Ren Xiangrong, Zhai Yiyue, Yang Na, Wang Bolun, Liu Shengzhong Frank
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, Shaanxi Key Laboratory for Advanced Energy Devices, Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi'an, 710119, P. R. China.
School of Civil and Architecture Engineering, Xi'an Technological University, Xi'an, 710021, P. R. China.
Adv Sci (Weinh). 2025 Feb;12(8):e2412679. doi: 10.1002/advs.202412679. Epub 2025 Jan 9.
Understanding the oxygen evolution reaction (OER) mechanism is pivotal for improving the overall efficiency of water electrolysis. Despite methylammonium lead halide perovskites (MAPbX) have shown promising OER performance due to their soft-lattice nature that allows lattice-oxygen oxidation of active α-PbO layer surface, the role of A-site MA or X-site elements in the electrochemical reconstruction and OER mechanisms has yet to be explored. Here, it is demonstrated that the OER mechanism of perovskite@zeolite composites is intrinsically dominated by the A-site group of lead-halide perovskites, while the type of X-site halogen is crucial for the reconstruction kinetics of the composites. Using CsPbBrI @AlPO-5 (x = 0, 1, 2, 3) as a model OER catalyst, it is found that the CsPbBr@AlPO-5 behaves oxygen-intercalation pseudocapacitance during surface restructuring due to absence of halogen-ion migration and phase separation in the CsPbBr, achieving a larger diffusion rate of OH within the core-shell structure. Moreover, distinct from the single-metal-site mechanism of MAPbBr@AlPO-5, experimental and theoretical investigations reveal that the soft lattice nature of CsPbBr triggers the oxygen-vacancy-site mechanism via the CsPbBr/α-PbO interface, resulting in excellent OER performance. Owing to the variety and easy tailoring of lead-halide perovskite compositions, these findings pave a way for the development of novel perovskite@zeolite type catalysts for efficient oxygen electrocatalysis.
理解析氧反应（OER）机制对于提高水电解的整体效率至关重要。尽管甲基铵卤化铅钙钛矿（MAPbX）由于其软晶格性质，能够使活性α-PbO层表面发生晶格氧氧化，从而展现出有前景的析氧反应性能，但A位的MA或X位元素在电化学重构和析氧反应机制中的作用尚未得到探索。在此，研究表明钙钛矿@沸石复合材料的析氧反应机制本质上由卤化铅钙钛矿的A位基团主导，而X位卤素的类型对于复合材料的重构动力学至关重要。以CsPbBrI@AlPO-5（x = 0, 1, 2, 3）作为模型析氧反应催化剂，研究发现CsPbBr@AlPO-5在表面重构过程中表现出氧嵌入赝电容，这是由于CsPbBr中不存在卤素离子迁移和相分离，从而在核壳结构内实现了更大的OH扩散速率。此外，与MAPbBr@AlPO-5的单金属位点机制不同，实验和理论研究表明CsPbBr的软晶格性质通过CsPbBr/α-PbO界面触发了氧空位位点机制，从而产生了优异的析氧反应性能。由于卤化铅钙钛矿组成的多样性和易于剪裁，这些发现为开发用于高效氧电催化的新型钙钛矿@沸石型催化剂铺平了道路。
