A‐Site Management Prompts the Dynamic Reconstructed Active Phase of Perovskite Oxide OER Catalysts

• Published in: Advanced energy materials Vol. 11; no. 12
• Main Authors: Sun, Yu, Li, Ran, Chen, Xiaoxuan, Wu, Jing, Xie, Yong, Wang, Xin, Ma, Kaikai, Wang, Li, Zhang, Zheng, Liao, Qingliang, Kang, Zhuo, Zhang, Yue
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 01.03.2021
• Subjects: active phase; A‐site management; Catalysts; Cerium; dynamic reconstruction; Electrocatalysts; oxygen evolution reaction; Oxygen evolution reactions; perovskite oxides; Perovskites; Reconstruction; Substitution reactions; X‐site atom behavior
• DOI: 10.1002/aenm.202003755
• ISSN: 1614-6832

Perovskites (ABX3) are promising oxygen evolution reaction (OER) catalysts for their highly intrinsic activity. The in‐depth understanding and the adjustment of dynamic reconstruction of active phases for perovskites in OER are still a daunting challenge. Here, a refined A‐site management strategy is proposed for perovskite oxides, which facilitates the surface reconstruction of the B‐site element based active phase to enhance the OER performance. Electrocatalyst LaNiO3 displays a dynamic reconstruction feature during OER with the growth of a self‐assembled NiOOH active layer, based on the in situ electrochemical Raman technology. Precise A‐site Ce doping lowers the reconstruction potential for the active phase and the dynamic structure–activity correlation is well established. Theoretical calculations demonstrate that A‐site Ce substitution upshifts the O 2p level for greater structural flexibility with optimized oxygen vacancy content, thereby activating the B‐site atom and promoting the active phase reconstruction. These results suggest that A‐site management prompts the B‐site element based active phase dynamic reconstruction via engineered X‐site content as a bridge. Therefore, indicating the strong correlation of each‐site component in perovskite oxides during OER and deepening the understanding of the fundamental processes of the structural transformation and further benefiting the accurate design of high‐efficiency perovskite OER electrocatalysts. An A‐site management strategy is proposed to prompt the active phase reconstruction of perovskite oxides LaNiO3 via tuning of the oxygen vacancy state, to acquire an elevated oxygen evolution reaction (OER) performance. The findings strengthen the strong correlation of each‐site components in perovskites regarding the structure evolution during their practically catalytic service, thus further guiding the accurate design of perovskite OER electrocatalysts.