Porphyrin-based covalent organic framework photocatalyst and application of porphyrin-based covalent organic framework photocatalyst in catalytic regeneration of coenzyme NADH

Abstract

The invention provides a porphyrin-based covalent organic framework photocatalyst and application of the porphyrin-based covalent organic framework photocatalyst to catalytic regeneration of coenzyme NADH, belongs to the technical field of photocatalysis, and aims to solve the technical problem of low efficiency of photocatalytic regeneration of coenzyme NADH. The two-dimensional porphyrin-based photocatalyst material with high crystallinity, high porosity and good stability is formed by covalent linkage of imine bonds formed by organic monomers through a Schiff base condensation reaction, the energy band gap of the two-dimensional porphyrin-based photocatalyst material is narrowed, the light absorption and utilization performance is high, the electron-hole recombination rate is low, and the electron transfer rate is high; the regeneration activity of the coenzyme NADH in the catalysis process can be enhanced. The porphyrin-based covalent organic framework photocatalyst has high selectivity and stability on catalytic regeneration of the coenzyme NADH under visible light, and the regeneration efficiency of the coenzyme NADH can reach 97% at most within 25 min.

Description

Technical Field

[0001] This invention relates to a porphyrin-based covalent organic framework photocatalyst and its application in catalytic regeneration of coenzyme NADH, belonging to the field of photocatalysis technology. Background Technology

[0002] Oxidoreductases are important biocatalysts that catalyze redox reactions between two molecules. During these reactions, a stoichiometric amount of reduced nicotinamide adenine dinucleotide (NADH) is required as a coenzyme to activate their redox properties. However, the production and purification of NADH is extremely costly, and its high price and poor stability limit its large-scale production. Therefore, employing cost-effective and efficient NADH regeneration technology to continuously and stably drive redox reactions is expected to reduce the overall cost of the reaction process. Currently, common NADH regeneration technologies include chemical catalysis, enzyme catalysis, electrocatalysis, and photocatalysis. Among these, photocatalytic regeneration of NADH is a technology inspired by natural photosynthesis. Photocatalytic NADH regeneration technology uses solar energy as its driving force and boasts advantages such as clean energy source, green reaction process, and strong system designability, showing great promise. However, existing photocatalysts suffer from low visible light absorption, high recombination rates of photogenerated electrons and holes, and low electron utilization efficiency, resulting in low regeneration efficiency and failing to meet practical application requirements. For example, our team previously developed a Ce / TCPP co-doped photocatalyst by introducing the photoresponsive unit TCPP and the rare earth element Ce into the metal-organic framework material UIO-66-NH2. This effectively reduced the band gap and improved the photogenerated carrier transfer rate, achieving a coenzyme NADH regeneration efficiency of 95% after 3 hours of illumination. However, the coenzyme NADH regeneration rate was still relatively low (Chemical Engineering Journal, 2024, 479, 147720).

[0003] Covalent organic frameworks (COFs) are novel porous crystalline polymers composed of organic monomers linked by covalent bonds. They typically possess strong visible light absorption capabilities and have shown great application potential in CO2 reduction, photocatalytic water splitting for hydrogen production, and pollutant degradation. However, currently reported COFs suffer from low photogenerated electron-hole separation efficiency, resulting in low photocatalytic efficiency. Therefore, it is necessary to design and synthesize more efficient COFs to enhance their light absorption and utilization performance, reduce electron-hole recombination rates, and increase electron transport rates, thereby achieving efficient regeneration of coenzyme NADH in photocatalysis and laying the foundation for establishing efficient industrial redox processes. Based on this, this invention selects porphyrin molecules with a conjugated macrocyclic structure of chlorophyll P700 molecules and corresponding dialdehydes or diamines as monomers for covalent organic frameworks. Through Schiff base condensation reactions, imine bonds are formed and covalently linked, successfully synthesizing a series of porphyrin-based covalent organic framework photocatalysts with high crystallinity, high porosity, and good stability. These photocatalysts are then applied to the photocatalytic regeneration process of coenzyme NADH. Summary of the Invention

[0004] To address the aforementioned problems in the prior art, this invention provides a porphyrin-based covalent organic framework photocatalyst and applies it to the photocatalytic regeneration reaction of coenzyme NADH. By rationally selecting organic monomers, a two-dimensional porphyrin-based photocatalyst material with high crystallinity, high porosity, good stability, and narrow band gap is designed and synthesized through imine bond covalent linkage. This enhances light absorption and utilization performance, reduces electron-hole recombination rate, and increases electron transfer rate, thereby achieving efficient regeneration of coenzyme NADH during the photocatalytic process.

[0005] Therefore, the first aspect of the present invention provides a porphyrin-based covalent organic framework photocatalyst, which is obtained by Schiff base condensation of organic monomer 5,10,15,20-tetra(4-aminophenyl)porphyrin and dialdehyde monomer or organic monomer 5,10,15,20-tetra(4-aldehydephenyl)porphyrin and diamine monomer.

[0006] According to some embodiments of the first aspect of the present invention, the dialdehyde monomer of the porphyrin-based covalent organic framework photocatalyst is (I) terephthalaldehyde, (II) 2,5-dimethoxyphenyl-1,4-dicarboxaldehyde, (III) 2,5-dibutoxyterephthalaldehyde, (IV) 2,5-dihydroxyterephthalaldehyde, (V) 2,5-difluoroterephthalaldehyde, (VI) 1,4-dialdehyde-2,5-divinylbenzene, and (VII) 2,5-bis(prop-2-yne-1) (VIII) 2,2′-bipyridine-5,5′-dicarboxaldehyde; wherein the diamine monomer is any one of (i) ethylenediamine, (ii) p-phenylenediamine, (iii) 2,5-dimethyl-p-phenylenediamine, (iv) 2,5-dimethoxy-p-phenylenediamine, (v) 2,5-dibromo-p-phenylenediamine, (vi) 1,4-diamino-2,5-dicyanophenylene, and (vii) 2,2′-bipyridine-5,5′-diamine.

[0007] According to a first aspect of the present invention, in (VIII) or (vii), the "porphyrin-based covalent organic framework photocatalyst with 2,2′-bipyridine-5,5′-dicarboxaldehyde as the dialdehyde monomer" is synthesized into a porphyrin-based covalent organic framework photocatalyst having a bipyridine group, and further synthesized with dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer through coordination to obtain a rhodium-based electronically modified porphyrin-based covalent organic framework photocatalyst.

[0008] The second aspect of this invention provides a method for synthesizing a porphyrin-based covalent organic framework photocatalyst, the method comprising the following steps: 1) ultrasonically dissolving or dispersing organic monomers 5,10,15,20-tetra(4-aminophenyl)porphyrin and dialdehyde monomers or organic monomers 5,10,15,20-tetra(4-aldehydephenyl)porphyrin and diamine monomers in a reaction solvent, and reacting with acetic acid as a catalyst; 2) after the reaction is completed, freezing and deoxygenating the product with liquid nitrogen, and then sealing and heating treatment; 3) after the treatment, filtering and Soxhlet extraction, and then heating and drying under vacuum to obtain the final product.

[0009] In step 1), the molar ratio of the organic monomer 5,10,15,20-tetra(4-aminophenyl)porphyrin and dialdehyde monomer or the organic monomer 5,10,15,20-tetra(4-aldehydephenyl)porphyrin and diamine monomer is 1:(1-4); the reaction solvent is an organic solvent mixture, and the organic solvent is selected from any combination of o-dichlorobenzene and ethanol, n-butanol or mesitylene, with a volume ratio of 1:1; the acetic acid concentration is 6-12M, and the total reaction volume is 1.1-6.3mL; the sealing heating conditions in step 2) are 110-130℃ and standing for 3-5 days; the Soxhlet extraction solvent in step 3) is tetrahydrofuran and acetone, the drying temperature is 70-90℃, and the drying time is 8-20h.

[0010] The third aspect of this invention provides a method for synthesizing a rhodium-based electronic medium-modified porphyrin-based covalent organic framework photocatalyst, the method comprising the following steps: 1) reacting the porphyrin-based covalent organic framework photocatalyst with a bipyridine group as described in the first aspect of this invention and a dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer in an organic solvent under light-protected stirring; 2) after the reaction is completed, filtering, washing and drying under vacuum conditions to obtain the final product, the rhodium-based electronic medium-modified porphyrin-based covalent organic framework photocatalyst.

[0011] The reaction solvent in step 1) is selected from any one of methanol, dimethyl sulfoxide, or tetrahydrofuran; the reaction time is 2 to 24 h; the molar ratio of the porphyrin-based covalent organic framework photocatalyst with bipyridine group and the dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer in the first aspect of the present invention is 1:(0.05 to 0.5); the washing solvent in step 2) is methanol and / or water; the drying temperature is 70 to 90 °C, and the drying time is 8 to 20 h.

[0012] A fourth aspect of this invention provides an application of a porphyrin-based covalent organic framework photocatalyst in the photocatalytic regeneration of the coenzyme NADH. The application method includes: modifying a porphyrin-based covalent organic framework photocatalyst with triethanolamine, a porphyrin-based covalent organic framework photocatalyst (and a rhodium-based electron medium), or a rhodium-based electron medium, and then applying the photocatalyst to NAD+. + Add the solution to degassed phosphate buffer and incubate in the dark for 30 minutes. Then irradiate with a xenon lamp to detect the regeneration rate of coenzyme NADH.

[0013] Preferably, the porphyrin-based covalent organic framework photocatalyst is obtained by Schiff base condensation of the organic monomer 5,10,15,20-tetrakis(4-aminophenyl)porphyrin as described in the first aspect of the present invention and any one of the dialdehyde monomers (I) to (VII) as described in the first aspect of the present invention, or by Schiff base condensation of the organic monomer 5,10,15,20-tetrakis(4-aldehydephenyl)porphyrin as described in the first aspect of the present invention and any one of the diamine monomers (i) to (vi) as described in the first aspect of the present invention. The rhodium-based electronically modified porphyrin-based covalent organic framework photocatalyst is obtained by Schiff base condensation of the organic monomer 5,10,15,20-tetra(4-aminophenyl)porphyrin as described in the first aspect of the present invention and the dialdehyde monomer in (VIII) as described in the first aspect of the present invention, or by Schiff base condensation of the organic monomer 5,10,15,20-tetra(4-aldehydephenyl)porphyrin as described in the first aspect of the present invention and the diamine monomer in (vii) as described in the first aspect of the present invention.

[0014] The concentration of triethanolamine in the reaction system is 5-20%wt, for example 5%wt, 7%wt, 10%wt, 12%wt, 15%wt, 16%wt, 18%wt or 20%wt, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but preferably 15%wt.

[0015] The concentration of the photocatalyst in the reaction system is 0.5 to 5 mg / mL, for example 0.5 mg / mL, 0.7 mg / mL, 1 mg / mL, 2 mg / mL, 3 mg / mL or 5 mg / mL, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but preferably 1 mg / mL.

[0016] The pH value of the reaction system is 6.5 to 8.5, for example 6.5, 6.8, 7.0, 7.2, 7.5, 7.8, 8.0, 8.5, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, and 7.0 is further preferred.

[0017] The reaction system temperature is 20–37°C, for example 20°C, 25°C, 27°C, 30°C, 32°C, 35°C, or 37°C, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific values ​​included in the range. More preferably, it is 25°C.

[0018] Coenzyme NAD in the reaction system + The concentration is 0.01 to 100 mM, for example 0.03 mM, 0.1 mM, 0.5 mM, 1 mM, 5 mM, 10 mM, 20 mM, 30 mM, 50 mM, 70 mM or 100 mM, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, and preferably 1 mM.

[0019] The time for the photocatalytic regeneration reaction of coenzyme NADH is 10 min to 6 h, preferably 25 min.

[0020] Preferably, the photocatalytic NADH regeneration reaction system is as follows: 15% wt triethanolamine, 1 mg / mL porphyrin-based covalent organic framework photocatalyst as described in the first aspect of the present invention (and rhodium-based electronic mediator [Cp*Rh(bpy)(H2O)]). 2+ ) or rhodium-based electronic mediator-modified porphyrin-based covalent organic framework photocatalysts, 1mM NAD +Add the solution to a degassed phosphate buffer solution at pH 7.0, incubate in the dark for 30 minutes, then irradiate with a xenon lamp to detect the regeneration rate of coenzyme NADH; the inert gas used for degassing is any one of nitrogen, argon, or helium.

[0021] This invention utilizes porphyrin molecules with strong visible light absorption and corresponding dialdehyde or diamine molecules as organic monomers, and forms a two-dimensional porphyrin-based photocatalyst material with high crystallinity, high porosity, and good stability through Schiff base condensation reaction to form imine bonds. This invention also provides the application of the constructed porphyrin-based covalent organic framework photocatalyst to the visible light-catalyzed regeneration reaction of coenzyme NADH. Compared with existing technologies, the porphyrin-based covalent organic framework photocatalyst provided by this invention has a narrower band gap, stronger light absorption and utilization performance, lower electron-hole recombination rate, and higher electron transport rate. It exhibits high selectivity and stability for the catalytic regeneration of coenzyme NADH under visible light, with a regeneration efficiency of up to 97% within 25 minutes, and good reusability. Attached Figure Description

[0022] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below.

[0023] Figure 1 SEM and N2 adsorption-desorption curves of the porphyrin-based covalent organic framework photocatalyst COF-II in Example 1;

[0024] Figure 2 SEM and N2 adsorption-desorption curves of COF-VIII, a porphyrin-based covalent organic framework photocatalyst with a bipyridine group, in Example 2;

[0025] Figure 3 Example 7 illustrates the effect of rhodium-based electron medium concentration on the photocatalytic regeneration of coenzyme NADH.

[0026] Figure 4 To demonstrate the stability of the porphyrin-based covalent organic framework photocatalyst COF-II for regenerating coenzyme NADH in Example 7;

[0027] Figure 5 Example 8 illustrates the photocatalytic regeneration performance of the rhodium-based electronic medium-modified porphyrin-based covalent organic framework photocatalyst Rh-COF-VIII for coenzyme NADH. Detailed Implementation

[0028] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] Example 1: Synthesis of Porphyrin-based Covalent Organic Framework Photocatalyst COF-II

[0030] The porphyrin-based covalent organic framework photocatalyst COF-II in this invention is synthesized from 5,10,15,20-tetratetra(4-aminophenyl)porphyrin and 2,5-dimethoxyphenyl-1,4-dicarboxaldehyde via a solvothermal method, comprising the following steps: 1) 0.027 g (0.04 mmol) of 5,10,15,20-tetratetra(4-aminophenyl)porphyrin and 0.0155 g (0.08 mmol) of 2,5-dimethoxyphenyl-1,4-dicarboxaldehyde are added to 6 mL of a mixed solvent of o-dichlorobenzene and n-butanol (v:v = 1:1), and then 6 M acetic acid (0.3... 1) The catalyst (mL) was ultrasonically treated for 15 min to mix, dissolve, and react; 2) After ultrasonic treatment, the reaction solution in the Pyrex tube was frozen, vacuumed, and thawed using liquid nitrogen, repeated three times to remove oxygen from the reaction system. The Pyrex tube was then sealed with a flame torch and placed in a vacuum drying oven at 120℃ for 72 h; 3) After the reaction was complete, a precipitate formed at the bottom of the tube. The product was obtained by centrifugation and washed successively with tetrahydrofuran, methanol, and ethanol until the filtrate was colorless. The precipitate was dried under vacuum at 80℃ for 12 h to obtain the porphyrin-based covalent organic framework photocatalyst COF-II. SEM and N2 adsorption-desorption curves are shown below. Figure 1 As shown, the porphyrin-based covalent organic framework photocatalyst COF-II exhibits a stacked spherical particle structure with a specific surface area of ​​321.5 m². 2 / g, with an average pore size of 1.4nm.

[0031] Example 2: Synthesis of porphyrin-based covalent organic framework photocatalyst COF-VIII

[0032] The porphyrin-based covalent organic framework photocatalyst COF-VIII in this invention is synthesized from 5,10,15,20-tetrakis(4-aminophenyl)porphyrin and 2,2′-bipyridine-5,5′-dicarboxaldehyde via a solvothermal method, comprising the following steps: 1) 0.0158 g (0.023 mmol) of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin and 0.006 g (0.028 mmol) of 2,2′-bipyridine-5,5′-dicarboxaldehyde are added to 1 mL of a mixed solvent of o-dichlorobenzene and n-butanol (v:v = 1:1), and then 6 M acetic acid (0.1... 1) The catalyst (mL) was ultrasonically treated for 15 min to mix, dissolve, and react; 2) After ultrasonic treatment, the reaction solution in the Pyrex tube was frozen, vacuumed, and thawed using liquid nitrogen, repeated three times to remove oxygen from the reaction system. The Pyrex tube was then sealed with a flame torch and placed in a vacuum drying oven at 120℃ for 72 h; 3) After the reaction was complete, a precipitate formed at the bottom of the tube. The product was obtained by centrifugation, and the precipitate was washed with tetrahydrofuran until the filtrate was colorless. The product was then dried under vacuum at 120℃ for 12 h to obtain the porphyrin-based covalent organic framework photocatalyst COF-VIII with a bipyridine group. SEM and N2 adsorption-desorption curves are shown below. Figure 2 As shown, the porphyrin-based covalent organic framework photocatalyst COF-VIII, containing a bipyridine group, also exhibits a stacked spherical particle structure with a specific surface area of ​​114.0 m². 2 / g, with an average pore size of 1.8nm; compared with the COF-II photocatalyst, its specific surface area decreased and the average pore size increased slightly, indicating that the COF-VIII and COF-II photocatalysts have similar pore structures inside.

[0033] Example 3: Synthesis of Rhodium-based electron-dielectric modified porphyrin-based covalent organic framework photocatalyst Rh-COF-VIII

[0034] In this invention, the rhodium-based electronic dielectric modified porphyrin-based covalent organic framework photocatalyst Rh-COF-VIII is prepared by reacting the porphyrin-based covalent organic framework photocatalyst COF-VIII with bipyridine groups described in Example 2 and dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer ([Cp*RhCl2]2) in a methanol solution with light-protected stirring. The amount of [Cp*RhCl2]2 added is determined based on the molar ratio of bipyridine groups to Rh in COF-VIII being 1:(0.05–0.5). The specific steps are as follows: 1) 10 mg of the porphyrin-based covalent organic framework photocatalyst COF-VIII with bipyridine groups described in Example 2 and 10.32 mg (0.017 mmol) of [Cp*RhCl2]2 were stirred in 10 mL of methanol solution in the dark for 2 h; 2) After the reaction, the solid product was separated by filtration, washed with a large amount of methanol and water, and dried under vacuum at 80 °C for 8 h to obtain the rhodium-based electronic medium-modified porphyrin-based covalent organic framework photocatalyst Rh-COF-VIII. SEM results showed that after [Cp*RhCl2]2 was immobilized on the porphyrin-based covalent organic framework photocatalyst COF-II, the overall structure did not change significantly, indicating that the [Cp*RhCl2]2 immobilization process did not damage the morphology and structure of the COF-II photocatalyst.

[0035] Example 4: Synthesis of porphyrin-based covalent organic framework photocatalyst COF-ii

[0036] The porphyrin-based covalent organic framework photocatalyst COF-ii in this invention is synthesized from 5,10,15,20-tetra(4-aldehyde-phenyl)porphyrin and p-phenylenediamine via a solvothermal method, comprising the following steps: 1) 0.029 g (0.04 mmol) of 5,10,15,20-tetra(4-aldehyde-phenyl)porphyrin and 0.0086 g (0.08 mmol) of p-phenylenediamine are added to a mixed solvent of o-dichlorobenzene and n-butanol (v:v = 1:1), and then 6M acetic acid (0.3 mL) is added as a catalyst, followed by ultrasonic treatment for 1 minute. 1) Mix, dissolve, and react for 5 minutes; 2) After ultrasonic treatment, freeze, vacuum, and thaw the reaction solution in the Pyrex tube using liquid nitrogen, repeating the operation three times to remove oxygen from the reaction system. Then, seal the Pyrex tube with a flame torch and place it in a vacuum drying oven at 120°C for 72 hours; 3) After the reaction is complete, a precipitate is formed at the bottom of the tube. The product is obtained by centrifugation. The precipitate is washed with tetrahydrofuran, methanol, and ethanol in sequence until the filtrate is colorless. The product is dried under vacuum at 80°C for 12 hours to obtain the porphyrin-based covalent organic framework photocatalyst COF-ii.

[0037] Example 5: Synthesis of porphyrin-based covalent organic framework photocatalyst COF-vii

[0038] The porphyrin-based covalent organic framework photocatalyst COF-vii with a bipyridine group in this invention is synthesized from 5,10,15,20-tetrakis(4-aldehydephenyl)porphyrin and 2,2′-bipyridine-5,5′-diamine via a solvothermal method, comprising the following steps: 1) adding 0.022 g (0.03 mmol) of 5,10,15,20-tetrakis(4-aldehydephenyl)porphyrin and 0.003 g (0.03 mmol) of 2,2′-bipyridine-5,5′-diamine to 1 mL of a mixed solvent of o-dichlorobenzene and n-butanol (v:v = 1:1), and then adding 6 M acetic acid (0 1) The catalyst was ultrasonically treated for 15 min to mix, dissolve and react; 2) After ultrasonic treatment, the reaction solution in the Pyrex tube was frozen, vacuumed and thawed using liquid nitrogen, and the operation was repeated three times to remove oxygen from the reaction system. The Pyrex tube was then sealed with a flame torch and placed in a vacuum drying oven at 120℃ for 72 h; 3) After the reaction was completed, a precipitate was generated at the bottom of the tube. The product was obtained by centrifugation. The precipitate was washed with tetrahydrofuran until the filtrate was colorless. The product was dried under vacuum at 120℃ for 12 h to obtain the porphyrin-based covalent organic framework photocatalyst COF-vii with bipyridine groups.

[0039] Example 6: Synthesis of Rhodium-based electron-dielectric modified porphyrin-based covalent organic framework photocatalyst Rh-COF-vii

[0040] In this invention, the rhodium-based electronic dielectric modified porphyrin-based covalent organic framework photocatalyst Rh-COF-vii is prepared by reacting the porphyrin-based covalent organic framework photocatalyst COF-vii with bipyridine groups described in Example 5 and dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer ([Cp*RhCl2]2) in a methanol solution with light-protected stirring. The amount of [Cp*RhCl2]2 added is determined based on the molar ratio of bipyridine groups to Rh in COF-vii being 1:(0.05~0.5). The specific steps are as follows: 1) 10 mg of the porphyrin-based covalent organic framework photocatalyst COF-vii with bipyridine group described in Example 2 and 9.27 mg (0.015 mmol) of [Cp*RhCl2]2 were stirred in 10 mL of methanol solution in the dark for 2 h; 2) After the reaction was completed, the solid product was separated by filtration and washed with a large amount of methanol and water, and dried under vacuum at 80 °C for 8 h to obtain the rhodium-based electronic medium modified porphyrin-based covalent organic framework photocatalyst Rh-COF-vii.

[0041] Example 7: Porphyrin-based covalent organic framework photocatalyst COF-II applied to photocatalytic regeneration of coenzyme NADH

[0042] The porphyrin-based covalent organic framework photocatalyst COF-II synthesized in Example 1 of this invention was applied to the regeneration of reduced nicotinamide adenine dinucleotide (NADH). The reaction system was as follows: 15% wt triethanolamine, 1 mg / mL porphyrin-based covalent organic framework photocatalyst COF-II, 1–7 mM rhodium-based electron medium, and 1 mM NAD. + The sample was added to degassed phosphate buffer at pH 7.0, incubated in the dark for 30 min, then irradiated with a CEL-S500 xenon lamp illuminator system simulating sunlight for 25 min, and the OD was measured using a multi-functional microplate reader. 340 The regeneration efficiency of coenzyme NADH was calculated using the rhodium-based electron medium [Cp*Rh(bpy)(H2O)] at different concentrations. 2+ Effects on photocatalytic regeneration of coenzyme NADH such as Figure 3 As shown, with the increase of the concentration of rhodium-based electron mediator in the reaction system, the regeneration efficiency of coenzyme NADH shows a trend of first increasing and then decreasing, and the highest regeneration efficiency of coenzyme NADH reaches 97% when the rhodium-based electron mediator is 5 mM. Regarding the cycle stability of the porphyrin-based covalent organic framework photocatalyst COF-II for photocatalytic regeneration of coenzyme NADH, as... Figure 4 As shown, after six cycles, the regeneration efficiency of coenzyme NADH remained essentially unchanged, indicating that the COF-II porphyrin-based covalent organic framework photocatalyst has good structural stability.

[0043] Example 8: Rhodium-based electron-dielectric modified porphyrin-based covalent organic framework photocatalyst Rh-COF-VIII applied to the photocatalytic regeneration of coenzyme NADH.

[0044] The rhodium-based electronically modified porphyrin-based covalent organic framework photocatalyst Rh-COF-VIII synthesized in Example 3 of this invention was applied to the regeneration of reduced nicotinamide adenine dinucleotide (NADH). The reaction system was as follows: 15% wt triethanolamine, 1 mg / mL rhodium-based electronically modified porphyrin-based covalent organic framework photocatalyst Rh-COF-VIII, and 1 mM NAD. + The sample was added to degassed phosphate buffer at pH 7.0, incubated in the dark for 30 minutes, and then irradiated with a CEL-S500 xenon lamp illuminator system simulating sunlight. The OD was measured using a multi-functional microplate reader. 340 The value was used to calculate the regeneration efficiency of coenzyme NADH. The results are as follows: Figure 5 As shown, the regeneration efficiency of coenzyme NADH reached 94% in 25 minutes.

[0045] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A porphyrin-based covalent organic framework photocatalyst, characterized in that, The porphyrin-based covalent organic framework photocatalyst is obtained by Schiff base condensation of organic monomers 5,10,15,20-tetra(4-aminophenyl)porphyrin and dialdehyde monomers or organic monomers 5,10,15,20-tetra(4-aldehydephenyl)porphyrin and diamine monomers.

2. The porphyrin-based covalent organic framework photocatalyst according to claim 1, characterized in that, The dialdehyde monomer is (I) terephthalaldehyde, (II) 2,5-dimethoxyphenyl-1,4-dicarboxaldehyde, (III) 2,5-dibutoxyterephthalaldehyde, (IV) 2,5-dihydroxyterephthalaldehyde, (V) 2,5-difluoroterephthalaldehyde, (VI) 1,4-dialdehyde-2,5-divinylbenzene, (VII) 2,5-bis(prop-2-yn-1-yloxy)terephthalaldehyde, (VIII) The diamine monomer is any one of 2,2′-bipyridine-5,5′-dicarboxaldehyde; the diamine monomer is any one of (i) ethylenediamine, (ii) p-phenylenediamine, (iii) 2,5-dimethyl-p-phenylenediamine, (iv) 2,5-dimethoxy-p-phenylenediamine, (v) 2,5-dibromo-p-phenylenediamine, (vi) 1,4-diamino-2,5-dicyanobenzene, and (vii) 2,2′-bipyridine-5,5′-diamine.

3. The porphyrin-based covalent organic framework photocatalyst according to claim 2(VIII) or (vii), characterized in that, A rhodium-based electronically modified porphyrin-based covalent organic framework photocatalyst was synthesized by coordination synthesis of a porphyrin-based covalent organic framework photocatalyst with a bipyridine group and a dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer.

4. The method for synthesizing the porphyrin-based covalent organic framework photocatalyst according to any one of claims 1 or 2, characterized in that, The synthesis method includes the following steps: 1) dissolving or dispersing organic monomers 5,10,15,20-tetra(4-aminophenyl)porphyrin and dialdehyde monomers or organic monomers 5,10,15,20-tetra(4-aldehydephenyl)porphyrin and diamine monomers in a reaction solvent by ultrasonication, and reacting with acetic acid as a catalyst; 2) after the reaction is completed, deoxygenating the product by freezing with liquid nitrogen and then heating it in a sealed container; 3) after the product is treated by filtration, Soxhlet extraction, and then drying it under vacuum to obtain the final product.

5. The method for synthesizing the porphyrin-based covalent organic framework photocatalyst according to claim 4, characterized in that, The reaction solvent in step 1) is a mixture of organic solvents, selected from any combination of o-dichlorobenzene and ethanol, n-butanol or mesitylene, with a volume ratio of 1:1; the acetic acid concentration is 6-12M, and the total reaction volume is 1.1-6.3mL; the sealed heating conditions in step 2) are 110-130℃ and standing for 3-5 days; the Soxhlet extraction solvent in step 3) is tetrahydrofuran and acetone, the drying temperature is 70-90℃, and the drying time is 8-20h.

6. The method for synthesizing the porphyrin-based covalent organic framework photocatalyst according to claim 4, characterized in that, The molar ratio of the organic monomer 5,10,15,20-tetra(4-aminophenyl)porphyrin and dialdehyde monomer or the organic monomer 5,10,15,20-tetra(4-aldehydephenyl)porphyrin and diamine monomer is 1:(1-4).

7. The method for synthesizing the rhodium-based electron-dielectric modified porphyrin-based covalent organic framework photocatalyst according to any one of claims 3, characterized in that, The synthesis method includes the following steps: 1) reacting the porphyrin-based covalent organic framework photocatalyst with bipyridine group as described in claim 5 and the dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer in an organic solvent under light-protected stirring; 2) after the reaction is completed, the product is obtained by filtration, washing and heating and drying under vacuum to obtain the final product, the rhodium-based electronic medium modified porphyrin-based covalent organic framework photocatalyst.

8. The method for synthesizing the rhodium-based electron dielectric modified porphyrin-based covalent organic framework photocatalyst according to claim 7, characterized in that, The reaction solvent in step 1) is selected from any one of methanol, dimethyl sulfoxide, or tetrahydrofuran; the reaction time is 2-24 h; the molar ratio of the porphyrin-based covalent organic framework photocatalyst with bipyridine group to the dichloro(pentamethylcyclopentadienyl)rhodium(III) dimer is 1:(0.05-0.5); the washing solvent in step 2) is methanol and / or water; the drying temperature is 70-90℃, and the drying time is 8-20 h.

9. The application of the porphyrin-based covalent organic framework photocatalyst according to any one of claims 1-8 in the photocatalytic regeneration of coenzyme NADH.

10. The application of the porphyrin-based covalent organic framework photocatalyst according to claim 9 in the photocatalytic regeneration of coenzyme NADH, characterized in that, Porphyrin-based covalent organic framework photocatalysts modified with triethanolamine, porphyrin-based covalent organic framework photocatalysts (and rhodium-based electronic mediators), or rhodium-based electronic mediators, and NAD + The enzyme was added to degassed phosphate buffer solution and incubated in the dark for 30 minutes. Then, it was irradiated with a xenon lamp to detect the regeneration rate of coenzyme NADH.

Images