Elucidating dz2 orbital selective catalytic activity in brownmillerite Ca2Mn2O5
3d-orbital filling in transition metal oxide is crucial to govern the catalytic activity in oxygen evolution reduction, nevertheless, it is not fundamentally accessible why specific orbital occupation produces a highest catalytic performance. Here, we utilize brownmillerite Ca2Mn2O5 to clarify the o...
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doaj-46884e2ab64848658b6bce4aff811c6a2020-11-24T22:10:03ZengAIP Publishing LLCAIP Advances2158-32262016-09-0169095210095210-710.1063/1.4963079045609ADVElucidating dz2 orbital selective catalytic activity in brownmillerite Ca2Mn2O5Yue Lu0Feng Lu1Zhi Yang2Jie Wu3Hongyun Yu4Xinjian Xie5Jianping Xu6Fangyi Cheng7Jun Chen8Ka Xiong9Hui Liu10Wei-Hua Wang11Jianzhou Zhao12Weichao Wang13Institute of Microstructure and Properties of Advanced Materials, Beijing University of Technology, Beijing 100124, P. R. ChinaDepartment of Electronics and Tianjin Key Laboratory of Photo-Electronic Thin Film Device and Technology, Nankai University, Tianjin 300071, ChinaDepartment of Electronics and Tianjin Key Laboratory of Photo-Electronic Thin Film Device and Technology, Nankai University, Tianjin 300071, ChinaCollege of Material Science and Engineering, Shandong University of Science and Technology, Qingdao 266590, ChinaCenter for Testing and Analyzing of Materials, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, ChinaCollege of Material Science and Engineering, Hebei University of Technology, Tianjin 300130, ChinaCollege of Science, Tianjin University of Technology, 300384, ChinaDepartment of Chemistry, Nankai University, Tianjin 300071, ChinaDepartment of Chemistry, Nankai University, Tianjin 300071, ChinaDongguan Innovative New Materials Co., Dongguan 523000, ChinaDepartment of Electronics and Tianjin Key Laboratory of Photo-Electronic Thin Film Device and Technology, Nankai University, Tianjin 300071, ChinaDepartment of Electronics and Tianjin Key Laboratory of Photo-Electronic Thin Film Device and Technology, Nankai University, Tianjin 300071, ChinaBeijing National Laboratory for Condensed Matter Physics, and Institute of Physics, Chinese Academy of Sciences, Beijing 100190, ChinaDepartment of Electronics and Tianjin Key Laboratory of Photo-Electronic Thin Film Device and Technology, Nankai University, Tianjin 300071, China3d-orbital filling in transition metal oxide is crucial to govern the catalytic activity in oxygen evolution reduction, nevertheless, it is not fundamentally accessible why specific orbital occupation produces a highest catalytic performance. Here, we utilize brownmillerite Ca2Mn2O5 to clarify the orbital selective catalytic behavior due to the crystal field splitting and on-site coulomb interactions. Within density functional theory plus dynamical mean field theory, Ca2Mn2O5 shows a paramagnetic Mott insulating behavior at room temperature, consistent with optical adsorption spectra and magnetic susceptibility. As the center of the dz2 orbital locates in the lower Hubbard sub-band, the unit occupation on dz2 orbital provides a moderate bonding with external O* species to cause a high catalytic activity of Ca2Mn2O5 with a square pyramid crystal field. Such concept of unit occupation of dz2 near Fermi level could be extended to other crystal fields for future design of oxide catalysts.http://dx.doi.org/10.1063/1.4963079 |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Yue Lu Feng Lu Zhi Yang Jie Wu Hongyun Yu Xinjian Xie Jianping Xu Fangyi Cheng Jun Chen Ka Xiong Hui Liu Wei-Hua Wang Jianzhou Zhao Weichao Wang |
spellingShingle |
Yue Lu Feng Lu Zhi Yang Jie Wu Hongyun Yu Xinjian Xie Jianping Xu Fangyi Cheng Jun Chen Ka Xiong Hui Liu Wei-Hua Wang Jianzhou Zhao Weichao Wang Elucidating dz2 orbital selective catalytic activity in brownmillerite Ca2Mn2O5 AIP Advances |
author_facet |
Yue Lu Feng Lu Zhi Yang Jie Wu Hongyun Yu Xinjian Xie Jianping Xu Fangyi Cheng Jun Chen Ka Xiong Hui Liu Wei-Hua Wang Jianzhou Zhao Weichao Wang |
author_sort |
Yue Lu |
title |
Elucidating dz2 orbital selective catalytic activity in brownmillerite Ca2Mn2O5 |
title_short |
Elucidating dz2 orbital selective catalytic activity in brownmillerite Ca2Mn2O5 |
title_full |
Elucidating dz2 orbital selective catalytic activity in brownmillerite Ca2Mn2O5 |
title_fullStr |
Elucidating dz2 orbital selective catalytic activity in brownmillerite Ca2Mn2O5 |
title_full_unstemmed |
Elucidating dz2 orbital selective catalytic activity in brownmillerite Ca2Mn2O5 |
title_sort |
elucidating dz2 orbital selective catalytic activity in brownmillerite ca2mn2o5 |
publisher |
AIP Publishing LLC |
series |
AIP Advances |
issn |
2158-3226 |
publishDate |
2016-09-01 |
description |
3d-orbital filling in transition metal oxide is crucial to govern the catalytic activity in oxygen evolution reduction, nevertheless, it is not fundamentally accessible why specific orbital occupation produces a highest catalytic performance. Here, we utilize brownmillerite Ca2Mn2O5 to clarify the orbital selective catalytic behavior due to the crystal field splitting and on-site coulomb interactions. Within density functional theory plus dynamical mean field theory, Ca2Mn2O5 shows a paramagnetic Mott insulating behavior at room temperature, consistent with optical adsorption spectra and magnetic susceptibility. As the center of the dz2 orbital locates in the lower Hubbard sub-band, the unit occupation on dz2 orbital provides a moderate bonding with external O* species to cause a high catalytic activity of Ca2Mn2O5 with a square pyramid crystal field. Such concept of unit occupation of dz2 near Fermi level could be extended to other crystal fields for future design of oxide catalysts. |
url |
http://dx.doi.org/10.1063/1.4963079 |
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