Nanosecond Laser Confined Bismuth Moiety with Tunable Structures on Graphene for Carbon Dioxide Reduction

Substrate-supported catalysts with atomically dispersed metal centers are promising for driving the carbon dioxide reduction reaction (CO₂RR) to produce value-added chemicals; however, regulating the size of exposed catalysts and optimizing their coordination chemistry remain challenging. In this study, we have devised a simple and versatile high-energy pulsed laser method for the enrichment of a Bi "single atom" (SA) with a controlled first coordination sphere on a time scale of nanoseconds. We identify the mechanistic bifurcation routes over a Bi SA that selectively produce either formate or syngas when bound to C or N atoms, respectively. In particular, C-stabilized Bi (Bi-C) exhibits a maximum formate partial current density of -29.3 mA cm^-2 alongside a TOF value of 2.64 s^-1 at -1.05 V vs RHE, representing one of the best SA-based candidates for CO₂-to-formate conversion. Our results demonstrate that the switchable selectivity arises from the different coupling states and metal-support interactions between the central Bi atom and adjacent atoms, which modify the hybridizations between the Bi center and *OCHO/*COOH intermediates, alter the energy barriers of the rate-determining steps, and ultimately trigger the branched reaction pathways after CO₂ adsorption. This work demonstrates a practical and universal ultrafast laser approach to a wide range of metal-substrate materials for tailoring the fine structures and catalytic properties of the supported catalysts and provides atomic-level insights into the mechanisms of the CO₂RR on ligand-modified Bi SAs, with potential applications in various fields.