Han Xue, Gao Qiang, Yan Zihao, Ji Mengxia, Long Christopher, Zhu Huiyuan
Department of Chemical Engineering, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061, USA.
Nanoscale. 2021 Jan 28;13(3):1515-1528. doi: 10.1039/d0nr08237f.
Catalysis in a confined space has attracted much attention due to the simultaneously designable nature of active sites and their microenvironment, leading to a broad spectrum of highly efficient chemical conversion schemes. Recent work has extended the scope of confined catalysis to electrochemical reactions. Mechanistic studies suggest that the confined environment in electrocatalysis can modulate mechanical, electronic, and geometric effects, stabilizing important charge-transfer intermediates and promoting reaction kinetics. In this minireview, we first discuss the fundamental concepts of confined catalysis by summarizing density functional theory (DFT) calculations and experimental investigations. We then present the rational design and applications of space-confined electrocatalysts with emphasis on the confined environment provided by carbon-based materials. We specifically focus on metal-based materials confined in carbon nanotubes (CNTs) and their applications in emerging electrochemical reactions including the oxygen reduction reaction (ORR), water-splitting reactions, carbon dioxide reduction reaction (CO2RR), and nitrogen reduction reaction (NRR). Finally, the existing challenges, opportunities, and future directions of electrocatalysis in confined spaces are highlighted.
受限空间中的催化作用因其活性位点及其微环境具有同时可设计的特性而备受关注，从而产生了一系列高效的化学转化方案。最近的研究工作已将受限催化的范围扩展到电化学反应。机理研究表明，电催化中的受限环境可以调节力学、电子和几何效应，稳定重要的电荷转移中间体并促进反应动力学。在这篇综述中，我们首先通过总结密度泛函理论（DFT）计算和实验研究来讨论受限催化的基本概念。然后，我们重点介绍空间受限电催化剂的合理设计及应用，特别强调碳基材料所提供的受限环境。我们具体关注限制在碳纳米管（CNT）中的金属基材料及其在新兴电化学反应中的应用，包括氧还原反应（ORR）、水分解反应、二氧化碳还原反应（CO2RR）和氮还原反应（NRR）。最后，强调了受限空间中电催化现存的挑战、机遇及未来发展方向。
