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CN-121972228-A - MOF-supported ferrocene composite material and preparation method and application thereof

CN121972228ACN 121972228 ACN121972228 ACN 121972228ACN-121972228-A

Abstract

The invention discloses a composite material of MOF supported ferrocene, a preparation method and application thereof, wherein the composite material takes a metal organic framework MOF-545 as a main framework, and iron porphyrin carboxylic acid ligand is used for constructing a photoactive center, and the ferrocene carboxylic acid ligand is anchored on a zirconium oxygen cluster node of the MOF-545 through a Zr-O coordination bond. Compared with an unmodified material, the material provided by the invention has better light absorption capacity, higher photon-generated carrier separation and migration efficiency and lower interfacial charge transfer impedance, and shows higher carbon monoxide generation activity and good cycle stability in photocatalytic carbon dioxide reduction reaction.

Inventors

  • CHU MINGMING
  • LI YUANHANG
  • JI JIALIN
  • LI YIMING

Assignees

  • 嘉兴大学

Dates

Publication Date
20260505
Application Date
20260326

Claims (10)

  1. 1. A composite material of MOF loaded ferrocene is characterized in that the composite material takes a metal organic framework MOF-545 as a main framework, an iron porphyrin carboxylic acid ligand is used for constructing a photoactive center, and the ferrocene carboxylic acid ligand is anchored on a zirconium oxygen cluster node of the MOF-545 through a Zr-O coordination bond.
  2. 2. The composite material of claim 1, wherein the ferrocenecarboxylic acid ligand is ferrocenecarboxylic acid or ferrocenecarboxylic acid.
  3. 3. The composite material of claim 1, wherein the iron porphyrin carboxylic acid ligand is iron tetra (4-carboxyphenyl) porphyrin.
  4. 4. A method for preparing a composite material according to any one of claims 1 to 3, wherein the composite material is prepared by an in-situ modification solvothermal method, and specifically comprises the steps of adding ferrotetra (4-carboxyphenyl) porphyrin and zirconium salt ZrOCl 2 ·8H 2 O into an organic solvent, mixing and dissolving, adding a regulator and ferrocenecarboxylic acid, placing the mixture into a closed reaction vessel for solvothermal reaction, and carrying out solid-liquid separation, washing and drying after the reaction to obtain the composite material.
  5. 5. The method according to claim 4, wherein the organic solvent is any one of N, N-dimethylacetamide, N-dimethylformamide and dimethylsulfoxide.
  6. 6. The method according to claim 4, wherein the regulator is any one of benzoic acid, trifluoroacetic acid, glacial acetic acid, hydrochloric acid and trifluoromethanesulfonic acid.
  7. 7. The method of claim 4, wherein the mass ratio of ferrocenecarboxylic acid to iron tetra (4-carboxyphenyl) porphyrin is 1:6-1.5:1.
  8. 8. The method according to claim 7, wherein the mass ratio of ferrocenecarboxylic acid to iron tetra (4-carboxyphenyl) porphyrin is 1:2.
  9. 9. The process of claim 4, wherein the solvothermal reaction is carried out at a temperature of 100-140℃and for a period of 12-36 hours.
  10. 10. Use of a composite material according to any one of claims 1-3 for photocatalytic CO 2 reduction to CO.

Description

MOF-supported ferrocene composite material and preparation method and application thereof Technical Field The invention belongs to the field of photocatalytic materials, and particularly relates to a MOF-supported ferrocene composite material, and a preparation method and application thereof. Background The greenhouse effect and the energy crisis caused by the large-scale emission of carbon dioxide are environmental and energy problems to be solved in the world at present, and the solar energy is utilized to drive the carbon dioxide to be converted into carbon-containing products with high added value, so that the method is an effective technical route for considering carbon emission reduction and energy conversion. The photocatalytic carbon dioxide also has the advantages of mild reaction conditions and direct utilization of solar energy, and becomes a research hot spot in the field. The traditional semiconductor photocatalyst (such as TiO 2, cdS and ZnO) has the inherent defects that the light absorption capacity is insufficient due to the limited band gap range, the photo-generated electron-hole recombination rate is high, and the catalytic active sites are rare and unevenly dispersed, so that the yield and the selectivity of a product of carbon dioxide photoreduction are difficult to meet the actual application demands. In the prior art, performance can be optimized through modes of carbon/nitrogen-based material doping, precious metal promoter (Pd, pt and the like) surface modification and the like, but the method lacks an atomic/molecular level precise structure regulation strategy, directional construction and function customization of a catalytic active site cannot be realized, and the use of precious metal greatly improves the preparation cost and limits large-scale application. The Metal Organic Framework (MOF) has the characteristics of large specific surface area, adjustable pore structure and designable metal nodes and organic ligands, and provides an excellent platform for constructing high-efficiency photocatalysts. The porphyrin-based MOF-545 has a light absorption unit and a catalytic active center, and has potential application value in the field of photocatalytic CO 2 reduction. However, the MOF-545 has the problems of limited charge transfer efficiency from the organic ligand to the metal node, long electron conduction path and large resistance, so that the MOF-545 is similar to most MOF photocatalysts, and has the defects of insufficient charge separation efficiency and low interfacial electron transfer rate. The conventional MOF modification technology mainly comprises ligand engineering and node engineering, wherein the ligand engineering can introduce a photosensitive element or a molecular catalytic center, but special ligands are required to be designed, the synthesis process is complex, the stability of a part of the introduced coordination structure is insufficient, long-term photocatalytic reaction is not facilitated, the node engineering can directly introduce functional components by utilizing coordination sites of metal cluster nodes, the photoelectric and catalytic properties of the material can be improved on the premise of keeping the overall structure of a framework stable, and the MOF modification technology is a modification mode with more application potential. The ferrocene compound is an easily-obtained organic metal compound, has a stable sandwich structure, has a pi electron conjugated system of d-orbit extensible cyclopentadienyl ligand, endows the ferrocene compound with excellent electron donating capability, and simultaneously has the reversible redox characteristic of iron ions, so that the ferrocene compound has high-efficiency charge transmission performance. If ferrocene is introduced into the zirconium oxygen cluster node position of MOF-545 in a stable coordination mode, a new electron transmission path is hopeful to be constructed in the frame, and the separation efficiency of a photon-generated carrier and the catalytic reaction activity are improved. In view of the above, the development of the ferrocene-node modified MOF-545 composite material and the application thereof in photocatalytic CO 2 reduction have important practical significance for carbon emission reduction and clean energy conversion. Disclosure of Invention The invention aims to solve the technical problem of overcoming the defects of the prior art and providing a MOF ferrocene-loaded composite material and a preparation method and application thereof. In order to achieve the above purpose, the technical scheme of the invention is as follows: in a first aspect, the invention provides a MOF-supported ferrocene composite material, which uses a metal organic framework MOF-545 as a main framework, and uses iron porphyrin carboxylic acid ligand to construct a photoactive center, wherein the ferrocene carboxylic acid ligand is anchored on a zirconium oxygen cluster node of the MOF-545 through