近日，美国加州大学伯克利分校D. Kwabena Bediako团队研究了界面电子传递中重组能的电子起源。该研究于2026年4月22日发表在《自然》杂志上。

电子转移反应是生物和非生物系统中能量转换与化学转化的基础。任何电子转移过程的效率都依赖于在最佳驱动力范围内实现所需的电子转移速率。Marcus理论提供了一个微观框架，通过一个关键参数——重组能，来理解电子转移的活化自由能（从而理解其速率）。长期以来，关于带电固液界面的传统认识是：只有电解质相中的因素决定了重组能，而电极的电子态密度仅仅用于决定电子转移的热可及通道数目。

研究组表明，电极的态密度在调控重组能方面扮演着核心角色，其重要性远超传统认知。利用原子层状异质结构，研究组调控了石墨烯的态密度，并测量了外球电子转移动力学。结果发现，电子转移速率随之产生的变化源于与电极中镜像势局域化相关的重组能的强烈调制。研究组重新定义了异相电子转移动力学的传统范式，揭示了电极电子结构在界面反应性中更深层次的作用。

附：英文原文

Title: Electronic origin of reorganization energy in interfacial electron transfer

Author: Maroo, Sonal, Coello Escalante, Leonardo, Wang, Yizhe, Erodici, Matthew P., Nessralla, Jonathon N., Tabo, Ayana, Taniguchi, Takashi, Watanabe, Kenji, Xu, Ke, Limmer, David T., Bediako, D. Kwabena

Issue&Volume: 2026-04-22

Abstract: Electron transfer (ET) reactions underpin energy conversion and chemical transformations in both biological1,2 and abiological3,4,5 systems. The efficiency of any ET process relies on achieving a desired ET rate within an optimal driving force range. Marcus theory6,7 provides a microscopic framework for understanding the activation free energy—and therefore the rate—of ET in terms of a key parameter: the reorganization energy. For electrified solid–liquid interfaces, it has long been conventionally understood that only factors in the electrolyte phase are responsible for determining the reorganization energy and that the electronic density of states (DOS) of the electrode only serves to dictate the number of thermally accessible channels for ET5,8,9,10,11,12. Here we show instead that the electrode DOS plays a central role in governing the reorganization energy, far outweighing its conventionally assumed role. Using atomically layered heterostructures, we tune the DOS of graphene and measure outer-sphere ET kinetics. We find the ensuing variation in ET rate arises from strong modulation in a reorganization energy associated with image potential localization in the electrode. Here we redefine the traditional paradigm of heterogeneous ET kinetics, revealing a deeper role of the electrode electronic structure in interfacial reactivity.

DOI: 10.1038/s41586-026-10311-2

Source: https://www.nature.com/articles/s41586-026-10311-2