Ulm University

Modelling of Reaction Mechanism

Recently, CO2 has been converted to solid carbonaceous products at room temperature and low voltage using cerium containing galinstan as electrocatalyst (Esrafilzadeh et al. (2019)). A reaction pathway including the formation of a Ce(III)-oxide layer at the surface of the liquid metal and its reduction to Ce(0) was proposed whereafter the actual catalytic step takes place:

Although several experimental techniques including operando Raman Spectroscopy and High Resolution Transmission Electron Microscopy confirmed the existence of Ce(III)2O3 and Ce(IV)O2 on the surface of the liquid metal electrode, the exact reaction mechanism could not be clarified in the experiment and remains subject to speculation. Here, atomistic modelling, as routinely conducted at the Institute of Theoretical Chemistry at Ulm University using periodic density functional theory (DFT) calculations, will provide access to information about the reaction mechanism including intermediate reaction products and catalytically active surface sites. Thus, an enhanced understanding of the reaction mechanism will be achieved, which in turn may yield viable input for the experimental co-workers in order to tune and optimize the entire process.