Electrocatalysis at Organic-Metal Interfaces: Identification of Structure-Reactivity Relationships for CO Reduction at Modified Cu Surfaces.

The limited selectivity of existing CO reduction catalysts and rising levels of CO in the atmosphere necessitate the identification of specific structure-reactivity relationships to inform catalyst development. Herein, we develop a predictive framework to tune the selectivity of CO reduction on Cu by examining a series of polymeric and molecular modifiers. We find that protic species enhance selectivity for H, hydrophilic species enhance formic acid formation, and cationic hydrophobic species enhance CO selectivity. ReaxFF reactive molecular dynamics simulations indicate that the hydrophilic/hydrophobic modifiers influence the formation of surface hydrides, which yield formic acid or H. These observations offer insights into how these modifiers influence catalytic behavior at the non-precious Cu surface and may aid in the future implementation of organic structures in CO reduction devices.