A heterogeneous metal photocatalyst and its preparation method and application

Abstract

The present invention discloses a heterogeneous metal photocatalyst and a preparation method and application thereof, wherein the heterogeneous metal photocatalyst comprises a metal organic framework material LIFM-28, a bipyridine-dicarboxylic acid organic ligand, a metal iridium photoredox photosensitive center, and a transition metal catalytic center, which are self-assembled by coordination. In the present invention, the ligands of the photoredox and transition metal catalytic sites are precisely combined into the metal organic framework material at a precise position, thereby giving the material the photosensitivity and catalytic activity required for the carbon-heteroatom bond cross-coupling reaction, so that it has a very high application prospect in the field of organic small molecule catalysis and drug molecule development.

Description

Technical Field

[0001] The present invention relates to the technical field of metal catalysts, and in particular to a heterogeneous metal photocatalyst and a preparation method and application thereof. Background Art

[0002] Over the past half century, transition metal catalysis has attracted widespread attention in the field of chemistry, especially in the three awards of the Nobel Prize: in 2001, Knowles, Noyori and Sharpless were awarded for their contributions to stereoselective catalysis; in 2005, Chauvin, Grubbs and Schrock were awarded for olefin metathesis; in 2010, Heck, Negishi and Suzuki were awarded for palladium-catalyzed cross-coupling reactions. These achievements have demonstrated that transition metal catalysis can rapidly construct a variety of valuable organic compounds from relatively simple starting materials through new chemical activation modes unprecedented in organic chemistry. However, the core challenges of transition metal catalysis lie in the careful design of complex ligand structures, the effective control of metal oxidation states and electronic excitations by introducing stoichiometric amounts of oxidants or reductants, and the coping with harsh reaction conditions. In recent years, the combination of photoredox and transition metal catalysis - metal photocatalysis (MPC) - has become a versatile platform for the development of photocatalytic synthetic chemistry. The high efficiency of MPCs stems from the fact that their photoredox centers generate long-lived photoexcited states upon light irradiation, which can interact with transition metal catalysts via single electron transfer (SET) or energy transfer (ET) to regulate the oxidation state of the metal complex.

[0003] In the MPC system, photocatalysts absorb energy under light and generate reactive free radical species from abundant natural chemicals, while metal catalysts manipulate these active free radical intermediates to promote chemical transformations under mild environmental conditions. This approach not only reduces the dependence on large amounts of stoichiometric oxidants or reductants, but also significantly alleviates the harshness of reaction conditions, promotes reaction development through a new substrate activation mode, and forms a complementary relationship with traditional transition metal catalysts. However, most MPC catalysts are homogeneous in nature, which brings challenges in catalyst recovery, structural stability, and product separation and purification. In addition, due to the low concentration of catalyst intermediates, the efficiency of single electron transfer or energy transfer between photocatalysis and metal catalysis cycles is limited, which restricts the practical application of this dual catalytic approach. Metal-organic framework materials (MOFs), as a class of hybrid porous crystalline materials, have been recognized as a powerful platform for simulating and studying artificial photosynthetic and transition metal catalytic systems. MOFs have unique structural and functional tunability, and photosensitizing centers or metal active sites can be incorporated into the framework for catalytic applications. The periodic structure, high specific surface area, and uniform pore size help expose active sites, promote substrate diffusion, and improve the transfer efficiency of key intermediates. The site isolation of active centers within MOFs can also alleviate the problem of catalyst deactivation. The confined pore environment provides a suitable enrichment space for key intermediate species, thereby increasing the collision probability of the reaction species. The heterogeneous characteristics endow MOFs catalysts with the ability to be recycled and regenerated. More importantly, by integrating photoredox components and metal active sites into the MOF structure, the high local concentration and close connection of these active centers may contribute to the efficient transfer of electrons and energy, thereby accelerating the catalytic cycle due to the space confinement effect. Therefore, the careful design and construction of MOF-based MPC platforms (MPC-MOFs) may greatly promote the development of MPC.

[0004] Nevertheless, methods for integrating photoredox and transition metal catalytic sites into MOFs to construct MPC-MOFs for light-driven multicomponent organic reactions are still limited. Existing methods are mainly achieved through de novo synthesis of mixed ligands or post-synthetic modification through ligand or metal exchange. However, precise control of the location and number of photoredox and transition metal catalytic centers in MOF matrices remains a daunting challenge, although it is essential to promote organic catalytic photoreactions through synergistic dual catalytic modes and elucidate the underlying catalytic mechanisms at the atomic level. With in-depth research, MPC-MOFs may play an increasingly important role in future organic synthesis, especially in the development of new catalytic systems that are environmentally friendly and highly efficient. By optimizing MOF structure and improving the synergistic effect of catalytic sites, MPC-MOF is expected to become an important tool to promote the development of chemical synthesis and materials science. Future research will continue to focus on solving existing challenges, such as catalyst recyclability, efficiency of catalytic cycles, and stability of catalyst structure, so that MPC-MOF technology can be more widely used in practical chemical synthesis. Summary of the invention

[0005] The present invention aims to solve at least one of the above technical problems existing in the prior art. To this end, the present invention aims to provide a heterogeneous metal photocatalyst and a preparation method and application thereof.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is:

[0007] The first aspect of the present invention provides a heterogeneous metal photocatalyst, which includes a metal organic framework material LIFM-28, a bipyridine-dicarboxylic acid organic ligand, a metal iridium photo-oxidation-reduction photosensitive center, and a transition metal catalytic center, which are self-assembled through coordination.

[0008] In the present invention, ligands for photoredox and transition metal catalytic sites are precisely incorporated into metal organic framework materials at precise positions, thereby endowing the materials with the photosensitivity and catalytic activity required for carbon-heteroatom bond cross-coupling reactions.

[0009] In some embodiments of the present invention, the molar ratio of the metal organic framework material LIFM-28, bipyridine-dicarboxylic acid organic ligand, metal iridium photo-oxidation-reduction photosensitive center, and transition metal catalytic center is 1:0.5~2:0.1~1:0.1~1.5.

[0010] In some embodiments of the present invention, the bipyridine-dicarboxylic acid organic ligand includes at least one of 2,2'-bipyridine-5,5'-dicarboxylic acid and 3,3'-(2,2'-bipyridine)-5,5'-diyl-diacrylic acid.

[0011] In some embodiments of the present invention, the metal iridium photoredox photosensitive center is provided by a photoredox complex comprising [Ir(dF(CF3)ppy)2].

[0012] In some embodiments of the present invention, the transition metal catalytic center is provided by a transition metal catalyst including nickel chloride, nickel bromide, nickel iodide, cobalt chloride, cobalt bromide, cobalt iodide, cupric chloride, cupric bromide, cupric iodide, cuprous iodide and hydrates of the above metal salts.

[0013] In some embodiments of the present invention, the metal organic framework material LIFM-28 is {[Zr6(μ3-O)8-(H2O)8(L)4]·(free solvent molecules)} (L=2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-dicarboxylate).

[0014] In some embodiments of the present invention, the metal organic framework material LIFM-28 is coordinated with the metal iridium photo-redox photosensitive center through 2,2'-bipyridine-5,5'-dicarboxylic acid; preferably, two nitrogen atoms on 2,2'-bipyridine-5,5'-dicarboxylic acid are coordinated with an Ir atom of the metal iridium photo-redox photosensitive center to form a structure composed of Ir and dF(CF3)ppy, i.e., bis[3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridyl], and the coordination environment after coordination self-assembly in the LIFM-28 crystal is as follows:

[0015] .

[0016] In some embodiments of the present invention, the metal organic framework material LIFM-28 is coordinated with the transition metal catalytic center through 3,3'-(2,2'-bipyridine)-5,5'-diyl-diacrylic acid; preferably, two nitrogen atoms on 3,3'-(2,2'-bipyridine)-5,5'-diyl-diacrylic acid are coordinated with a transition metal atom of the photosensitive center, and the coordination environment after coordination self-assembly in the LIFM-28 crystal is as follows:

[0017] .

[0018] In some embodiments of the present invention, in the heterogeneous metal photocatalyst, the distance between the metal iridium photoredox photosensitive center and the transition metal catalytic center is 0.8 to 0.9 nm, such as 0.81 nm, 0.82 nm, 0.83 nm, 0.84 nm, 0.85 nm, 0.86 nm, 0.87 nm, 0.88 nm, and 0.89 nm. In the present invention, the metal iridium photoredox photosensitive center and the transition metal catalytic center maintain this distance, which can effectively promote the transfer of electrons and nearby thiol radicals and other reaction intermediates at the photoredox site and the transition metal catalytic center site from the photosensitive center to the catalytic center, thereby synergistically accelerating the rate of the catalytic reaction.

[0019] In some embodiments of the present invention, the heterogeneous metal photocatalyst has a morphology including block, rod, plate or cone, and a particle size of 1 nm to 1 μm.

[0020] In some embodiments of the present invention, the molecular formula unit of the heterogeneous metal photocatalyst is C 92 H 40 Cl2F 24 Ir 0.1 N4NiO 32 Zr6; belongs to tetragonal phase, P 42 / mmc Space group.

[0021] In some embodiments of the present invention, the structural formula of the heterogeneous metal photocatalyst is [Zr6O4(OH)6(H2O)2(L)4(BPYDC) 0.92 (Ir[dF(CF3)ppy]2) 0.37 (BPV) 0.93 (NiCl2) 0.91 ]·x Solvent ).

[0022] In some embodiments of the present invention, the specific surface area of ​​the heterogeneous metal photocatalyst is 730 to 860 cm³ / g; as the photocatalytic reaction occurs, the specific surface area of ​​the heterogeneous metal photocatalyst increases.

[0023] The second aspect of the present invention provides a method for preparing a heterogeneous metal photocatalyst, comprising the following steps: reacting a metal organic framework material LIFM-28, an organic ligand, a photoredox complex and a transition metal catalyst by a solvent-assisted method to obtain the heterogeneous metal photocatalyst.

[0024] In some embodiments of the present invention, the method for preparing the heterogeneous metal photocatalyst comprises the following steps: reacting the metal organic framework material LIFM-28 with an organic ligand, a photoredox complex, an organic ligand, and a transition metal catalyst in a solvent-assisted manner to obtain the heterogeneous metal photocatalyst.

[0025] In some embodiments of the present invention, the reaction temperature of the solvent-assisted reaction is 80-150°C, such as 85°C, 90°C, 100°C, 110°C, 120°C, 130°C, etc.; and the reaction time is 1-3 days.

[0026] In some embodiments of the present invention, the solvent for the solvent-assisted reaction includes at least one of N,N-dimethylformamide, acetonitrile and methanol.

[0027] In some embodiments of the present invention, when performing the solvent-assisted reaction, fresh solvent is replaced 3 to 5 times a day.

[0028] In some embodiments of the present invention, the method for preparing the heterogeneous metal photocatalyst also includes subjecting the reaction product to a reduced pressure drying and activation treatment; the reduced pressure drying and activation treatment includes vacuum treatment at 18 to 35°C for 4 to 8 hours, and then vacuum treatment at 80 to 90°C for 10 to 14 hours.

[0029] The third aspect of the present invention provides the use of the heterogeneous metal photocatalyst in photocatalytic carbon-heteroatom bond cross-coupling and / or carbonylation reaction, photocatalytic degradation reaction, photocatalytic field hydrogen reaction, and photocatalytic conversion of carbon dioxide into carbon alcohol compounds and / or hydrocarbon compounds.

[0030] In some embodiments of the present invention, the carbon-heteroatom bond comprises CC, CO, CS, CN.

[0031] In some embodiments of the present invention, during the photocatalysis, the wavelength of the light source is 350-650nm, and the power is 1-100W.

[0032] The beneficial effects of the present invention are:

[0033] The present invention synthesizes a heterogeneous metal photocatalyst based on a dynamic ligand installation strategy. The ligands of the photoredox and transition metal catalytic sites are precisely incorporated into the prototype MOF material in precise positions and quantities, thereby giving the material the photosensitivity and catalytic activity required for the carbon-heteroatom bond cross-coupling reaction. More importantly, in the photosensitizer prepared by this strategy, the distance between the photosensitive center and the catalytic center is only 0.83 nm, which can effectively promote the transfer of reaction intermediates such as thiol free radicals near the iridium photoredox site and the catalytic site from the photosensitive center to the catalytic center, thereby synergistically accelerating the rate of the catalytic reaction. The heterogeneous metal photocatalyst synthesized by this method has extremely high application prospects for multifunctional metal-organic framework materials in the fields of organic small molecule catalysis and drug molecule development. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is a crystal structure diagram of the material in Example 1 of the present invention.

[0035] Figure 2 This is a crystal structure diagram of the material in Example 1 of the present invention.

[0036] Figure 3 This is a crystal structure diagram of the material in Example 1 of the present invention.

[0037] Figure 4 Schematic diagram showing the positional relationship between metal iridium and nickel in the crystal structure of the catalyst in Example 1 of the present invention.

[0038] Figure 5 This is a 77K nitrogen adsorption curve of the material in Example 1 of the present invention.

[0039] Figure 6 This is the X-ray powder diffraction pattern of the material in Example 1 of the present invention.

[0040] Figure 7 This is the X-ray powder diffraction pattern of the material in Example 1 of the present invention.

[0041] Figure 8 This is the XPS photoelectron spectrum of the catalyst before and after catalysis in Example 1 of the present invention.

[0042] Fig. 9 This is a TEM image of the catalyst in Example 1 of the present invention.

[0043] Fig.10 This is the ESD diagram of the catalyst in Example 1 of the present invention.

[0044] Fig.11 This is the HADDF-STEM image of the catalyst in Example 1 of the present invention.

[0045] Fig.12This is a CS cross-coupling photocatalytic cycle diagram of the catalyst in Example 1 of the present invention.

[0046] Fig.13 This is a diagram showing the CS cross-coupling substrate universality of the catalyst in Example 1 of the present invention. DETAILED DESCRIPTION

[0047] The present invention is further described in detail below by specific examples. Unless otherwise specified, the raw materials, reagents or devices used in the examples and comparative examples can be obtained from conventional commercial sources or can be obtained by prior art methods. Unless otherwise specified, the experiments or test methods are conventional methods in the art.

[0048] Example 1

[0049] This example prepares a heterogeneous metal photocatalyst, and the specific process is as follows:

[0050] (1) Preparation of dynamic coordination space metal organic framework material LIFM-28: 100 mg (0.40 mmol) zirconium chloride, 140 mg (0.37 mmol) 2,5'-bis(trifluoromethyl)-4,4'-biphenyldicarboxylic acid, 1 mL (13.46 mmol) trifluoroacetic acid and 20 mL N,N-dimethylformamide were added to a 40 mL glass bottle, and the solution was clarified by ultrasonication, and then heated at 120°C for three days to obtain colorless block crystals. Subsequently, the solvent was exchanged with fresh N,N-dimethylformamide three to four times a day for three days, and then stored in N,N-dimethylformamide solvent for use.

[0051] (2) Preparation of the metal organic framework material LIFM-80 that can modify the photosensitive central ligand: LIFM-28 (100 mg, 0.04 mmol), 12 mg (0.05 mmol) 2,2'-bipyridine-5,5'-dicarboxylic acid and 10 mL N,N-dimethylformamide were added to a glass bottle and heated at 120°C for two days to obtain colorless block crystals. The solvent was exchanged with fresh N,N-dimethylformamide three to four times every day for three days, and then the solvent was exchanged with acetonitrile three to four times. Finally, the sample was stored in acetonitrile solvent for future use.

[0052] (3) Preparation of LIFM-XYY-10, a metal organic framework material containing iridium photoredox photosensitive center: LIFM-80 (100 mg, 0.04 mmol), 43 mg (0.05 mmol) [Ir(dF(CF3)ppy)2(CH3CN)2]PF6 complex and 10 mL acetonitrile were added to a glass bottle and heated at 85°C for two days to obtain yellow block crystals. The solvent was exchanged with fresh acetonitrile three to four times a day. After two days of exchange, the solvent was stored in acetonitrile for future use.

[0053] (4) Preparation of the metal organic framework material LIFM-XYY-11 that can modify the catalytic center ligand: LIFM-XYY-10 (100 mg, 0.04 mmol), 16 mg (0.05 mmol) 3,3'-(2,2'-bipyridine)-5,5'-diyl-diacrylic acid and 10 mL acetonitrile were added to a glass bottle and heated at 120°C for two days to obtain yellow block crystals. The solvent was exchanged with fresh N,N-dimethylformamide three to four times every day for three days, and then the solvent was exchanged with methanol three to four times. Finally, the sample was stored in methanol solvent for future use.

[0054] (5) Preparation of catalyst LIFM-XYY-12 containing photosensitive center and catalytic center: LIFM-XYY-11 (100 mg, 0.04 mmol), 23 mg (0.1 mmol) nickel chloride hexahydrate and 10 mL methanol were added to a glass bottle and heated at 85°C for two days to obtain yellow block crystals. The solvent was exchanged with fresh methanol three to four times a day. After two days of exchange, the sample was centrifuged and the lower solid was transferred to a vacuum container. The solution was first treated under reduced pressure at room temperature for 6 hours, and then the temperature was adjusted to 85°C and the reduced pressure treatment was continued for 12 hours to finally obtain a dry heterogeneous metal photocatalyst.

[0055] Sample characterization and catalytic performance analysis:

[0056] The structures of samples LIFM-XYY-10~12 and catalysts were characterized by X-ray single crystal diffractometer. The relevant crystallographic parameters of the samples are shown in Table 1:

[0057] Table 1 Crystallographic parameters and refinement results of materials

[0058]

[0059] In addition, if Figures 1 to 3 As shown, the sample structure is clear, which is helpful for the subsequent catalytic mechanism analysis. Figure 4The positional relationship between metal iridium and nickel in the catalyst is shown. The distance between the two is 0.83 nm, which helps to increase the migration rate of the catalytic reaction intermediates and thus increase the reaction rate.

[0060] The specific surface area (BET) was tested by the N2 isotherm adsorption curve at 77K, such as Figure 5 As shown in the figure, the specific surface areas of LIFM-80, LIFM-XYY-10~12 and the catalysts before and after catalysis are 2041 cm³ / g, 1629 cm³ / g, 1213 cm³ / g, 737 cm³ / g and 851 cm³ / g, respectively. With the introduction of ligands and metals, the specific surface area gradually decreases, but the catalysts can still maintain a high porosity before and after catalysis.

[0061] X-ray powder diffraction (PXRD) analysis results (see Figures 6-7 ) showed that LIFM-XYY-12 could maintain the crystallinity of the metal-organic framework material before and after catalysis, indicating that it has high structural stability and is suitable for cyclic catalysis.

[0062] XPS photoelectron spectroscopy test (see Figure 8 ) showed that the photosensitive center iridium in the sample maintained a valence of +3 before and after catalysis, and the catalytic center nickel maintained a valence of +2, and no change in the metal valence state was observed, which indicates that the sample can maintain a stable valence state before and after catalysis.

[0063] High-resolution transmission electron microscopy analysis results (see Fig. 9 ) shows that the material is a bulk crystal, and in high-angle annular bright field or dark field mode, the metal is dispersed in the material in the form of single atoms. Figures 10-11 ) further shows that the elements are evenly distributed in the material.

[0064] In summary, the present invention successfully prepared a heterogeneous metal photocatalyst LIFM-XYY-12 with single-atom dispersion characteristics. Through the precise modification of dynamic coordination space ligands and transition metals, the obtained catalyst has photosensitivity and catalytic centers with high porosity and high dispersion, which can provide more catalytic reaction sites and facilitate the full contact between the catalyst and the reactants. More importantly, the spatial distance between the photosensitive center and the catalytic center is close, which effectively promotes the transfer rate of the reaction intermediates, thereby significantly improving the efficiency of the catalytic reaction. The catalyst shows extremely high application prospects in the field of organic small molecule catalysis and drug molecule development of functionalized nanomaterials.

[0065] Example 2

[0066] In this example, a heterogeneous metal photocatalyst is applied to a photocatalytic CS cross-coupling reaction, and the specific process is as follows:

[0067] (1) Photocatalytic CS cross-coupling catalysis

[0068] In the glove box, weigh 20 mg of catalyst LIFM-XYY-12, place it in a 10 mL glass bottle, and add 4-iodotrifluorotoluene (37 μL, 0.25 mmol), 4-methoxythiophenol (46 μL, 0.375 mmol), pyridine (41 μL, 0.5mmol) and 5 mL acetonitrile in sequence. Add a magnetic bar and tighten the bottle cap. After taking the sample bottle out of the glove box, light reaction is carried out under 30 W power and 456 nm wavelength LED light for 24 hours. After the reaction is completed, the reaction solution is filtered, and the filtrate is dried by spin drying and 0.5 mL of deuterated chloroform is added to perform nuclear magnetic resonance hydrogen and fluorine spectrum tests. The catalyst is recovered by centrifugation, and the above catalytic steps are repeated after vacuum drying. Six rounds of catalysis are carried out continuously, and the results are as follows. Fig.12 As shown, the product yields were 98.4%, 98.1%, 99.5%, 99.3% and 99.4%, respectively.

[0069] (2) Exploration of substrate adaptability

[0070] In the glove box, weigh 10 mg of catalyst LIFM-XYY-12 and place it in a 10 mL glass bottle, 4-iodotrifluorotoluene (37 μL, 0.25 mmol), 4-methoxythiophenol (46 μL, 0.375 mmol), pyridine (41 μL, 0.5 mmol) and 5 mL acetonitrile. Add a magnetic bar and tighten the bottle cap. Outside the glove box, irradiate with a 30 W LED lamp at a wavelength of 456 nm for 48 hours. After the reaction is completed, the reaction solution is filtered, and the filtrate is dried and 0.5 mL of deuterated chloroform is added for nuclear magnetic resonance hydrogen and fluorine spectrum tests. Subsequently, the iodine-terminated and thiol-terminated organic small molecule substrates with different electron-pushing and electron-withdrawing groups are replaced, and the above experimental steps are repeated to test the catalytic performance of the material on different substrates. The experimental results are shown in the figure. Fig.13 As shown, it indicates that the catalyst exhibits higher catalytic adaptability in the presence of electron-withdrawing groups.

[0071] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. An application of a heterogeneous metal photocatalyst in photocatalytic carbon-heteroatom bond cross coupling, characterized in that: The heterogeneous metal photocatalyst comprises a metal organic framework material LIFM-28, a bipyridine-dicarboxylic acid organic ligand, a metal iridium photoredox photosensitive center, and a transition metal catalytic center, which are self-assembled through coordination; The bipyridine-dicarboxylic acid organic ligand includes 2,2'-bipyridine-5,5'-dicarboxylic acid and 3,3'-(2,2'-bipyridine)-5,5'-diyl-diacrylic acid; The metal organic framework material LIFM-28 is coordinated with the metal iridium photoredox photosensitive center through 2,2'-bipyridine-5,5'-dicarboxylic acid; The metal organic framework material LIFM-28 is coordinated with the transition metal catalytic center through 3,3'-(2,2'-bipyridine)-5,5'-diyl-diacrylic acid; In the heterogeneous metal photocatalyst, the distance between the metal iridium photoredox photosensitive center and the transition metal catalytic center is 0.8 to 0.9 nm.

2. The use according to claim 1, characterized in that: The metal iridium photoredox photosensitive center is provided by a photoredox complex including [Ir(dF(CF3)ppy)2].

3. The use according to claim 1, characterized in that: The transition metal catalytic center is provided by a transition metal catalyst including nickel chloride, nickel bromide, nickel iodide, cobalt chloride, cobalt bromide, cobalt iodide, cupric chloride, cupric bromide, cupric iodide, cuprous iodide or hydrates of the above metal salts.

4. The use according to claim 1, characterized in that: The metal organic framework material LIFM-28 is coordinated with an Ir atom of the metal iridium photo-redox photosensitive center through two nitrogen atoms on 2,2'-bipyridine-5,5'-dicarboxylic acid.

5. The use according to claim 1, characterized in that: The metal organic framework material LIFM-28 is coordinated with a transition metal atom of the transition metal catalytic center through two nitrogen atoms on 3,3'-(2,2'-bipyridine)-5,5'-diyl-diacrylic acid.

6. The use according to claim 1, characterized in that: In the heterogeneous metal photocatalyst, the distance between the metal iridium photoredox photosensitive center and the transition metal catalytic center is 0.8 to 0.86 nm.

7. The use according to claim 1, characterized in that: The molecular formula unit of the heterogeneous metal photocatalyst is C 92 H 40 Cl2F 24 Ir 0.1 N4NiO 32 Zr6; belongs to tetragonal phase, P 42 / mmc Space group.

8. The use according to claim 1, characterized in that: The heterogeneous metal photocatalyst satisfies at least any one of the following conditions: (i) the morphology of the heterogeneous metal photocatalyst includes block, rod, plate or cone; (ii) the particle size of the heterogeneous metal photocatalyst is 1 nm to 1 μm.

9. The use according to any one of claims 1 to 8, characterized in that: The preparation method of the heterogeneous metal photocatalyst comprises the following steps: subjecting the metal organic framework material LIFM-28, the organic ligand, the photoredox complex and the transition metal catalyst to a solvent-assisted reaction to obtain the heterogeneous metal photocatalyst.

Images