厦门大学田中群团队近日取得一项新成果。他们揭示了直接电子转移在等离子体介导的电化学反应中的作用。该研究于2025年3月3日发表于国际一流学术期刊《美国化学会杂志》上。

结合电化学暗场散射光谱、光电化学方法和密度泛函理论计算，提供了DET在化学反应过程中的证据，并对DET和IET的贡献进行了解耦，建立了化学反应活性与DET效率之间的关系。

此外，课题组人员发现DET对不同的反应具有选择性，例如，对氧还原反应的增强作用远大于析氢反应。这项工作提供了通过DET优化反应选择性的可能性，并推进了等离子体电荷转移的机理见解。

据悉，金属-分子界面上电荷和能量流动的机制引起了人们的广泛关注，特别是近年来用于光化学转换的等离子体纳米材料的兴起。尽管许多研究已经证明了高能电子对加速化学反应的不可替代的作用，但理清直接电子转移（DET）和间接电子转移（IET）并理解它们的作用仍然具有挑战性。

附：英文原文

Title: Uncovering the Role of Direct Electron Transfer in Plasmon-Mediated Electrochemical Reactions

Author: Shu-Yi Zhu, Feng Xue, Qing-Chen Bai, Yan-Li He, Li-Jun Wang, Lin-Lin Wang, Wei-Jie Liu, Xia-Guang Zhang, Chao Zhan, Zhong-Qun Tian

Issue&Volume: March 3, 2025

Abstract: The mechanism of the charge and energy flow at the metal–molecule interface has attracted much attention, especially with the recent rise of plasmonic nanomaterials for light-to-chemical conversion. Although numerous studies have demonstrated the irreplaceable effects of energetic electrons on accelerating chemical reactions, detangling the direct electron transfer (DET) from indirect electron transfer (IET) and understanding their roles are still challenging. Here, by combining electrochemical dark field scattering spectroscopy, the photoelectrochemical method, and  density functional theory calculation, we provided the evidence of DET during chemical reactions, alongside  decoupling the contributions of DET and IET, and then established the relationship between chemical reactivity and  DET efficiency. Moreover, we discovered that DET is selective for different reactions, e.g., enhancing the oxygen reduction reaction much more than the hydrogen evolution reaction. This work offers the possibility to optimize reaction selectivity via DET and advances mechanistic insights into plasmonic charge transfer.

DOI: 10.1021/jacs.4c17754

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c17754