skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Cations in Octahedral Sites: A Descriptor for Oxygen Electrocatalysis on Transition-Metal Spinels

Abstract

Exploring efficient and low-cost electrocatalysts for the oxygen-reduction reaction (ORR) and oxygen-evolution reaction (OER) is critical for developing renewable energy technologies such as fuel cells, metal–air batteries, and water electrolyzers. A rational design of a catalyst can be guided by identifying descriptors that determine its activity. Here, a descriptor study on the ORR/OER of spinel oxides is presented. With a series of MnCo2O4, the Mn in octahedral sites is identified as an active site. This finding is then applied to successfully explain the ORR/OER activities of other transition-metal spinels, including MnxCo3-xO4 (x = 2, 2.5, 3), LixMn2O4 (x = 0.7, 1), XCo2O4 (X = Co, Ni, Zn), and XFe2O4 (X = Mn, Co, Ni). A general principle is concluded that the eg occupancy of the active cation in the octahedral site is the activity descriptor for the ORR/OER of spinels, consolidating the role of electron orbital filling in metal oxide catalysis.

Authors:
 [1];  [2];  [3];  [4];  [5];  [6]
  1. School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue 639798 Singapore
  2. School of Chemical, Biological, and Environmental Engineering, Oregon State University, Corvallis OR 97331 USA
  3. TUM-CREATE, One Create Way 138602 Singapore
  4. Department of Life Sciences, Imperial College London, London SW7 2AZ UK; Solar Fuels Laboratory, Nanyang Technological University, 50 Nanyang Avenue 639798 Singapore
  5. Materials Science and Engineering Department, Massachusetts Institute of Technology, Cambridge MA 02139 USA; Electrochemical Energy Laboratory, Massachusetts Institute of Technology, Cambridge MA 02139 USA
  6. School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue 639798 Singapore; Solar Fuels Laboratory, Nanyang Technological University, 50 Nanyang Avenue 639798 Singapore; Energy Research Institute @ Nanyang Technological University, 50 Nanyang Avenue 639798 Singapore
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
FOREIGN
OSTI Identifier:
1372924
Resource Type:
Journal Article
Resource Relation:
Journal Name: Advanced Materials; Journal Volume: 29; Journal Issue: 23
Country of Publication:
United States
Language:
ENGLISH
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wei, Chao, Feng, Zhenxing, Scherer, Günther G., Barber, James, Shao-Horn, Yang, and Xu, Zhichuan J. Cations in Octahedral Sites: A Descriptor for Oxygen Electrocatalysis on Transition-Metal Spinels. United States: N. p., 2017. Web. doi:10.1002/adma.201606800.
Wei, Chao, Feng, Zhenxing, Scherer, Günther G., Barber, James, Shao-Horn, Yang, & Xu, Zhichuan J. Cations in Octahedral Sites: A Descriptor for Oxygen Electrocatalysis on Transition-Metal Spinels. United States. doi:10.1002/adma.201606800.
Wei, Chao, Feng, Zhenxing, Scherer, Günther G., Barber, James, Shao-Horn, Yang, and Xu, Zhichuan J. Mon . "Cations in Octahedral Sites: A Descriptor for Oxygen Electrocatalysis on Transition-Metal Spinels". United States. doi:10.1002/adma.201606800.
@article{osti_1372924,
title = {Cations in Octahedral Sites: A Descriptor for Oxygen Electrocatalysis on Transition-Metal Spinels},
author = {Wei, Chao and Feng, Zhenxing and Scherer, Günther G. and Barber, James and Shao-Horn, Yang and Xu, Zhichuan J.},
abstractNote = {Exploring efficient and low-cost electrocatalysts for the oxygen-reduction reaction (ORR) and oxygen-evolution reaction (OER) is critical for developing renewable energy technologies such as fuel cells, metal–air batteries, and water electrolyzers. A rational design of a catalyst can be guided by identifying descriptors that determine its activity. Here, a descriptor study on the ORR/OER of spinel oxides is presented. With a series of MnCo2O4, the Mn in octahedral sites is identified as an active site. This finding is then applied to successfully explain the ORR/OER activities of other transition-metal spinels, including MnxCo3-xO4 (x = 2, 2.5, 3), LixMn2O4 (x = 0.7, 1), XCo2O4 (X = Co, Ni, Zn), and XFe2O4 (X = Mn, Co, Ni). A general principle is concluded that the eg occupancy of the active cation in the octahedral site is the activity descriptor for the ORR/OER of spinels, consolidating the role of electron orbital filling in metal oxide catalysis.},
doi = {10.1002/adma.201606800},
journal = {Advanced Materials},
number = 23,
volume = 29,
place = {United States},
year = {Mon Apr 10 00:00:00 EDT 2017},
month = {Mon Apr 10 00:00:00 EDT 2017}
}