Sun Mingxu, Rocabado David S Rivera, Cheng Jiamin, Noguchi Tomohiro G, Donoshita Masaki, Matsuu Takahiro, Higashi Manabu, Fujigaya Tsuyohiko, Ishimoto Takayoshi, Yamauchi Miho
Institute for Frontier Science, State Key Laboratory of Mechanics and Control of Mechanical Structure and Key Laboratory for Intelligent Nano Materials and Devices of the Ministry of Education, Nanjing University of Aeronautics and Astronautics, Nanjing, 210016, China.
Institute for Materials Chemistry and Engineering (IMCE), Kyushu University, Motooka 744, Nishi-ku, Fukuoka, 819-0395, Japan.
Angew Chem Int Ed Engl. 2025 Jul 21;64(30):e202502740. doi: 10.1002/anie.202502740. Epub 2025 May 24.
Electrocatalytic carbon dioxide (CO) reduction reaction (CORR) has emerged as a promising strategy for sustainable energy conversion and carbon utilization. Despite intensive research efforts, the understanding of intermediates and pathways leading from CORR to multicarbon (C) chemicals remains incomplete. The challenge is to gain insight into the activation of adsorbed CO and the subsequent pathways. Here, we design a specially tailored Cu nanowire array facing a hydrophobic interface as an electrode to highly enhance Raman signals in the in situ environment, allowing sensitive observation of the sequential change of various elusive intermediates during CORR, such as CO, CH, CO coexisting with CH, CHCO, and CH. Density functional theory calculations reveal that the C─C coupling during CORR originates from an asymmetric coupling between CH and CO to form CHCO, identified as the rate-determining step in the formation of C products. These findings deepen the understanding of the C─C coupling processes, which are crucial for advancing catalyst development in electrochemical CO upgrading.
电催化二氧化碳（CO₂）还原反应（CORR）已成为一种可持续能源转换和碳利用的有前景的策略。尽管进行了大量研究，但对于从CORR到多碳（C）化学品的中间体和途径的理解仍不完整。挑战在于深入了解吸附态CO的活化以及后续途径。在此，我们设计了一种面向疏水界面的特制铜纳米线阵列作为电极，以在原位环境中高度增强拉曼信号，从而能够灵敏地观察CORR过程中各种难以捉摸的中间体的相继变化，例如CO、CH、与CH共存的CO、CH₂CO和CH₃。密度泛函理论计算表明，CORR过程中的C─C偶联源于CH和CO之间的不对称偶联以形成CH₂CO，这被确定为C产物形成过程中的速率决定步骤。这些发现加深了对C─C偶联过程的理解，这对于推进电化学CO₂升级中的催化剂开发至关重要。
