Yang Timothy T, Saidi Wissam A
Department of Materials Science and Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States.
J Phys Chem Lett. 2022 Jun 8:5310-5315. doi: 10.1021/acs.jpclett.2c01411.
The volcano trend has been widely utilized to forecast new optimum catalysts in computational chemistry while the Butler-Volmer relationship is the norm to explain current-potential characteristics from cyclic voltammetry in analytical chemistry. Herein, we develop an electrochemical model for hydrogen evolution reaction exchange currents that reconciles device-level chemistry, atomic-level volcano trend, and the Butler-Volmer relation. We show that the model is a function of the easy-to-compute hydrogen adsorption energy invariably obtained from first-principles atomic simulations. In addition, the model reproduces with high fidelity the experimental exchange currents for elemental metal catalysts over 15 orders of magnitude and is consistent with the recently proposed analytical model based on a data-driven approach. Our findings based on fundamental electrochemistry principles are general and can be applied to other reactions including CO reduction, metal oxidation, and lithium (de)intercalation reactions.
火山趋势已被广泛用于预测计算化学中的新型最佳催化剂，而巴特勒-沃尔默关系则是解释分析化学中循环伏安法电流-电位特性的标准。在此，我们开发了一种用于析氢反应交换电流的电化学模型，该模型协调了器件级化学、原子级火山趋势和巴特勒-沃尔默关系。我们表明，该模型是易于计算的氢吸附能的函数，该氢吸附能总是从第一性原理原子模拟中获得。此外，该模型以高保真度再现了超过15个数量级的元素金属催化剂的实验交换电流，并且与最近基于数据驱动方法提出的分析模型一致。我们基于基本电化学原理的发现具有普遍性，可应用于其他反应，包括CO还原、金属氧化和锂（脱）嵌反应。
