Gupta Shiva, Kellogg William, Xu Hui, Liu Xien, Cho Jaephil, Wu Gang
Department of Chemical and Biological Engineering, University at Buffalo, The State University of New York, Buffalo, New York, 14260, United States.
Giner Inc., Newton, MA, 02466, United States.
Chem Asian J. 2016 Jan;11(1):10-21. doi: 10.1002/asia.201500640. Epub 2015 Sep 4.
Oxygen electrocatalysis, namely of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), governs the performance of numerous electrochemical energy systems such as reversible fuel cells, metal-air batteries, and water electrolyzers. However, the sluggish kinetics of these two reactions and their dependency on expensive noble metal catalysts (e.g, Pt or Ir) prohibit the sustainable commercialization of these highly innovative and in-demand technologies. Bifunctional perovskite oxides have emerged as a new class of highly efficient non-precious metal catalysts (NPMC) for oxygen electrocatalysis in alkaline media. In this review, we discuss the state-of-the-art understanding of bifunctional properties of perovskites with regards to their OER/ORR activity in alkaline media and review the associated reaction mechanisms on the oxides surface and the related activity descriptors developed in the recent literature. We also summarize the present strategies to modify their electronic structure and to further improve their performance for the ORR/OER through highlighting the new concepts relating to the role of surface redox chemistry and oxygen deficiency of perovskite oxides for the ORR/OER activity. In addition, we provide a brief account of recently developed advanced perovskite-nanocarbon hybrid bifunctional catalysts with much improved performances.
氧电催化,即氧还原反应(ORR)和析氧反应(OER),决定了许多电化学能量系统的性能,如可逆燃料电池、金属空气电池和水电解槽。然而,这两个反应缓慢的动力学以及它们对昂贵贵金属催化剂(如Pt或Ir)的依赖性阻碍了这些极具创新性且需求旺盛的技术的可持续商业化。双功能钙钛矿氧化物已成为一类新型的高效非贵金属催化剂(NPMC),用于碱性介质中的氧电催化。在本综述中,我们讨论了关于钙钛矿在碱性介质中的OER/ORR活性的双功能性质的最新认识,并综述了氧化物表面相关的反应机理以及近期文献中提出的相关活性描述符。我们还总结了目前通过强调与表面氧化还原化学作用和钙钛矿氧化物的氧缺陷对ORR/OER活性的作用相关的新概念来修饰其电子结构并进一步提高其ORR/OER性能的策略。此外,我们简要介绍了最近开发的性能有显著提高的先进钙钛矿-纳米碳混合双功能催化剂。