Fig. 1: Pathway modification via surface ligand interactions.
From: Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity
a A schematic showing the impact of surface ligands on the product selectivity. Geometry optimized DFT results of (b), the RDS for the C2+ electrosynthesis: reduction and proton transfer to CO* on alkanethiolated slab of copper showing an interaction between C and S. This interaction leads to a higher p-orbital character on C and, therefore, facilitates its conversion to CHO and (c) Origins of selectivity toward acetate: stabilizing the (HOOC–CH2) * intermediate drives reaction toward acetate instead of ethylene. (HOOC–CH2)* on alkanethiolated slab of copper showing the interaction between S and C of –COOH group. (HOHC–CH2O)* that yields ethylene, lacks this interaction and therefore is not stabilized.
