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journal article·2016-09-01Open access

Elucidating dz2 orbital selective catalytic activity in brownmillerite Ca2Mn2O5

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

AIP Advances· Volume 6· Issue 9
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Source abstract

Abstract

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.
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Research context

Catalysis & surfaces

OpenAlex topics: Magnetic and transport properties of perovskites and related materials · Advanced Condensed Matter Physics · Electronic and Structural Properties of Oxides

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Beijing University of Technology 1 Institute of Microstructure and Properties of Advanced Materials, , Beijing 100124, P. R. China

Nankai University 2 Department of Electronics and Tianjin Key Laboratory of Photo-Electronic Thin Film Device and Technology, , Tianjin 300071, China

Shandong University of Science and Technology 3 College of Material Science and Engineering, , Qingdao 266590, China

Tsinghua University 4 Center for Testing and Analyzing of Materials, School of Materials Science and Engineering, , Beijing 100084, China

Hebei University of Technology 5 College of Material Science and Engineering, , Tianjin 300130, China

Tianjin University of Technology 6 College of Science, , 300384, China

Nankai University 7 Department of Chemistry, , Tianjin 300071, China

Dongguan Innovative New Materials Co. 8 , Dongguan 523000, China

Chinese Academy of Sciences 9 Beijing National Laboratory for Condensed Matter Physics, and Institute of Physics, , Beijing 100190, China

Funding

National Natural Science Foundation of China

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