Regulating Efficient and Selective Single‐atom Catalysts for Electrocatalytic CO2 Reduction

Abstract Anchoring transition metal (TM) atoms on suitable substrates to form single‐atom catalysts (SACs) is a novel approach to constructing electrocatalysts. Graphdiyne with sp−sp 2 hybridized carbon atoms and uniformly distributed pores have been considered as a potential carbon material for supporting metal atoms in a variety of catalytic processes. Herein, density functional theory (DFT) calculations were performed to study the single TM atom anchoring on graphdiyne (TM 1 −GDY, TM=Sc, Ti, V, Cr, Mn, Co and Cu) as the catalysts for CO 2 reduction. After anchoring metal atoms on GDY, the catalytic activity of TM 1 −GDY (TM=Mn, Co and Cu) for CO 2 reduction reaction (CO 2 RR) are significantly improved comparing with the pristine GDY. Among the studied TM 1 −GDY, Cu 1 −GDY shows excellent electrocatalytic activity for CO 2 reduction for which the product is HCOOH and the limiting potential (U L ) is −0.16 V. Mn 1 −GDY and Co 1 −GDY exhibit superior catalytic selectivity for CO 2 reduction to CH 4 with U L of −0.62 and −0.34 V, respectively. The hydrogen evolution reaction (HER) by TM 1 −GDY (TM=Mn, Co and Cu) occurs on carbon atoms, while the active sites of CO 2 RR are the transition metal atoms . The present work is expected to provide a solid theoretical basis for CO 2 conversion into valuable hydrocarbons.