Confined Intermediates Boost C2+ Selectivity in CO<sub>2</sub> Electroreduction
Wanhe Li, Yahui Chen, Chengqi Guo, Shuhan Jia, Yiying Zhou, Zhonghuan Liu, Enhui Jiang, Xiaoke Chen, Yue Zou, Pengwei Huo, Y.F. YAN, Yongshneg Yan, Zhi Zhu, Yun Hau Ng, Yanjun Gong, John C. Crittenden, Yan Yan, Yan Yan
Abstract
Addressing the efficient electrochemical conversion of CO 2 (CO 2 RR) into valuable multicarbon (C2+) products necessitates innovative strategies to boost carbon (C1) intermediate coupling on catalyst surfaces. In this work, we introduce a surface-confinement strategy on Cu 2 O nanoparticles by long alkyl chain grafting to create a spatially confined environment, impeding C1 intermediate detachment and promoting C–C coupling in the CO 2 RR. The optimized C12–Cu 2 O sample exhibits a Faradaic efficiency (FE) over 63.0% for C 2 H 4, more than double the yield of pristine Cu 2 O (FE = 25.7%). In situ ATR-FTIR spectroscopy provides direct evidence of rapid C1 intermediate enrichment and restricted diffusion within the surface-confined environment. Molecular dynamics simulations further support these findings by identifying a prolonged residency time that is proportionate to the alkyl chain length, thereby maximizing C2+ selectivity. This surface-confinement approach marks a previously overlooked but immensely promising paradigm in the catalyst design for the CO 2 RR.