Enhanced CO Electroreduction Selectivity toward Ethylene on Pyrazolate-Stabilized Asymmetric Ni-Cu Hybrid Sites.

Metal-organic frameworks (MOFs) possess well-defined, designable structures, holding great potential in enhancing product selectivity for electrochemical CO reduction (COR) through active site engineering. Here, we report a novel MOF catalyst featuring pyrazolate-stabilized asymmetric Ni/Cu sites, which not only maintains structural stability under harsh electrochemical conditions but also exhibits extraordinarily high ethylene (CH) selectivity during COR. At a cathode potential of -1.3 V versus RHE, our MOF catalyst, denoted as CuNi-BDP, manifests a CH Faradaic efficiency (FE) of 52.7% with an overall current density of 0.53 A cm in 1.0 M KOH electrolyte, surpassing that on prevailing Cu-based catalysts. More remarkably, the CuNi-BDP MOF exhibits a stable performance with only 4.5% reduction in CH FE during 25 h of CO electrolysis. A suite of characterization tools─such as high-resolution transmission electron microscopy, X-ray absorption spectroscopy, X-ray diffraction, and infrared spectroscopy─and density functional theory calculations collectively reveal that the cubic pyrazolate-metal coordination structure and the asymmetric Ni-Cu sites in the MOF catalyst synergistically facilitate the stable formation of CH from CO.