Enhanced CO 2 Electroreduction Selectivity toward Ethylene on Pyrazolate-Stabilized Asymmetric Ni–Cu Hybrid Sites

作者：Liang Huang, Ziao Liu, Ge Gao, Cailing Chen, Yanrong Xue, Jiwu Zhao, Qiong Lei, Mengtian Jin, Chongqin Zhu, Yu Han, Joseph S. Francisco, Lu Xu · 发表于：Journal of the American Chemical Society · 年份：2023 · DOI：10.1021/jacs.3c10600 · 被引用次数：107 · 研究领域：CO2 Reduction Techniques and Catalysts、Ionic liquids properties and applications、Advanced battery technologies research

Metal–organic frameworks (MOFs) possess well-defined, designable structures, holding great potential in enhancing product selectivity for electrochemical CO 2 reduction (CO 2 R) 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 (C 2 H 4 ) selectivity during CO 2 R. At a cathode potential of −1.3 V versus RHE, our MOF catalyst, denoted as Cu 1 Ni-BDP, manifests a C 2 H 4 Faradaic efficiency (FE) of 52.7% with an overall current density of 0.53 A cm –2 in 1.0 M KOH electrolyte, surpassing that on prevailing Cu-based catalysts. More remarkably, the Cu 1 Ni-BDP MOF exhibits a stable performance with only 4.5% reduction in C 2 H 4 FE during 25 h of CO 2 electrolysis. A suite of characterization tools─such as high-resolution transmission electron microscopy, X-ray absorption spectroscopy, operando 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 C 2 H 4 from CO 2 .