Engineering the Coordination Environment of Metal Centers for Selective and High-Current CO<sub>2</sub> Electromethanation
Chang Zhu, Dashuai Wang, Libin Zeng, Guanghui Feng, Yi Liang, Wanzhen Zheng, Weixiao Lin, Xianyun Peng, Zhibin Liu, Xiahan Sang, Bin Yang, Zhongjian Li, Qinghua Zhang, Lecheng Lei, Yang Hou
Abstract
Renewable energy-driven CO 2 to CH 4 conversion represents a pivotal strategy for achieving carbon neutrality, with the primary scientific challenge residing in controllably accelerating protonation kinetics. Atomically precise engineering of metal coordination catalysts offers a promising route to tailor reaction pathways. Herein, we construct a dual-active-site catalyst featuring Cu–S and Eu–N coordination centers. Through atomic-level engineering of active site microenvironments, the optimized catalyst demonstrates performance comparable to state-of-the-art systems, achieving a remarkable CH 4 Faradaic efficiency of 75.8% alongside CH 4 partial current density of 303.3 mA cm –2 . Mechanistic studies reveal that isolated Cu sites hinder C–C coupling, while the strategically dispersed Eu sites facilitate efficient water activation, which is a critical process that generates abundant protons to accelerate the rate-limiting *CO hydrogenation step. This study establishes fundamental design principles for steering selective reaction pathways through atomic-scale modulation of active site architectures and their catalytic microenvironments.