Precisely Constructing Orbital Coupling-Modulated Dual-Atom Fe Pair Sites for Synergistic CO 2 Electroreduction

作者：Ying Wang, Byoung Joon Park, Vinod K. Paidi, Rui Huang, Yechan Lee, Kyung‐Jong Noh, Kug‐Seung Lee, Jeong Woo Han · 发表于：ACS Energy Letters · 年份：2022 · DOI：10.1021/acsenergylett.1c02446 · 被引用次数：311 · 研究领域：CO2 Reduction Techniques and Catalysts、Electrocatalysts for Energy Conversion、Ionic liquids properties and applications

Electrochemical reduction of CO 2 (CO 2 RR) provides an attractive pathway to achieve a carbon-neutral energy cycle. Single-atom catalysts (SAC) have shown unique potential in heterogeneous catalysis, but their structural simplicity prevents them from breaking linear scaling relationships. In this study, we develop a feasible strategy to precisely construct a series of electrocatalysts featuring well-defined single-atom and dual-site iron anchored on nitrogen-doped carbon matrix (Fe 1 –N–C and Fe 2 –N–C). The Fe 2 –N–C dual-atom electrocatalyst (DAC) achieves enhanced CO Faradaic efficiency above 80% in wider applied potential ranges along with higher turnover frequency (26,637 h –1 ) and better durability compared to SAC counterparts. Furthermore, based on in-depth experimental and theoretical analysis, the orbital coupling between the iron dual sites decreases the energy gap between antibonding and bonding states in *CO adsorption. This research presents new insights into the structure–performance relationship on CO 2 RR electrocatalysts at the atomic scale and extends the application of DACs for heterogeneous electrocatalysis and beyond.