Computational Investigation of Pt-Based Alloys as Electrocatalysts for Formic Acid Oxidation

Exploration of a closed carbon loop based on electrochemical oxidation of formic acid to CO₂ along with the inverse process provides an interesting pathway to integrate renewable energy into portable energy conversion devices for power generation and CO₂ mitigation. Significant work has revealed competing oxidative reaction pathway from dehydration to dehydrogenation, and while the kinetics of direct formate oxidation can be quite rapid, other pathways both minor or major can lead to CO production that results in poisoning of the performance and lifetime of these devices. While bulk Pt is very susceptible to this poisoning, experimental and computational studies have found that Pt-based alloys can drastically improve the resistance to the formation of surface CO bonds. We use density functional theory (DFT) to explore a series of alloys to determine surface stability relative to the susceptibility of poisoning these materials.