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CN-121988398-A - Bionic photocatalytic liposome system for carbon dioxide reduction and hydrogen evolution

CN121988398ACN 121988398 ACN121988398 ACN 121988398ACN-121988398-A

Abstract

A bionic photocatalytic liposome system for carbon dioxide reduction and hydrogen evolution belongs to the technical field of artificial light synthesis and catalytic materials. The system comprises a long-chain alkyl modified ruthenium complex photosensitizer, a long-chain alkyl modified cobalt tetrabipyridine catalyst and liposome vesicles formed by phospholipid self-assembly. The photosensitizer and the catalyst are embedded into the vesicle membrane through a hydrophobic chain, and are arranged in a space order in the water phase. Under the irradiation of visible light, the system takes sodium ascorbate as an electron donor, can efficiently catalyze the reduction of carbon dioxide into carbon monoxide, and can efficiently catalyze the reduction of protons to hydrogen in an argon atmosphere. The system simulates the functions of space separation and electron directional transfer of a membrane system in natural photosynthesis, effectively improves the charge separation efficiency, and provides a new way for constructing an integrated artificial photosynthesis platform.

Inventors

  • LI FEI
  • GAO HUA
  • LI XIAONA

Assignees

  • 大连理工大学

Dates

Publication Date
20260508
Application Date
20260129

Claims (9)

  1. 1. A dual-function biomimetic photocatalytic liposome system for carbon dioxide reduction and hydrogen evolution, the system comprising: (a) Long chain alkyl modified ruthenium complex photosensitizers; (b) Long chain alkyl modified cobalt tetrapyridyl catalysts; (c) Liposome vesicles formed from phospholipid self-assembly; wherein, the photosensitizer and the catalyst are embedded into a double-layer membrane structure of the liposome vesicle through long-chain alkyl groups; The long-chain alkyl modified ruthenium complex photosensitizer has a structure of Ru (bpy) 2 (C 9 -bpy)Cl 2 , wherein C 9 -bpy is 4,4 '-dinonyl-2, 2' -bipyridine; The long-chain alkyl modified cobalt tetrabipyridine catalyst has a structure of Co (qPyC 10 )Cl 2 , wherein qPyC 10 is a decaoxy chain modified ligand; The phospholipids are 1, 2-dimyristoyl-sn-glycero-3-phosphorylcholine and pegylated phospholipids.
  2. 2. The system of claim 1, wherein the pegylated phospholipid is 1, 2-distearoyl-sn-glycero-3-phosphoethanolamine-N- [ methoxy (polyethylene glycol) -2000].
  3. 3. The system of claim 1, wherein the molar ratio of photosensitizer to catalyst in the vesicle membrane is (1:1) - (10:1).
  4. 4. A method for preparing the bifunctional biomimetic photocatalytic liposome system of any one of claims 1-3, comprising the steps of: (1) Preparing the long-chain alkyl modified ruthenium complex photosensitizer and a long-chain alkyl modified cobalt tetrabipyridine catalyst respectively; (2) Dissolving photosensitizer, catalyst, phospholipid and polyethylene glycol phospholipid in organic solvent, and mixing uniformly; (3) Removing the organic solvent in the mixed solution in the step (2) to form a lipid film; (4) And adding a buffer solution into the lipid film, and performing hydration, freeze thawing cycle and film extrusion treatment to obtain liposome vesicle suspension with uniform particle size, thus obtaining the system.
  5. 5. The method according to claim 4, wherein in the step (4), the membrane extrusion treatment uses a polycarbonate membrane having a pore size of 100 to 400 nm.
  6. 6. Use of a bifunctional biomimetic photocatalytic liposome system according to any one of claims 1-3 for photocatalytic reduction of carbon dioxide to carbon monoxide.
  7. 7. The use according to claim 6, wherein the photocatalytic reaction is carried out under irradiation with visible light and ascorbate is used as electron donor.
  8. 8. Use of a bifunctional biomimetic photocatalytic liposome system according to any one of claims 1-3 for photocatalytic hydrogen evolution reactions.
  9. 9. The use according to claim 8, wherein the photocatalytic reaction is carried out under irradiation with visible light and ascorbate is used as electron donor.

Description

Bionic photocatalytic liposome system for carbon dioxide reduction and hydrogen evolution Technical Field The invention relates to the technical field of artificial light synthesis, photocatalysis materials and nano bionics, in particular to a biomimetic photocatalysis system which is constructed based on liposome vesicles and integrates double functions of carbon dioxide reduction and hydrogen evolution, and a preparation method and application thereof. Background The reduction of carbon dioxide (CO 2) to valuable carbon-based fuels (e.g., carbon monoxide, CO) or the water splitting to produce hydrogen (H 2) using solar-driven photocatalytic reactions is an ideal way to achieve sustainable energy production. Among them, molecular catalysts, particularly metal complexes having well-defined active sites, are of great interest because of their high activity and high selectivity. However, this technology still faces several key challenges in practical applications. In terms of carbon dioxide reduction, high-efficiency molecular catalysts (such as cobalt tetrabipyridine complexes) generally perform well in organic solvents (such as N, N-dimethylformamide), but are poorly water-soluble and difficult to directly apply to greener, sustainable aqueous systems. In addition, the homogeneous catalysis system has the problems of serious photo-generated charge recombination, easy catalyst deactivation and the like, and limits the overall energy conversion efficiency. In the aspect of the construction of a bionic platform, the natural photosynthesis has the core advantages that the natural photosynthesis has subtle spatial organization that a thylakoid membrane physically separates a light system II from a light system I, realizes the directional and relay type transmission of electrons, and establishes a proton gradient to drive ATP synthesis. The self-assembled liposome vesicle is utilized to simulate the biomembrane structure, thereby providing a potential platform for an artificial photosynthetic system. Liposomes are capable of providing a containment environment for hydrophobic molecules and may facilitate electron transfer through spatial arrangement. How to design a catalyst with both water phase compatibility and membrane anchoring capability, and construct an integrated liposome photocatalysis system which can efficiently drive CO 2 reduction and hydrogen evolution reaction simultaneously and simulate the spatial tissue advantage of natural photosynthesis, is still a problem to be solved in the field. Based on the state of the art, the invention aims at solving the following core technical bottlenecks existing in the field of artificial photosynthesis, in particular to an integrated photocatalytic system of a molecular catalyst: 1. The water phase application problem of the high-efficiency molecular catalyst is that the high-efficiency and high-selectivity carbon dioxide reduction molecular catalyst represented by the cobalt tetrabipyridine complex generally has extremely poor water solubility, cannot be directly dispersed or stably exist in a green and sustainable water phase reaction medium, and severely restricts the performance exertion and scale potential of the catalyst under the condition close to the practical application environment. 2. The problem of low electron transfer efficiency between the photosensitizer and the catalyst is that in a homogeneous phase or simply mixed heterogeneous system, the transfer process of electrons generated by the excitation of the photosensitizer to the catalyst is limited by the molecular diffusion rate, and the transfer path is random and long, so that a large amount of electrons are lost in the transfer process and are composited with holes, and the method becomes a key kinetic barrier for limiting the overall quantum efficiency and the reaction rate. 3. The problems of single function and insufficient integration level of the bionic catalytic platform are that the existing bionic photocatalytic research based on self-assembled membranes (such as liposome) is mostly focused on carrying single type catalytic reaction (such as only realizing hydrogen evolution or only realizing carbon dioxide reduction), and the inherent spatial organization capacity of a biological membrane system is not fully utilized to coordinate and integrate a plurality of catalytic function modules, so that a multifunctional platform capable of simultaneously or selectively driving different reduction reactions (such as CO 2 to CO and H + to H 2) is constructed. 4. The slow regeneration process of photosensitizers (dyes) is problematic in that the rate of regeneration of the oxidized state photosensitizers (i.e., the re-acquisition of electrons from an electron donor) is critical to maintaining continuous catalysis during the photocatalytic cycle. If the regeneration process is slow, not only the turnover efficiency of the photosensitizer is reduced, but also the oxidized photosensitizer is accu