Confined Intermediates Boost C2+ Selectivity in CO2 Electroreduction

• Published in: ACS catalysis 2024-09, Vol.14 (17), p.13400-13407
• Main Authors: Li, Wanhe, Chen, Yahui, Guo, Chengqi, Jia, Shuhan, Zhou, Yiying, Liu, Zhonghuan, Jiang, Enhui, Chen, Xiaoke, Zou, Yue, Huo, Pengwei, Yan, Yongshneg, Zhu, Zhi, Ng, Yun Hau, Gong, Yanjun, Crittenden, John Charles, Yan, Yan
• Format: Article
• Language: English
• ISSN: 2155-5435; 2155-5435
• DOI: 10.1021/acscatal.4c02823

Addressing the efficient electrochemical conversion of CO2 (CO2RR) 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 Cu2O nanoparticles by long alkyl chain grafting to create a spatially confined environment, impeding C1 intermediate detachment and promoting C–C coupling in the CO2RR. The optimized C12–Cu2O sample exhibits a Faradaic efficiency (FE) over 63.0% for C2H4, more than double the yield of pristine Cu2O (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 CO2RR.