2S 3. The chalcogen cluster compound of claim 2, wherein, The crystalline substance is a blocky crystalline substance; The color of the crystal of the crystalline substance is dark or light or colorless, and different metal ions correspond to crystals of different colors; The size of the crystal of the crystalline substance is 20-200 μm.

4. The chalcogen cluster compound of claim 2, wherein, The (nBuSn)4M4M'2S 16 The chemical formula of the cluster is C 16 H 36 Cd2In4Sn4S 16 ; (nBuSn)4M4M'2S 16 The space group of the crystalline substance of the cluster is I 41 / a, with the cell parameters: a = b = 19.5219 A, c = 27.0483 A, α = 90 o , β = 90 o , γ = 90 o , V = 10308.2 A 3 ; (nBuSn)4M4M'2S 16 The crystal system of the crystal state of the cluster compound is tetragonal.

5. The chalcogen cluster compound of claim 4, wherein, (nBuSn)4M4M'2S 16 The crystalline state of the cluster is a bulk crystalline state. When the (nBuSn)4M4M'2S 16 When M is In and M' is Cd in the cluster compound, the crystals of the crystalline compound are light yellow or light red.

6. The chalcogen cluster compound of claim 2, wherein, (nBuSn)4M4M'2S 16 The crystal parameters of the cluster are shown in Table 1 below: Table 1 7. The chalcogen cluster compound of claim 2, wherein, The (PhSn)4M4M'2S 16 The chemical formula of the cluster is C 24 H 20 Cd2In4Sn4S 16 ; said (PhSn)4M4M'2S 16 The space group of the crystalline substance of the cluster is Fd-3m, and the cell parameters are: a = b = c = 27.71 Å, α is 90 o , β is 90 o , γ is 90 o , V is 21278 Å 3 ; said (PhSn)4M4M'2S 16 The crystal system of the crystalline substance of the cluster compound is cubic.

8. The chalcogen cluster compound of claim 7, wherein, said (PhSn)4M4M'2S 16 The crystalline state of the cluster is a bulk crystalline state. When the (PhSn)4M4M'2S 16 When M is In and M' is Cd in the cluster compound, the crystals of the crystalline compound are light yellow in color.

9. The chalcogen cluster compound of claim 2, wherein, said (PhSn)4M4M'2S 16 The crystal parameters of the cluster are shown in Table 2 below: Table 2 10. A method for the synthesis of a crystalline form of a chalcogen cluster compound as defined in any one of claims 1 to 9, characterized in that, The synthesis method comprises the following steps: 1) uniformly mixing organotin salt, other main group metal salt, transition metal salt, and sulfur source, uniformly mixing in a reaction solvent, and then performing a solvothermal reaction under a sealed condition to obtain a mixture; the molar ratio of the organotin salt, the other main group metal salt, the transition metal salt, and the sulfur source is 1:0.2-2:0.1-1:1-15; 2) separating and purifying the mixture obtained after the reaction in step 1) to prepare a crystalline substance of a chalcogenide cluster; The organotin salt is selected from butyltin or phenyltin; The other main group metal salt is selected from at least one of chloride, sulfate, nitrate, and acetate of other main group metals; The transition metal salt is selected from at least one of chloride, sulfate, nitrate, and acetate of transition metals; in the transition metal salt, the transition metal is selected from at least one of Zn, Cd, and Mn; The sulfur source is selected from at least one of organic sulfur source, inorganic sulfide, and elemental sulfur.

11. The method of synthesis of claim 10, wherein, In step 1), the reaction solvent is selected from organic amine and / or organic alcohol; In step 1), the reaction temperature of the solvothermal reaction is 40-160 ℃; In step 1), the reaction time of the solvothermal reaction is 72-360 hours; In step 2), the purification comprises washing with a washing solvent and optionally drying; The washing solvent is selected from alcohol solvent and / or amine solvent.

12. Use of the chalcogenide cluster according to any one of claims 1-9 in the field of nonlinear optics.

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