C 2 product formation in the CO 2 electroreduction on boron-doped graphene anchored copper clusters.

A possible remedy for the increasing atmospheric CO 2 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 2 reduction reaction. Although C 2+ products have a higher economic value, the formation of C 1 products was investigated most thoroughly. Graphene is a promising support for small copper clusters in the electrochemical reduction of CO 2 . 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 2 . We found facile reaction pathways towards various C 1 (carbon-monoxide, formic acid, formaldehyde, methanol or methane) and C 2 (ethanol or ethylene) products on Cu 4 and Cu 7 clusters on BDG. The reactivity is cluster-size tunable with Cu 4 being the more reactive agent, while Cu 7 shows a higher selectivity towards C 2 products.