Modulating the Hydrogenation Mechanism of Electrochemical CO<sub>2</sub> Reduction Using Ruthenium Atomic Species on Bismuth
Xiao Liu, Cheng Zhen, Junxiu Wu, Xiao You, Yudong Wu, Qi Hao, Gang Yu, Meng Gu, Kai Liu, Jun Lü
Abstract
Abstract The conversion of CO 2 into formate through electrochemical methods is emerging as an elegant approach for industrial‐scale CO 2 utilization in the near future. Although Bismuth (Bi)‐based materials have shown promise thank to their excellent selectivity, their limited reactivity remains a challenge. Herein, this study demonstrates a significant enhancement in the CO 2 ‐to‐formate efficiency of Bi by incorporating ruthenium (Ru) atomic species. Ru single atom doped Bi exhibited a nearly twofold higher partial current density compared with pure Bi and Ru clusters doped Bi, while over 95% Faradaic efficiency (FE) is maintained. Through comprehensive investigations using a combined approach of electrochemical techniques, operando spectroscopy, and theoretical calculations, this study elucidates that the presence of Ru single atom promotes H 2 O dissociation and H* migration to Bi sites for CO 2 ‐to‐formate conversion by significantly reducing the energy barrier via a H* spillover path. Besides, it is constructed Ru–Bi bridge sites for efficient CO 2 hydrogenation via a non‐spillover path, which served as the major mechanism for CO 2 ‐to‐formate conversion in Ru single atom doped Bi.