Metal cooperativity for visible-light driven CO2 reduction with new photosensitizers and catalysts (CO2-COP)

• Applicants: Professor Dr. Ulf-Peter Apfel; Professor Dr. Marc Robert; Professor Dr. Oliver S. Wenger
• Subject Area: Inorganic Molecular Chemistry - Synthesis and Characterisation ; Physical Chemistry of Molecules, Liquids and Interfaces, Biophysical Chemistry
• Term: from 2020 to 2023
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 428643898

• Final Report Year: 2024

Final Report Abstract

A circular economy based on renewable energies and CO2 as a raw material is essential to replace fossil fuels for a sustainable future. The development of efficient CO2 reduction processes and consequently of efficient catalysts, both homogeneous and heterogeneous, is therefore crucial. While heterogeneous catalysis is preferred for industrial applications, molecular transition metal complexes can provide valuable mechanistic insights due to their modifiability and versatility. Most catalysts known in the literature for sunlight -driven processes have a single metal center as the active site. However, naturally occurring CO2-reducing enzymes suggest that bimetallic active sites are of high importance for selective and efficient CO2 reduction. In this project, therefore, both homo- and heterobimetallic catalysts based on 3d transition metals were tested as catalysts for light -induced CO2 reduction. The obtained results show a fascinating interplay between the type of metal centers and the role of co-substrates on different product selectivity and possible reaction pathways. Furthermore, it was shown how the distance between the metals and the surrounding type of ligand influences the stability of the catalysts and the product distribution.

Publications

• An asymmetric cryptand for the site-specific coordination of 3d metals in multiple oxidation states. Dalton Transactions, 50(41), 14602-14610.
  Jökel, Julia; Nyßen, Frauke; Siegmund, Daniel & Apfel, Ulf-Peter
  
• #RSCPoster Twitter Conference, Online, “An asymmetric cryptand for the site - specific coordination of 3d metals in multiple oxidation states”. Poster, 2022.
  J. Jökel, F. Nyßen, D. Siegmund & U.-P. Apfel
  
• A CuICoII cryptate for the visible light-driven reduction of CO2. Chemical Science, 14(44), 12774-12783.
  Jökel, Julia; Boydas, Esma Birsen; Wellauer, Joël; Wenger, Oliver S.; Robert, Marc; Römelt, Michael & Apfel, Ulf-Peter
  
• Visible-Light-Driven CO2 Reduction with Homobimetallic Complexes. Cooperativity between Metals and Activation of Different Pathways. Journal of the American Chemical Society, 145(46), 25195-25202.
  Bharti, Jaya; Chen, Lingjing; Guo, Zhenguo; Cheng, Lin; Wellauer, Joël; Wenger, Oliver S.; von Wolff, Niklas; Lau, Kai-Chung; Lau, Tai-Chu; Chen, Gui & Robert, Marc