Ferrocene‐Engineered Bimetallic MOF Nanoflowers Boost Selective CO <sub>2</sub> ‐to‐CH <sub>4</sub> Electrocatalysis via Dual‐Metal Synergy and Structural Precision
Yanchao Xu, Yinggui Xia, Shuyan Fan, Wenyue Gao, Zhu Gao, Cui‐Juan Wang
Abstract
Abstract Electrocatalytic CO 2 reduction to methane (CH 4 ) is a promising route for sustainable energy conversion and carbon neutrality. However, limited control over intermediates and competition from the hydrogen evolution reaction (HER) restrict selectivity and efficiency. To address these challenges, a ferrocene‐based bimetallic metal‐organic framework MOF catalyst (Ni x In y ‐Fc/NF) with a hierarchical nanoflower architecture is developed, where dual‐metal synergy modulates the electronic structure at active sites. Incorporating redox‐active ferrocene units and optimizing the Ni/In ratio enhances active‐site accessibility and tunes the electronic environment. Structural and compositional analyses, including scanning electron microscopy (SEM) and energy‐dispersive X‐ray spectroscopy (EDS), confirm that Ni 5 In 3 ‐Fc/NF possesses a 3D porous nanoflower morphology, while X‐ray photoelectron spectroscopy (XPS) reveals electronic interactions between Ni and In. Electrochemical tests show that the catalyst achieves 76% CH 4 Faradaic efficiency at −0.8 V versus RHE and suppresses H 2 evolution. Ni 5 In 3 ‐Fc/NF maintains stability and CH 4 selectivity over 16 000 s of electrolysis. Density‐functional theory (DFT) indicates that the bimetallic interface reduces the energy barrier for the rate‐limiting *CO formation step, thereby accelerating the CO 2 ‐to‐CH 4 pathway. This study presents a synergistic strategy integrating dual‐metal interaction and structural precision to enhance performance and durability in CO 2 electroreduction, offering insights into the rational design of high‐performance MOF catalysts.