近日，美国劳伦斯伯克利国家实验室的Haimei Zheng及其研究团队取得一项新进展。经过不懈努力，他们揭示液电池TEM中带电固液界面的原子动力学。相关研究成果已于2024年6月19日在国际权威学术期刊《自然》上发表。

该研究团队开发了用于透射电子显微镜(TEM)的先进聚合物电化学液体电池，研究人员能够直接监测铜(Cu)催化CO₂电还原反应(CO₂ERs)过程中ESLIs的原子动力学。这一观察揭示了一个动态变化的液态无定形界面，该界面在通电的Cu表面上可逆地进行晶态与非晶态的结构转变，并伴随着界面层的流动，从而通过界面层介导结晶Cu表面重构和质量损失。实时观察和理论计算的结合揭示了由电荷激活的电解质表面反应引起的非晶化介导的复合机制。通过利用原位成像能力，这项研究结果为探索原子动力学及其在涉及ESLIs的广泛系统中的影响提供了诸多机会。

据悉，带电固液界面在与能源、生物和地球化学相关的各种电化学过程中起着关键作用。带电界面上的电子和质量传递可能导致结构改变，从而显著影响反应路径。例如，电催化剂在反应过程中的表面复合会对催化机理和反应产物产生实质性的影响。尽管它很重要，但直接探测电偏置下固液界面的原子动力学是具有挑战性的，因为它被埋在液体电解质中，而且目前通过液体进行原位成像的技术空间分辨率有限。

附：英文原文

Title: Atomic dynamics of electrified solid–liquid interfaces in liquid-cell TEM

Author: Zhang, Qiubo, Song, Zhigang, Sun, Xianhu, Liu, Yang, Wan, Jiawei, Betzler, Sophia B., Zheng, Qi, Shangguan, Junyi, Bustillo, Karen C., Ercius, Peter, Narang, Prineha, Huang, Yu, Zheng, Haimei

Issue&Volume: 2024-06-19

Abstract: Electrified solid–liquid interfaces (ESLIs) play a key role in various electrochemical processes relevant to energy, biology and geochemistry. The electron and mass transport at the electrified interfaces may result in structural modifications that markedly influence the reaction pathways. For example, electrocatalyst surface restructuring during reactions can substantially affect the catalysis mechanisms and reaction products. Despite its importance, direct probing the atomic dynamics of solid–liquid interfaces under electric biasing is challenging owing to the nature of being buried in liquid electrolytes and the limited spatial resolution of current techniques for in situ imaging through liquids. Here, with our development of advanced polymer electrochemical liquid cells for transmission electron microscopy (TEM), we are able to directly monitor the atomic dynamics of ESLIs during copper (Cu)-catalysed CO₂ electroreduction reactions (CO₂ERs). Our observation reveals a fluctuating liquid-like amorphous interphase. It undergoes reversible crystalline–amorphous structural transformations and flows along the electrified Cu surface, thus mediating the crystalline Cu surface restructuring and mass loss through the interphase layer. The combination of real-time observation and theoretical calculations unveils an amorphization-mediated restructuring mechanism resulting from charge-activated surface reactions with the electrolyte. Our results open many opportunities to explore the atomic dynamics and its impact in broad systems involving ESLIs by taking advantage of the in situ imaging capability.

DOI: 10.1038/s41586-024-07479-w

Source: https://www.nature.com/articles/s41586-024-07479-w