A triphenylene carboxylic acid ligand modified with vicinal thiol, a metal organic framework material containing MS2O2 sites, and preparation methods and applications thereof

Abstract

The present invention discloses a triphenylene carboxylic acid ligand modified with ortho-thiol, a metal organic framework material containing MS2O2 sites, and its preparation method and application. The ligand has a triphenylene main π conjugated structure and ortho-modified carboxyl and thiol groups, and is coordinated with metal ions through a solvent thermal reaction. The bond length of the S-M bond formed by the coordination is shorter than the bond length of the O-M bond formed by the coordination of the carboxyl group and the metal ion, so that the d-π conjugation between the coordinated metal ion and the π conjugated organic ligand is strengthened, which is conducive to improving the rate of electron conduction in the metal organic framework material, thereby further improving the reaction activity of the metal organic framework material. In particular, the material with Co as the coordinated metal ion can achieve a photocatalytic hydrogen evolution rate (HER) of 4126.01μmol g ‑ 1 h ‑1 , with excellent photocatalytic hydrogen evolution activity. Metal-organic framework materials can be produced by solvent thermal reaction. The preparation process is mature, the steps are simple, the yield is high, and they can be prepared in large quantities.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal organic framework functional materials, and specifically relates to an ortho-thiol-modified triphenylene carboxylic acid ligand, a metal organic framework material containing MS2O2 sites, and a preparation method and application thereof. Background Art

[0002] With the growing demand for energy and increasing environmental protection worldwide, the application of clean energy is gradually expanding. At the same time, urbanization and industrial production inevitably cause water pollution. Therefore, the discovery and application of new energy production technologies and environmental governance methods are urgent.

[0003] Hydrogen is considered one of the most ideal clean energy sources due to its high energy density, high combustion efficiency, and the fact that it produces no greenhouse gases. Therefore, hydrogen energy has important research implications. Photocatalysis, as a green and efficient technology, converts widely available solar energy into chemical energy and is a hot research topic in the energy and environment fields. The design and synthesis of photocatalysts are key steps in achieving efficient solar energy conversion. However, problems such as low photogenerated carrier migration efficiency and poor photostability greatly limit their application. Therefore, developing stable photocatalytic hydrogen evolution catalysts with high photogenerated carrier migration efficiency is key to improving the rate of photocatalytic hydrogen evolution. Efficient photocatalytic hydrogen evolution catalyst materials must have the ability to transport electrons and active sites to accept electrons and protons.

[0004] Metal-organic frameworks (MOFs) are porous, ordered frameworks formed by coordination bonds between metals or metal clusters and organic ligands. Due to their unique advantages, such as large surface area, highly tunable structure, and well-defined active sites, MOFs have attracted considerable attention and research in areas such as heavy metal adsorption, energy storage, and photoelectrocatalysis. However, traditional three-dimensional MOFs have low electrical conductivity and are unable to provide the ability to transport electrons.

[0005] In recent years, two-dimensional metal-organic frameworks have attracted widespread attention from scientists in the field of photocatalysis due to their good photochemical properties. Summary of the Invention

[0006] Based on the above reasons, the first object of the present invention is to provide a triphenylene carboxylic acid ligand modified with an ortho-thiol, wherein the ortho position of the carboxyl group of the triphenylene carboxylic acid is modified with a thiol, so that the ligand can coordinate with the metal ion simultaneously through the carboxyl group and the thiol, and the π-conjugated d-π conjugation with the ligand triphenylene structure is strengthened, thereby providing a possibility for enhancing the electron conduction rate.

[0007] The second object of the present invention is to provide a method for preparing an ortho-thiol-modified triphenylene carboxylic acid ligand.

[0008] The third object of the present invention is to provide a metal-organic framework material containing MS2O2 sites; wherein the bond length of MS is shorter than that of MO, so that the d-π conjugation between the coordinated metal ions and the π-conjugated organic ligands is strengthened, which is beneficial to enhance the rate of electron conduction and improve the photocatalytic performance of the material.

[0009] The fourth object of the present invention is to provide a method for preparing a metal organic framework material containing MS2O2 sites, which is prepared by a solvent thermal reaction, has a simple preparation method and is suitable for industrial preparation.

[0010] The fifth object of the present invention is to provide an application of a metal organic framework material containing MS2O2 sites.

[0011] The first object of the present invention can be achieved by adopting the following technical solutions:

[0012] A triphenylene carboxylic acid ligand modified with an ortho-thiol, wherein the ligand is a compound having a structure shown in Formula I;

[0013]

[0014] The second object of the present invention can be achieved by adopting the following technical solutions:

[0015] A method for preparing an ortho-thiol-modified triphenylene carboxylic acid ligand, comprising reacting a compound of formula II with a sulfhydride in a 1,3-dimethyl-2-imidazolidinone solution, followed by acidification to obtain an ortho-thiol-modified triphenylene carboxylic acid ligand of formula I.

[0016]

[0017] The third object of the present invention can be achieved by adopting the following technical solutions:

[0018] A metal organic framework material containing MS2O2 sites, comprising a ligand of a compound having a structure shown in formula I and a metal ion M,

[0019] In one of the compounds of the structure shown in Formula I, the carboxyl oxygen atom and the adjacent mercaptosulfur atom on the ligand are coordinated and connected with the same metal ion M, and each metal ion M is coordinated and connected with two ligands to form an MS2O2 connection site.

[0020] Furthermore, the metal ion M is one or a combination of two or more of Ni, Co, Zn or In.

[0021] The fourth object of the present invention can be achieved by adopting the following technical solutions:

[0022] A method for preparing a metal organic framework material containing MS2O2 sites, comprising: performing a solvothermal reaction between a compound having a structure shown in formula I and a precursor of a metal ion M to prepare the metal organic framework material containing MS2O2 sites.

[0023] Furthermore, the precursor of the metal ion M is acetate, nitrate, chloride or hydrate of Ni, Co, Zn or In.

[0024] Furthermore, the molar ratio of the compound of the structure shown in Formula I to the precursor of the metal ion M is 1:(2-2.5).

[0025] Furthermore, the conditions for the solvent thermal reaction are:

[0026] A mixed reagent of DMF and / or DMA and water is used as a solvent; the reaction is carried out in a sealed manner at 110-140° C. for 6-72 hours; the volume ratio of DMF and / or DMA to water is (1-10):1.

[0027] Furthermore, the molar volume ratio of the compound of the structure represented by Formula I to the solvent is (6-20) μmol:1 mL.

[0028] Furthermore, the reaction includes a separation and washing process; after separation, the solid is washed with DMF and acetone; and then treated with Soxhlet extraction, and the solution of Soxhlet extraction is methanol or THF.

[0029] The fifth object of the present invention can be achieved by adopting the following technical solutions:

[0030] Application of any of the above metal organic framework materials containing MS2O2 sites as a photocatalytic hydrogen production catalyst.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] 1. The present invention discloses an ortho-thiol-modified triphenylene carboxylic acid ligand. The main structure of the triphenylene is a strong π-conjugated structure, which makes the ligand have high stability and reactivity. In particular, the S-containing thiol group is a soft group. Coordinating with the metal ion at the same time as the carboxyl group can shorten the distance between the metal ion and the ligand, enhance the d-π conjugation between the metal ion and the ligand, and improve the performance of the complex.

[0033] 2. In a metal-organic framework material containing MS2O2 sites of the present invention, when the ligand coordinates with the metal ion through the ortho-carboxyl and thiol groups, the bond length of the SM bond formed by the coordination of the thiol group ortho to the carboxyl group and the metal ion is shorter than the bond length of the OM bond formed by the coordination of the carboxyl group and the metal ion, thereby strengthening the d-π conjugation between the coordinated metal ion and the π-conjugated organic ligand, which is beneficial to improving the rate of electron conduction in the metal-organic framework material, thereby further improving the reaction activity of the metal-organic framework material.

[0034] 3. The preparation method of the metal organic framework material containing MS2O2 sites of the present invention can be produced and prepared by solvent thermal reaction. The preparation process is mature, the steps are simple, the yield is high, and it can be prepared in large quantities.

[0035] 4. The application of the metal organic framework material containing MS2O2 sites of the present invention as a photocatalytic hydrogen production catalyst, especially the material with Co as the coordinated metal ion, can achieve a photocatalytic hydrogen evolution rate (HER) of 4126.01 μmol g -1 h -1 , with excellent photocatalytic hydrogen evolution activity. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 The molecular structure diagram of the metal organic framework material containing MS2O2 sites of the present invention;

[0037] Figure 2 This is the H NMR spectrum of the ortho-thiol-modified triphenylene carboxylic acid ligand prepared in Example 1-3;

[0038] Figure 3 This is the mass spectrum of the ortho-thiol-modified triphenylene carboxylic acid ligand prepared in Example 1-3;

[0039] Figure 4 X-ray powder diffraction patterns of the metal-organic framework materials containing MS2O2 sites prepared in Examples 4-7;

[0040] Figure 5 Schematic diagram of the TPTM-Ni stacking structure prepared in Example 4;

[0041] Figure 6 Fourier transform infrared spectra of TPTM prepared in Example 1, TPTM-Ni, TPTM-Co, TPTM-Zn and TPTM-In prepared in Examples 4 to 7;

[0042] Figure 7 Figure 2 is a graph of photocatalytic hydrogen evolution rates under different reaction conditions. DETAILED DESCRIPTION

[0043] The technical solutions of the present invention will be described clearly and completely below with reference to specific embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are also within the scope of protection of the present invention.

[0044] The two-dimensional hydroxy metal organic framework is composed of conjugated organic ligands containing multidentate ortho-substituted -OH (HHTP, HATN-6OH, etc.) and metal ions (such as Fe 2+ 、Co 2+ 、Ni 2+ ) coordination to form a two-dimensional network structure. Due to its inherent porosity, clear active sites (MO4) and π-d conjugation, it provides an effective electron transfer pathway, which is conducive to efficient photocatalytic hydrogen production. However, the active site (MO4) of the two-dimensional hydroxyl metal organic framework is relatively single, and the long MO bond limits the rate of electron conduction, which has limitations in the field of photocatalysis.

[0045] Therefore, the present invention provides an ortho-thiol-modified triphenylene carboxylic acid ligand, a metal organic framework material containing MS2O2 sites, and its preparation method and application, and prepares a π-conjugated two-dimensional metal organic framework containing a novel active site (such as MS2O2) for application in the field of photocatalysis. The S-containing group is a soft group. When S is coordinated with a metal ion, the bond length of MS is shorter than that of MO, thereby strengthening the d-π conjugation between the coordinated metal ion and the π-conjugated organic ligand, which is beneficial to increasing the rate of electron conduction, thereby improving the photocatalytic performance.

[0046] A triphenylene carboxylic acid ligand modified with an ortho-thiol, wherein the ligand is a compound having a structure shown in Formula I;

[0047]

[0048] The ligand's main structure is triphenylene, which exhibits strong π-conjugation. The carboxyl and thiol groups within the ligand act as coordinating groups with the metal ion, allowing the ligand to extend around the metal ion as a node, forming a two-dimensional metal-organic framework. The sulfur-containing thiol group is particularly soft, and its simultaneous coordination with the carboxyl group to the metal ion shortens the distance between the metal ion and the ligand, enhancing the d-π conjugation between the metal ion and the ligand and improving the performance of the complex.

[0049] The present invention also provides a method for preparing an ortho-thiol-modified triphenylene carboxylic acid ligand. The compound of the structure shown in Formula II reacts with a sulfhydride in a 1,3-dimethyl-2-imidazolidinone solution, and after acidification, an ortho-thiol-modified triphenylene carboxylic acid ligand of the structure shown in Formula I is prepared. The reaction process is as follows:

[0050]

[0051] As one embodiment, the hydrosulfide is sodium hydrosulfide or potassium hydrosulfide; preferably, the hydrosulfide is sodium hydrosulfide.

[0052] As one embodiment, the molar ratio of the compound of formula II to the hydrosulfide is 1:(3-4).

[0053] In one embodiment, the reaction is carried out under an inert gas atmosphere at 20-40° C. for 1-4 hours.

[0054] As one embodiment, the acid used for acidification is dilute hydrochloric acid and / or dilute sulfuric acid; in this embodiment, the acidification is performed to a pH value less than or equal to 2.

[0055] The present invention also provides a metal organic framework material containing MS2O2 sites, comprising a ligand of a compound having a structure shown in formula I and a metal ion M.

[0056] In one of the compounds of formula I, the carboxyl oxygen atom and the adjacent thiol sulfur atom on the ligand are coordinated with the same metal ion M, and each metal ion M is coordinated with two ligands to form a MS2O2 connection site; the structure is as follows Figure 1 shown.

[0057] The triphenylene in the ligand of the compound of the structure shown in Formula I has a rigid planar structure. When the carboxyl group and the ortho-thiol group thereon coordinate with the metal ion, an MS2O2 connection site is formed. The triphenylene structure of the ligand is extended through the connection site to form a two-dimensional metal-organic framework network structure. In particular, the bond length of the SM bond formed by the coordination of the thiol group and the metal ion is shorter than the bond length of the OM bond formed by the coordination of the carboxyl group and the metal ion, thereby strengthening the d-π conjugation between the coordinated metal ion and the π-conjugated organic ligand. The longer bond length of MO4 in the traditional two-dimensional hydroxy metal-organic framework prolongs the electron conduction time, resulting in a lower electron conduction rate. The MS2O2 connection site of the present invention is conducive to improving the rate of electron conduction in the metal-organic framework material, thereby further improving the reactivity of the metal-organic framework material.

[0058] As one embodiment, the metal ion M is one or a combination of two or more of Ni, Co, Zn or In. The present invention can use a variety of metal ions to coordinate with ligands to form connection sites, all of which show enhanced activity.

[0059] The present invention also provides a method for preparing a metal organic framework material containing MS2O2 sites, wherein the compound of the structure shown in Formula I is subjected to a solvent thermal reaction with a precursor of the metal ion M to prepare the metal organic framework material containing MS2O2 sites.

[0060] In one embodiment, the precursor of the metal ion M is an acetate, nitrate, chloride, or hydrate of Ni, Co, Zn, or In. Preferably, the precursor of the metal ion M is an acetate, or a hydrate of Ni, Co, or Zn; and the precursor of the metal ion M is a chloride of In.

[0061] As one embodiment, the molar ratio of the compound of the structure shown in Formula I to the precursor of the metal ion M is 1:(2-2.5).

[0062] As one embodiment, the conditions for the solvent thermal reaction are:

[0063] A mixed reagent of DMF and / or DMA and water is used as a solvent; the reaction is carried out in a sealed manner at 110-140° C. for 6-72 hours; the volume ratio of DMF and / or DMA to water is (1-10):1.

[0064] As one embodiment, the molar volume ratio of the compound of the structure represented by Formula I to the solvent is (6-20) μmol:1 mL.

[0065] As one embodiment, the reaction includes a separation and washing process; after separation, the solid is washed with DMF and acetone; and then treated with Soxhlet extraction, and the solution extracted with Soxhlet is

[0066] The present invention also provides the use of any of the above metal organic framework materials containing MS2O2 sites as a photocatalytic hydrogen production catalyst.

[0067] The following is a further description with reference to specific embodiments.

[0068] Example 1

[0069]

[0070] 0.22 mmol of the compound of formula II and 0.66 mmol of NaHS were weighed into a reaction flask, and the mixture was evacuated and purged with nitrogen three times. 10 mL of pre-degassed and dried 1,3-dimethyl-2-imidazolidinone (DMEU) was added, and the mixture was stirred at room temperature for 2 h. After the reaction was completed, 5% HCl was added under nitrogen protection to acidify the mixture to pH <2, and the residue was filtered to obtain the ortho-thiol-modified triphenylene carboxylic acid ligand of formula I, named TPTM. The NMR spectrum is shown in FIG. Figure 2 As shown, the mass spectrum Figure 3shown.

[0071] Example 2

[0072]

[0073] 0.22 mmol of the compound of formula II and 0.7 mmol of KHS were weighed into a reaction flask and evacuated with nitrogen three times. 10 mL of pre-degassed and dried 1,3-dimethyl-2-imidazolidinone (DMEU) was added, and the mixture was stirred at 20°C for 4 h. After the reaction was completed, 5% sulfuric acid was added under nitrogen to acidify the mixture to pH <2. The mixture was filtered and the residue was collected to obtain the compound of formula I, named TPTM.

[0074] Example 3

[0075]

[0076] 0.22 mmol of the compound of formula II and 0.88 mmol of NaHS were weighed into a reaction flask, and the mixture was evacuated and purged with nitrogen three times. 10 mL of pre-degassed and dried 1,3-dimethyl-2-imidazolidinone (DMEU) was added, and the mixture was stirred at 40°C for 1 hour. After the reaction was completed, 5% hydrochloric acid was added under nitrogen protection to acidify the mixture to pH <2, and the residue was filtered to obtain an ortho-thiol-modified triphenylene carboxylic acid ligand of formula I, which was named TPTM.

[0077] Example 4 Preparation Method of TPTM-Ni

[0078] 0.006 mmol of TPTM and 0.013 mmol of Ni(OAc)2·4H2O were weighed into a glass tube (8×150 mm), 0.4 mL of DMF and 0.4 mL of H2O were added, and the mixture was then sonicated for 10 min. The glass tube was sealed with an oxyhydrogen flame and reacted in a 120°C oven for 48 h, followed by natural cooling to room temperature. The powder was collected by centrifugation, washed with DMF (3×3 mL) and acetone (3×3 mL), then Soxhlet extracted in methanol solution for 1 day and dried in vacuum to obtain a metal-organic framework material containing NiS2O2 sites, named TPTM-Ni.

[0079] Example 5 Preparation of TPTM-Co

[0080] 0.006 mmol of TPTM and 0.015 mmol of Co(OAc)2·4H2O were weighed into a glass tube (8×150 mm), 0.8 mL of DMF and 0.2 mL of H2O were added, and the mixture was then sonicated for 10 min. The glass tube was sealed with an oxyhydrogen flame and reacted in an oven at 110°C for 72 h, followed by natural cooling to room temperature. The powder was collected by centrifugation, washed with DMF (3×3 mL) and acetone (3×3 mL), then Soxhlet extracted in methanol solution for 1 day and dried in vacuum to obtain a metal-organic framework material containing CoS2O2 sites, named TPTM-Co.

[0081] Example 6 Preparation Method of TPTM-Zn

[0082] 0.006 mmol of TPTM and 0.014 mmol of Zn(OAc)2·2H2O were weighed into a glass tube (8×150 mm), 0.27 mL of DMF and 0.03 mL of H2O were added, and the mixture was then sonicated for 10 min. The glass tube was sealed with an oxyhydrogen flame and reacted in an oven at 140°C for 6 h, followed by natural cooling to room temperature. The powder was collected by centrifugation, washed with DMF (3×3 mL) and acetone (3×3 mL), then Soxhlet extracted in THF solution for 1 day and dried in vacuum to obtain a metal-organic framework material containing ZnS2O2 sites, named TPTM-Zn.

[0083] Example 7 Preparation Method of TPTM-In

[0084] 0.006 mmol of TPTM and 0.013 mmol of InCl3 were weighed into a glass tube (8×150 mm), 0.5 mL of DMF and 0.05 mL of H2O were added, and the mixture was then sonicated for 10 min. The glass tube was sealed with an oxyhydrogen flame and reacted in an oven at 120°C for 48 h, then naturally cooled to room temperature. The powder was collected by centrifugation, washed with DMF (3×3 mL) and acetone (3×3 mL), then Soxhlet extracted in THF solution for 1 day, and dried in vacuum to obtain a metal-organic framework material containing InS2O2 sites, named TPTM-In.

[0085] Test example:

[0086] (1) Use Material Studio to establish the AA stacking structure model of TPTM and Ni coordination, such as Figure 5 TPTM-Ni, TPTM-Co, TPTM-Zn and TPTM-In prepared in Example 4-Example 7 were subjected to X-ray powder diffraction, and the X-ray powder diffraction pattern was as shown Figure 4 shown.

[0087] A stacking structure model of TPTM coordinated with Ni was established using Material Studio. The simulated theoretical X-ray diffraction spectrum is highly consistent with the experimentally measured XRD spectrum of TPTM-Ni. Moreover, the XRD patterns of TPTM-Co, TPTM-Zn, and TPTM-In also correspond to the theoretical XRD patterns, indicating that the MOFs assembled from these four different metals are isostructural.

[0088] (2) TPTM prepared in Example 1, TPTM-Ni, TPTM-Co, TPTM-Zn and TPTM-In prepared in Examples 4 to 7 were subjected to Fourier transform infrared spectroscopy. The results are as follows: Figure 6 shown.

[0089] from Figure 6 The infrared spectrum shows that the stretching vibration peak of the C=O bond of the carbonyl group on the carboxyl group of TPTM-M is shifted compared with that of the TPTM ligand, indicating that the metal and the carboxylic acid are coordinated; and the 2500cm -1 The peak of α disappeared, indicating that the metal coordinated with sulfur. It can be seen that the metal coordinated with sulfur and oxygen to form MS2O2 sites.

[0090] Test example:

[0091] In order to study the photocatalytic hydrogen production performance of TPTM-M with different metals, 2 mg powder samples of TPTM-Ni, TPTM-Co, TPTM-Zn and TPTM-In prepared in Examples 4-7 were dispersed in 2.5 mL of DMF and 2.5 mL of deionized water as photocatalysts, and 8 mg of 1,3-dimethylbenzimidazole (BIH) was added as a sacrificial agent. Argon was bubbled for 30 minutes and then sealed. An LED lamp was used as a visible light source. After 4 hours of photocatalytic experiment, the sample was injected and the hydrogen was quantitatively determined by gas chromatography analysis. The catalytic reaction without sacrificial agent and catalyst was used as a control experiment. The results are shown in Figure 2. Figure 7 shown.

[0092] from Figure 7 It can be seen that without the sacrificial agent, almost no hydrogen is produced, and without the catalyst, the hydrogen evolution rate is less than 250 μmol g -1 h -1 , which shows that sacrificial agent and catalyst are indispensable.

[0093] Under the conditions of TPTM-Ni, TPTM-Co, TPTM-Zn, and TPTM-In catalysts, the photocatalytic hydrogen evolution rate (HER) of TPTM-Co was 4126.01 μmol g -1h -1 The photocatalytic hydrogen evolution rate (HER) of TPTM-Ni was 682.13 μmol g -1 h -1 The photocatalytic hydrogen evolution rate (HER) of TPTM-In was 458.78 μmol g -1 h -1 The photocatalytic hydrogen evolution rate (HER) of TPTM-Zn was 249.01 μmol g -1 h -1 It can be seen that TPTM-M has good HER performance, and TPTM-Co has the best HER performance. The possible reason is that Co is more tightly bound to the conjugated system, resulting in faster electron transfer rate, thereby improving the photocatalytic hydrogen evolution rate.

[0094] In summary, the present invention discloses an ortho-thiol-modified triphenylene carboxylic acid ligand, a metal-organic framework material containing MS2O2 sites, and its preparation method and application. A synthetic route for the ortho-thiol-modified triphenylene carboxylic acid organic ligand was designed and successfully synthesized. Furthermore, a π-conjugated two-dimensional metal-organic framework, TPTM-M, containing MS2O2 sites was assembled using TPTM and metal under solvothermal conditions. The bond length of MS in the MS2O2 sites is shorter than that of MO, which strengthens the d-π conjugation between the coordinated metal ion and the π-conjugated organic ligand, thereby enhancing the rate of electron conduction and thereby increasing the rate of photocatalytic hydrogen evolution.

[0095] The above embodiments are only preferred embodiments of the present invention and cannot be used to limit the scope of protection of the present invention. Any non-substantial changes and replacements made by technicians in this field on the basis of the present invention fall within the scope of protection required by the present invention.

Claims

1. A triphenylene carboxylic acid ligand modified with an ortho-thiol, characterized in that: The ligand is a compound having a structure shown in Formula I; 2. The method for preparing an ortho-thiol-modified triphenylene carboxylic acid ligand according to claim 1, characterized in that: The compound of formula II reacts with a sulfhydride in a 1,3-dimethyl-2-imidazolidinone solution, and after acidification, an ortho-thiol-modified triphenylene carboxylic acid ligand of formula I is prepared; 3. A metal organic framework material containing MS2O2 sites, characterized in that: The compound comprising the structure shown in formula I and the metal ion M, The carboxyl oxygen atom and the adjacent thiol sulfur atom on the compound of the structure shown in Formula I are coordinated and connected to the same metal ion M, and each metal ion M is coordinated and connected to two compounds to form an MS2O2 connection site; The metal ion M is one or a combination of two or more of Ni, Co, Zn or In.

4. The method for preparing a metal organic framework material containing MS2O2 sites according to claim 3, characterized in that: The compound of the structure shown in formula I is subjected to a solvothermal reaction with a precursor of the metal ion M to prepare the metal organic framework material containing MS2O2 sites.

5. The method for preparing a metal organic framework material containing MS2O2 sites according to claim 4, characterized in that: The precursor of the metal ion M is acetate, nitrate or chloride of Ni, Co, Zn or In.

6. The method for preparing a metal organic framework material containing MS2O2 sites according to claim 4, characterized in that: The molar ratio of the compound of the structure shown in formula I to the precursor of the metal ion M is 1:(2-2.5).

7. The method for preparing a metal organic framework material containing MS2O2 sites according to claim 4, characterized in that: The conditions for the solvothermal reaction are: A mixture of DMF and / or DMA and water is used as a solvent; the reaction is carried out in a sealed manner at 110-140° C. for 6-72 hours; the volume ratio of DMF and / or DMA to water is (1-10):1; The molar volume ratio of the compound represented by the structure of Formula I to the solvent is (6-20) μmol:1 mL.

8. The method for preparing a metal organic framework material containing MS2O2 sites according to claim 4, characterized in that: After the reaction, a separation and washing process is included; After separation, the solid was washed with DMF and acetone and then processed by Soxhlet extraction with methanol or THF.

9. Use of the metal organic framework material containing MS2O2 sites as claimed in claim 3 as a photocatalytic hydrogen production catalyst.

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