CO2 chemisorption and catalytic C-C coupling to valorized products on asymmetric sites of doped Cu-based 2D thin-layer electrocatalysts

• Applicant: Dr. Liang Liang
• Subject Area: Physical Chemistry of Solids and Surfaces, Material Characterisation
• Term: since 2022
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 511496123

The German Energy Transition (“Energiewende”) aims at decreasing net emissions of carbon dioxide (CO2) by 95% and increase the renewable energy fraction to 60% by 2050. To achieve these goals, direct electrochemical conversion of CO2 into chemicals is regarded as a promising technology component. Today’s efficiency of the catalytic CO2 electroreduction, however, is still quite low and does require new fundamental understanding of the interfacial catalytic process. Improved Cu-based electrocatalysts for the production of carbonaceous products are thereby a priority. In this project, we will introduce precisely controlled asymmetric atomic surface sites in Cu-based 2D thin-layer catalysts using novel doping strategies. We study their properties of capture and selective electroreduction of CO2 to C2 products. Our working hypothesis is that 1) surface engineering helps Cu-based 2D thin-layer electrocatalyst expose abundant CO2 adsorbed and reactive sites, 2) doped on the surface introduces asymmetric sites in Cu-based 2D thin-layer electrocatalysts, which can regulate the electronic structure of CO2 adsorbed sites and thereby lead to an unconventional adsorption behaviors, 3) such asymmetric sites further serve as active sites on the Cu-based 2D thin-layer electrocatalysts, which alleviate the dipole–dipole interaction of adjacent C1 intermediates, selectively enhance C-C coupling, and thus accelerating CO2 reduction to C2 fuels. To test and validate our hypothesis, we will employ advanced characterization techniques such as in situ electrochemical Fourier transform infrared (FTIR), operando differential electrochemical mass spectrometry (DEMS), CO2 adsorption isotherms, CO2 temperature-programmed desorption (TPD), and density functional theory (DFT) calculations. The combination of these techniques will reveal the adsorption and activation behavior of asymmetric atomic surface sites in Cu-based based 2D thin-layer electrocatalysts, especially C-C coupling, hence optimizing the reaction process. Overall, this project will include fundamental and practical new insights into asymmetric atomic surface sites for chemisorption and selective electroreduction of CO2, and thus will make important contributions to realize efficient CO2 reduction to C2 fuels in the future.

• DFG Programme: Research Grants