Fig. 7: Computational details on eCO2RR pathways predicted for UiO-66-Bi systems.
From: Local CO2 reservoir layer promotes rapid and selective electrochemical CO2 reduction
a DFT computed relation between N(2p) HOMO energy and CO2 adsorption energy (Eads CO2) for different interfaces signifies that the interaction between CO2 and interface improves as the HOMO-Fermi gap of the interface decreases. The synergistic effect of Bi-UiO-66-CN leads to lowest HOMO-Fermi gap and CO2 adsorption energy. b Schematic illustration of the 2 eCO2RR pathways towards HCOOH generation as computed with DFT(PBE)-CHE. c Reaction energetics for both HCOOH production mechanisms with reaction path illustrations. The solid lines represent HCOOH production via CO2 adsorption and activation followed by a PCET step (M1) and dashed lines represent Heyrovsky mechanism (M2) with initial hydride formation on the surface. Inset highlights the OCO adsorption energy in M1.
