Kramarenko Aleksandr S, Sharapa Dmitry I, Pidko Evgeny A, Studt Felix
Institute of Catalysis Research and Technology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
Inorganic Systems Engineering Group, Department of Chemical Engineering, Faculty of Applied Sciences, Delft University of Technology, Delft 2628 CN, The Netherlands.
J Phys Chem A. 2024 Oct 17;128(41):9063-9070. doi: 10.1021/acs.jpca.4c04923. Epub 2024 Oct 3.
The current state-of-the-art electron-transfer modeling primarily focuses on the kinetics of charge transfer between an electroactive species and an inert electrode. Experimental studies have revealed that the existing Butler-Volmer model fails to satisfactorily replicate experimental voltammetry results for both solution-based and surface-bound redox couples. Consequently, experimentalists lack an accurate tool for predicting electron-transfer kinetics. In response to this challenge, we developed a density functional theory-based approach for accurately predicting current peak potentials by using the Marcus-Hush model. Through extensive cyclic voltammetry simulations, we conducted a thorough exploration that offers valuable insights for conducting well-informed studies in the field of electrochemistry.
当前最先进的电子转移建模主要集中在电活性物种与惰性电极之间电荷转移的动力学上。实验研究表明，现有的巴特勒-沃尔默模型无法令人满意地复制基于溶液和表面结合的氧化还原对的实验伏安法结果。因此，实验人员缺乏预测电子转移动力学的准确工具。为应对这一挑战，我们开发了一种基于密度泛函理论的方法，通过使用马库斯-胡什模型准确预测电流峰值电位。通过广泛的循环伏安法模拟，我们进行了全面的探索，为在电化学领域进行明智的研究提供了有价值的见解。
