Ortho-thiol modified triphenylene carboxylic acid ligand, MS2O2 site-containing metal organic framework material as well as preparation methods and application of ortho-thiol modified triphenylene carboxylic acid ligand and MS2O2 site-containing metal organic framework material

Abstract

The invention discloses an ortho-thiol modified triphenylene carboxylic acid ligand, an MS2O2 site-containing metal organic framework material as well as a preparation method and application of the ortho-thiol modified triphenylene carboxylic acid ligand and the MS2O2 site-containing metal organic framework material. The ligand has a triphenylene main body pi conjugated structure and ortho-position modified carboxyl and thiol groups, and is coordinated with metal ions through solvothermal reaction, and the bond length of an S-M bond formed by coordination is shorter than that of an O-M bond formed by coordination of the carboxyl and the metal ions, so that d-pi conjugation of the coordinated metal ions and the pi conjugated organic ligand is enhanced, and the metal ions and the pi conjugated organic ligand are combined to form the pi conjugated organic ligand. The electron conduction rate in the metal organic framework material is favorably improved, so that the reaction activity of the metal organic framework material is further improved. Especially, the photocatalytic hydrogen evolution rate (HER) can reach 4126.01 [mu] mol g <-1 > h <-1 > by taking Co as a coordination metal ion material, and the material has excellent photocatalytic hydrogen evolution activity. The metal organic framework material can be produced and prepared through solvothermal reaction, the preparation process is mature, the steps are simple, the yield is high, and large-scale preparation can be achieved.

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 continuous growth of energy demand and the increasing environmental protection in countries around the world, the application scope of clean energy has gradually expanded, which has become an inevitable trend. At the same time, urbanization and industrial production will inevitably cause pollution to environmental water bodies. Therefore, it is urgent to discover and apply new energy production technologies and environmental governance methods.

[0003] Hydrogen has the characteristics of high energy density, high combustion efficiency and no greenhouse gas production. It is considered to be one of the most ideal clean energy sources. Therefore, hydrogen energy has important research significance. Photocatalytic technology, as a green and efficient technology, converts the widely available solar energy into chemical energy and is one of the hot research directions in the field of energy and environment. The design and synthesis of photocatalysts are the key steps to achieve efficient conversion of solar energy. However, its low efficiency of photogenerated carrier migration and poor photostability greatly limit its application scope. Therefore, the development of stable photocatalytic hydrogen evolution catalysts with high photogenerated carrier migration efficiency is the key to improving the rate of photocatalytic hydrogen evolution. Efficient photocatalytic hydrogen evolution catalyst materials must have the ability to transmit electrons and have active sites to accept electrons and protons.

[0004] Metal-organic framework compounds (MOFs) are porous ordered framework materials formed by metals or metal clusters and organic ligands through coordination bonds. MOFs have attracted the attention and research of many scientists in the fields of heavy metal adsorption, energy storage, photoelectrocatalysis, etc. due to their unique advantages such as large specific surface area, highly adjustable height and clear active sites. However, traditional three-dimensional MOFs have low conductivity and are difficult 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 through the carboxyl group and the thiol at the same time, 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 purpose 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 enhancing the rate of electron conduction and improving 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 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 a structure shown in formula II with a sulfhydride in a 1,3-dimethyl-2-imidazolidinone solution, and then acidifying to obtain an ortho-thiol-modified triphenylene carboxylic acid ligand of a structure shown in 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 mercapto sulfur atom on the ligand are coordinated and connected to the same metal ion M, and each metal ion M is coordinated and connected to two ligands to form a 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 solvent; the reaction is carried out in a closed state 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 triphenylene carboxylic acid ligand modified by ortho-thiol of the present invention has a strong π-conjugated structure as the main structure of the triphenylene, so that the ligand has high stability and reactivity; in particular, the thiol group containing S is a soft group, and the coordination 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 metal organic framework material containing MS2O2 sites of the present invention is used as a photocatalytic hydrogen production catalyst, especially the material with Co as the coordinated metal ion, and the photocatalytic hydrogen evolution rate (HER) can reach 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 The mass spectrum of the ortho-thiol-modified triphenylene carboxylic acid ligand prepared in Example 1-3;

[0039] Figure 4 X-ray powder diffraction pattern of the metal organic framework material containing MS2O2 sites prepared in Example 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 the photocatalytic hydrogen evolution rate under different reaction conditions. DETAILED DESCRIPTION

[0043] The technical solution of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only partial embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are 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 path, 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 a triphenylene carboxylic acid ligand modified by ortho-thiol, a metal organic framework material containing MS2O2 sites, and a preparation method and application thereof, 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, and when S is coordinated with a metal ion, the bond length of MS is shorter than that of MO, so that the d-π conjugation between the coordinated metal ion and the π-conjugated organic ligand is strengthened, which is beneficial to improving 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 main structure of the ligand is triphenylene, which has strong π conjugation; the carboxyl and thiol groups can serve as coordination groups with metal ions, allowing the ligand to extend with the metal ions as nodes to form a two-dimensional metal-organic framework. In particular, the S-containing thiol group is a soft group, and 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.

[0049] The present invention also provides a method for preparing an ortho-thiol-modified triphenylene carboxylic acid ligand, wherein a 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 the structure represented by Formula II to the hydrosulfide is 1:(3-4).

[0053] As 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 and connected to the same metal ion M, and each metal ion M is coordinated and connected to 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, and when the carboxyl group and the thiol group at the adjacent position coordinate with the metal ion, an MS2O2 connection site is formed, and the triphenylene structure of the ligand is extended through the connection site to form a two-dimensional metal organic framework network structure. In particular, in the formed MS2O2 connection site, 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, so that the d-π conjugation of the coordinated metal ion and the π conjugated organic ligand is strengthened, and the longer bond length of MO4 in the traditional two-dimensional hydroxy metal organic framework prolongs the conduction time of the electron, 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 reaction activity 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 a compound having a structure shown in formula I is subjected to a solvothermal reaction with a precursor of a metal ion M to prepare the metal organic framework material containing MS2O2 sites.

[0060] As 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 hydrate of Ni, Co, Zn; 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 solvent; the reaction is carried out in a closed state 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; then Soxhlet extraction is used for treatment, and the solution extracted with Soxhlet

[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] Weigh 0.22mmol of the compound of formula II and 0.66mmol of NaHS into a reaction flask, evacuate and pass nitrogen for three times, add 10mL of pre-degassed and dried 1,3-dimethyl-2-imidazolidinone (DMEU), and then stir at room temperature for 2h; after the reaction, add 5% HCl under nitrogen protection to acidify to pH <2, filter, collect the filter residue to obtain the ortho-thiol-modified triphenylene carboxylic acid ligand of formula I, named TPTM; the NMR spectrum is as follows 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 the vacuum was evacuated and nitrogen was passed through for three times. 10 mL of 1,3-dimethyl-2-imidazolidinone (DMEU) which had been pre-degassed and dried was added, and then stirred at 20° C. for 4 h. After the reaction was completed, 5% sulfuric acid was added under nitrogen protection to acidify to pH < 2, and the filter was filtered and the residue was collected to obtain a compound of formula I, which was 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 vacuum was evacuated and nitrogen was passed through for three times. 10 mL of 1,3-dimethyl-2-imidazolidinone (DMEU) which had been pre-degassed and dried was added, and then the reaction was stirred at 40° C. for 1 hour. After the reaction was completed, 5% hydrochloric acid was added under nitrogen protection to acidify to pH < 2, and the filter was filtered and the residue was collected to obtain the ortho-thiol-modified triphenylene carboxylic acid ligand of formula I, which was named TPTM.

[0077] Example 4 Preparation method of TPTM-Ni

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

[0079] Example 5 Preparation of TPTM-Co

[0080] 0.006mmol of TPTM and 0.015mmol of Co(OAc)2·4H2O were weighed into a glass tube (8×150mm), 0.8mL of DMF and 0.2mL of H2O were added, and the mixture was then ultrasonically treated for 10min; the glass tube was sealed with an oxyhydrogen flame and reacted in an oven at 110°C for 72h, and then naturally cooled to room temperature; the powder was collected by centrifugation, and the powder sample was washed with DMF (3×3mL) and acetone (3×3mL), then Soxhlet extracted in a methanol solution for 1 day, and dried in a 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 ultrasonically treated for 10 min; the glass tube was sealed with an oxyhydrogen flame and reacted in an oven at 140°C for 6 h, and then naturally cooled to room temperature; the powder was collected by centrifugation, and the powder sample was 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] 0.006mmol of TPTM and 0.013mmol of InCl3 were weighed into a glass tube (8×150mm), 0.5mL of DMF and 0.05mL of H2O were added, and the mixture was then ultrasonically treated for 10min; the glass tube was sealed with an oxyhydrogen flame, and reacted in an oven at 120°C for 48h, and then naturally cooled to room temperature; the powder was collected by centrifugation, and the powder sample was washed with DMF (3×3mL) and acetone (3×3mL), 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 build the AA stacking structure model of TPTM and Ni coordination, such as Figure 5 As shown; TPTM-Ni, TPTM-Co, TPTM-Zn and TPTM-In prepared in Example 4 to Example 7 were subjected to X-ray powder diffraction, and the X-ray powder diffraction pattern was as shown Figure 4 shown.

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

[0088] (2) The TPTM prepared in Example 1, TPTM-Ni, TPTM-Co, TPTM-Zn and TPTM-In prepared in Examples 4 to 7 were detected by Fourier transform infrared spectroscopy. The results are as follows: Figure 6 as 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 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 of 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 DMF and 2.5 mL deionized water as photocatalysts, and 8 mg of 1,3-dimethylbenzimidazole (BIH) was added as a sacrificial agent. Bubble argon for 30 minutes and then seal. Use LED lamp as visible light source, carry out photocatalytic experiment for 4 hours before sampling, and the hydrogen quantity is determined by gas chromatography analysis; the catalytic reaction without sacrificial agent and catalyst is used as a control experiment, and the results are as follows Figure 7 shown.

[0092] from Figure 7 It can be seen that without the sacrificial agent, almost no hydrogen is produced, while 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 is 682.13 μmol g -1 h -1 ; The photocatalytic hydrogen evolution rate (HER) of TPTM-In is 458.78 μmol g -1 h -1 ; The photocatalytic hydrogen evolution rate (HER) of TPTM-Zn is 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 a triphenylene carboxylic acid ligand modified by ortho-thiol, a metal organic framework material containing MS2O2 sites, and a preparation method and application thereof, designs a synthetic route for triphenylene carboxylic acid organic ligand modified by ortho-thiol, and successfully synthesizes it. At the same time, a π-conjugated two-dimensional metal organic framework TPTM-M containing MS2O2 sites is assembled by using TPTM and metal under solvent thermal conditions. The bond length of MS in the MS2O2 site is shorter than that of MO, so that the d-π conjugation between the coordinated metal ion and the π-conjugated organic ligand is strengthened, which is beneficial to strengthening the rate of electron conduction, thereby improving the rate of photocatalytic hydrogen evolution.

[0095] The above-mentioned 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 substitutions made by technicians in this field on the basis of the present invention shall 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 of the structure shown in Formula I; 2. A method for preparing an ortho-thiol-modified triphenylene carboxylic acid ligand, characterized in that: 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; 3. A metal organic framework material containing MS2O2 sites, characterized in that: A ligand comprising a compound having a structure shown in Formula I and a metal ion M, In one of the compounds of the structure shown in Formula I, the carboxyl oxygen atom and the adjacent mercapto sulfur atom on the ligand are coordinated and connected to the same metal ion M, and each metal ion M is coordinated and connected to two ligands to form a MS2O2 connection site.

4. A metal organic framework material containing MS2O2 sites according to claim 3, characterized in that: The metal ion M is one or a combination of two or more of Ni, Co, Zn or In.

5. A method for preparing a metal organic framework material containing MS2O2 sites, 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.

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

7. The method for preparing a metal organic framework material containing MS2O2 sites according to claim 5, 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).

8. The method for preparing a metal organic framework material containing MS2O2 sites according to claim 5, characterized in that: The conditions for the solvent thermal reaction are: Using a mixed reagent of DMF and / or DMA and water as solvent; reacting in a sealed state 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 of the structure represented by Formula I to the solvent is (6-20) μmol:1 mL.

9. The method for preparing a metal organic framework material containing MS2O2 sites according to claim 5, characterized in that: After the reaction, a separation and washing process is included; After separation, the solid was washed with DMF and acetone; it was then processed using Soxhlet extraction with either methanol or THF.

10. Use of the metal organic framework material containing MS2O2 sites as claimed in any one of claims 3 to 9 as a photocatalytic hydrogen production catalyst.

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