C product formation in the CO electroreduction on boron-doped graphene anchored copper clusters.

A possible remedy for the increasing atmospheric CO concentration is capturing and reducing it into valuable chemicals like methane, methanol, ethylene, and ethanol. However, a suitable catalyst for this process is still under extensive research. Small sized copper clusters have gained attention in recent years due to their catalytic activity in the CO reduction reaction. Although C products have a higher economic value, the formation of C products was investigated most thoroughly. Graphene is a promising support for small copper clusters in the electrochemical reduction of CO. It exhibits good mechanical and electrical properties, but the weak interaction between copper and graphene is an issue. Our DFT computations reveal that small Cu clusters on the boron-doped graphene (BDG) support are promising catalysts for the electrochemical reduction of CO. We found facile reaction pathways towards various C (carbon-monoxide, formic acid, formaldehyde, methanol or methane) and C (ethanol or ethylene) products on Cu and Cu clusters on BDG. The reactivity is cluster-size tunable with Cu being the more reactive agent, while Cu shows a higher selectivity towards C products.