Topotactic phase transformations by concerted dual-ion migration of B-site cation and oxygen in multivalent cobaltite La–Sr–Co–Ox films. (December 2020)

• Record Type: Journal Article
• Authors: Li, Jia; Guan, Meng-Xue; Nan, Peng-Fei; Wang, Jing; Ge, Bing-Hui; Qiao, Kai-Ming; Zhang, Hong-Rui; Liang, Wen-Hui; Hao, Jia-Zheng; Zhou, Hou-Bo; Shen, Fei-Ran; Liang, Fei-Xiang; Zhang, Cheng; Liu, Miao; Meng, Sheng; Zhu, Tao; Hu, Feng-Xia; Wu, Tom; Guo, Jian-Dong; Sun, Ji-Rong; Shen, Bao-Gen
• Is Part Of: Nano energy. Volume 78(2020)
• Publication Date: 2020-12
• Subjects: Topotactic phase transformation -- Perovskite cobalt oxides -- B-site cation transfer -- Brownmillerite structure -- Electrocatalyst; Nanoscience -- Periodicals; Nanotechnology -- Periodicals; Nanostructured materials -- Periodicals; Power resources -- Technological innovations -- Periodicals; Nanoscience; Nanostructured materials; Nanotechnology; Power resources -- Technological innovations; Periodicals; 621.042
• DOI: 10.1016/j.nanoen.2020.105215
• Languages: English
• ISSNs: 2211-2855

Abstract

Abstract: Manipulating topotactic phase transformations via orderly ion transfer in complex oxides ABOx is ubiquitous in advanced applications such as ionotronics, ion-batteries and catalysts. Most of such ion-mediated transformations are accomplished by the transfer of oxygen or A-site ions. However, implementing the transformation via the transfer of B-site ions, despite the great challenge to overcome a large cohesive energy, has unique advantage since they host most functional properties of materials. Here, we present a tri-state phase transformation from perovskite (P) to brownmillerite (BM) and to single-layered perovskite (SL) structure via the concerted migration of oxygen and B-site Co-ions in La0.7 Sr0.3 CoO3 thin films. Ac-STEM, XPS, XAS, PNR, magnetic and electric measurements demonstrated that presented B-site Co-cation transfer is along the CoO4 tetrahedral sub-layer of the BM film, which leads to the reconfiguration of 3 d -electrons and spin state in remanent Co ions and causes tremendous changes in magnetic and electric properties: from canted-antiferromagnetic insulator in BM phase to ferromagnetic insulator in SL phase. First-principles calculations revealed that the La 3+ -doping at A-site largely reduces the cohesive energy of Co-ions in CoO4 and destabilize the CoO4 tetrahedron of BM phase, which explains the formation of Co-ions transfer channel in the CoO4 tetrahedral sub-layer. The present study highlights the effectiveness of regulating topotactic transformation via B-site ions transfer and provides a new pathway for manipulating the topotactic transformation with diverse functionalities. Graphical abstract: Tri-state topotactic transformation induced by B-site Co ion transfer was firstly realized in La0.7 Sr0.3 CoO3 film. A unique transfer channel for Co-ions is demonstrated to be facilitated by the instability of CoO4 due to A-site La-doping. The reconfiguration of 3d-electrons due to Co transfer leads to tremendous changes in magnetic and electric properties. Such new topotactic transformation driven by B-site ion transfer offers opportunity to exploit new types of electrocatalyst with rich functionalities. Image 1 Highlights: Tri-state topotactic transformation induced by B-site Co ion transfer was firstly realized in La0.7 Sr0.3 CoO3 film. A unique transfer channel for Co-ions is demonstrated to be facilitated by the instability of CoO4 due to A-site La-doping. The concerted transfer of Co and O ions drive tremendous changes in magnetic and electric properties. Such B-site ion transfer provides a new pathway for exploiting electrocatalyst with diverse functionalities.