A Structure‐Defined Cu(I) Dual‐Atom Catalyst with a Cu ₂ N ₆ Motif in a Metal‐Organic Framework for CO Electroreduction

Abstract The electroreduction of carbon monoxide (CO) provides a sustainable pathway to valuable multi‐carbon (C 2+ ) products, contributing to carbon neutrality. Enhancing coupling efficiency and selectivity for C 2+ formation hinges on precise control of the spatial arrangement of catalytic sites where CO molecules adsorb. Here, we introduce a structurally well‐defined Cu(I) dual‐atom catalyst (DAC) embedded in a metal‐organic framework (MOF) that is synthesized via a thermal transformation. Single‐crystal X‐ray diffraction (SCD) reveals Cu 2 N 6 motifs with a Cu–Cu distance of 3.6 Å, stabilized by tetrazolate within a 2D layer, ensuring CO accessibility and efficient coupling. The catalyst achieves a Faradaic efficiency (FE) of 72% for C 2+ products at a partial current density of −430 mA cm −2 , and a maximum C 2+ FE of 86% at a total current density of −200 mA cm −2 . In situ spectroscopy and density functional theory (DFT) calculations reveal that the paired Cu nodes stabilize key C 2 intermediates via distinct binding configurations, underpinning the system's exceptional performance.