From C1 to C2 Products: DFT Investigation of Boron-Doped Fullerene Monolayers as a Metal-Free Catalyst for CO Reduction Reaction

The pursuit of metal-free catalysts is ongoing, as these catalysts are low-cost, highly durable, and environmentally friendly, making them promising alternatives to metal-based catalysts. Recently, a two-dimensional fullerene monolayer network (qHP-C 60 ) with excellent stability was successfully synthesized [Hou et al. Nature 2022, 606, 507–510], making it a promising material for photocatalysis and electrocatalysis due to its high surface area and abundant active sites. Since the pristine material is inactive for the CO reduction reaction (CORR), we propose a boron-doped fullerene monolayer (B-qHP-C 60 ) as a metal-free dual-atom catalyst (DAC) for the electrochemical reduction of CO. Using dispersion-corrected density functional theory (DFT-D3) and ab initio molecular dynamics (AIMD) simulations, we investigated the structure, stability, selectivity, and CORR activity of B-qHP-C 60 for the formation of C1 and C2 products. The doped boron atoms effectively activate the CO molecule through a donation-backdonation mechanism, promoting CORR while suppressing the hydrogen evolution reaction (HER). The product selectivity of B-qHP-C 60 depends on CO coverage. At high CO coverage, *CO*CO intermediate formed via C–C coupling is reduced to ethanol with a limiting potential of −0.44 V, while at low CO coverage, *CO is converted to methane with a limiting potential of −0.16 V. These findings provide fundamental insights and pave the way for the development of metal-free DACs for CORR and other electrocatalytic reactions.