Nanosecond Laser Confined Bismuth Moiety with Tunable Structures on Graphene for Carbon Dioxide Reduction
Mengnan Zhu, Haoqing Jiang, Bowen Zhang, Min‐Rui Gao, Peng‐Fei Sui, Renfei Feng, Karthik Shankar, Steven H. Bergens, Gary J. Cheng, Jing‐Li Luo
Abstract
Substrate-supported catalysts with atomically dispersed metal centers are promising for driving the carbon dioxide reduction reaction (CO 2 RR) 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 CO 2 -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 CO 2 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 CO 2 RR on ligand-modified Bi SAs, with potential applications in various fields.