Moore Yoshua H, Johnson Ben A, Plumeré Nicolas
Technical University of Munich (TUM), Campus Straubing for Biotechnology and Sustainability, Uferstraße 53, 94315 Straubing, Germany.
ACS Electrochem. 2025 Jun 2;1(8):1258-1273. doi: 10.1021/acselectrochem.5c00091. eCollection 2025 Aug 7.
The pore structure is a key design parameter for optimizing electrocatalytic systems that utilize porous electrodes, necessitating characterization at scales relevant to catalysis (∼0.1-100 μm). In this Review, we examine how diffusion during faradaic processes is impacted by the electrode pore geometry, defined by the concavity/convexity of its surface curvature, and by pore size, defined by the finiteness of the diffusion domain. We briefly outline experimental considerations for correlating experimental and simulated data from porous electrodes, and then outline the current theories for modeling diffusional voltammetry at various electrodes with finite diffusion spaces (direct problem), including planar redox-active films, concave inverse opals and hollow tubes, and convex pillar arrays and particle arrays. Finally, we describe how these theoretical frameworks can be applied to characterize the electrode pore structure by analyzing experimental voltammetric current responses (inverse problem).
孔隙结构是优化利用多孔电极的电催化系统的关键设计参数，因此需要在与催化相关的尺度（约0.1 - 100μm）上进行表征。在本综述中，我们研究了在法拉第过程中扩散如何受到电极孔隙几何形状（由其表面曲率的凹凸性定义）和孔径（由扩散域的有限性定义）的影响。我们简要概述了关联多孔电极实验数据和模拟数据的实验注意事项，然后概述了当前用于模拟各种具有有限扩散空间的电极上的扩散伏安法的理论（正问题），包括平面氧化还原活性膜、凹面反蛋白石和空心管，以及凸面柱状阵列和颗粒阵列。最后，我们描述了如何通过分析实验伏安电流响应（反问题）将这些理论框架应用于表征电极孔隙结构。
