Covalency competition dominates the water oxidation structure-activity relationship on spinel oxides

Spinel oxides have attracted growing interest over the years for catalysing the oxygen evolution reaction (OER) due to their efficiency and cost-effectiveness, but fundamental understanding of their structure–property relationships remains elusive. Here we demonstrate that the OER activity on spinel...

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Main Authors: Sun, Yuanmiao, Liao, Hanbin, Wang, Jiarui, Chen, Bo, Sun, Shengnan, Ong, Samuel Jun Hoong, Xi, Shibo, Diao, Caozheng, Du, Yonghua, Wang, Jia-Ou, Breese, Mark B. H., Li, Shuzhou, Zhang, Hua, Xu, Jason Zhichuan
Other Authors: School of Materials Science and Engineering
Format: Article
Language:English
Published: 2021
Subjects:
Online Access:https://hdl.handle.net/10356/148451
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Institution: Nanyang Technological University
Language: English
id sg-ntu-dr.10356-148451
record_format dspace
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic Engineering::Materials
Electrocatalysis
Water Oxidation
Spinel Oxides
Covalency Competition
spellingShingle Engineering::Materials
Electrocatalysis
Water Oxidation
Spinel Oxides
Covalency Competition
Sun, Yuanmiao
Liao, Hanbin
Wang, Jiarui
Chen, Bo
Sun, Shengnan
Ong, Samuel Jun Hoong
Xi, Shibo
Diao, Caozheng
Du, Yonghua
Wang, Jia-Ou
Breese, Mark B. H.
Li, Shuzhou
Zhang, Hua
Xu, Jason Zhichuan
Covalency competition dominates the water oxidation structure-activity relationship on spinel oxides
description Spinel oxides have attracted growing interest over the years for catalysing the oxygen evolution reaction (OER) due to their efficiency and cost-effectiveness, but fundamental understanding of their structure–property relationships remains elusive. Here we demonstrate that the OER activity on spinel oxides is intrinsically dominated by the covalency competition between tetrahedral and octahedral sites. The competition fabricates an asymmetric MT−O−MO backbone where the bond with weaker metal–oxygen covalency determines the exposure of cation sites and therefore the activity. Driven by this finding, a dataset with more than 300 spinel oxides is computed and used to train a machine-learning model for screening the covalency competition in spinel oxides, with a mean absolute error of 0.05 eV. [Mn]T[Al0.5Mn1.5]OO4 is predicted to be a highly active OER catalyst and subsequent experimental results confirm its superior activity. This work sets mechanistic principles of spinel oxides for water oxidation, which may be extendable to other applications.
author2 School of Materials Science and Engineering
author_facet School of Materials Science and Engineering
Sun, Yuanmiao
Liao, Hanbin
Wang, Jiarui
Chen, Bo
Sun, Shengnan
Ong, Samuel Jun Hoong
Xi, Shibo
Diao, Caozheng
Du, Yonghua
Wang, Jia-Ou
Breese, Mark B. H.
Li, Shuzhou
Zhang, Hua
Xu, Jason Zhichuan
format Article
author Sun, Yuanmiao
Liao, Hanbin
Wang, Jiarui
Chen, Bo
Sun, Shengnan
Ong, Samuel Jun Hoong
Xi, Shibo
Diao, Caozheng
Du, Yonghua
Wang, Jia-Ou
Breese, Mark B. H.
Li, Shuzhou
Zhang, Hua
Xu, Jason Zhichuan
author_sort Sun, Yuanmiao
title Covalency competition dominates the water oxidation structure-activity relationship on spinel oxides
title_short Covalency competition dominates the water oxidation structure-activity relationship on spinel oxides
title_full Covalency competition dominates the water oxidation structure-activity relationship on spinel oxides
title_fullStr Covalency competition dominates the water oxidation structure-activity relationship on spinel oxides
title_full_unstemmed Covalency competition dominates the water oxidation structure-activity relationship on spinel oxides
title_sort covalency competition dominates the water oxidation structure-activity relationship on spinel oxides
publishDate 2021
url https://hdl.handle.net/10356/148451
_version_ 1705151278307344384
spelling sg-ntu-dr.10356-1484512021-07-03T20:11:21Z Covalency competition dominates the water oxidation structure-activity relationship on spinel oxides Sun, Yuanmiao Liao, Hanbin Wang, Jiarui Chen, Bo Sun, Shengnan Ong, Samuel Jun Hoong Xi, Shibo Diao, Caozheng Du, Yonghua Wang, Jia-Ou Breese, Mark B. H. Li, Shuzhou Zhang, Hua Xu, Jason Zhichuan School of Materials Science and Engineering The Cambridge Centre for Advanced Research and Education in Sinpagore, Sinpagpre Singapore–HUJ Alliance for Research and Enterprise (SHARE), Nanomaterials for Energy and Energy–Water Nexus (NEW), Campus for Research Excellence and Technological Enterprise (CREATE), Singapore, Singapore Institute of Chemical and Engineering Science A*Star, Singapore Singapore Synchrotron Light Source (SSLS), National University of Singapore, Singapore Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, China Department of Chemistry, City University of Hong Kong, Hong Kong, China Hong Kong Branch of National Precious Metals Material Engineering Research Center (NPMM), City University of Hong Kong, Hong Kong, China Beijing Key Laboratory for Magnetoelectric Materials and Devices (BKLMMD), Beijing Innovation Center for Engineering Science and Advanced Technology (BIC-ESAT), Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing, China. National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY, USA Energy Research Institute @ NTU (ERI@N) Solar Fuels Laboratory Engineering::Materials Electrocatalysis Water Oxidation Spinel Oxides Covalency Competition Spinel oxides have attracted growing interest over the years for catalysing the oxygen evolution reaction (OER) due to their efficiency and cost-effectiveness, but fundamental understanding of their structure–property relationships remains elusive. Here we demonstrate that the OER activity on spinel oxides is intrinsically dominated by the covalency competition between tetrahedral and octahedral sites. The competition fabricates an asymmetric MT−O−MO backbone where the bond with weaker metal–oxygen covalency determines the exposure of cation sites and therefore the activity. Driven by this finding, a dataset with more than 300 spinel oxides is computed and used to train a machine-learning model for screening the covalency competition in spinel oxides, with a mean absolute error of 0.05 eV. [Mn]T[Al0.5Mn1.5]OO4 is predicted to be a highly active OER catalyst and subsequent experimental results confirm its superior activity. This work sets mechanistic principles of spinel oxides for water oxidation, which may be extendable to other applications. Ministry of Education (MOE) National Research Foundation (NRF) Accepted version This work was supported by Singapore Ministry of Education Tier 2 Grant (MOE2018-T2-2-027) and the Singapore National Research Foundation under its Campus for Research Excellence And Technological Enterprise (CREATE) programme. We thank the Facility for Analysis, Characterization, Testing, and Simulation (FACTS) in Nanyang Technological University. This research used resources of the National Synchrotron Light Source II, a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. We also appreciate the XAS measurements from SSLS, soft X-ray and ultraviolet beamline. Y.S. and Z.X. thank A. Lapkin (University of Cambridge) for helpful discussion on machine-learning concepts and thank L. Zeng (Southern University of Science and Technology) for helpful discussion on catalyst performance. H.Z. gives thanks for the support from ITC via the Hong Kong Branch of National Precious Metals Material (NPMM) Engineering Research Center, and the start-up grant (project no. 9380100) and grants (project no. 9610478 and 1886921) in City University of Hong Kong 2021-05-28T05:00:55Z 2021-05-28T05:00:55Z 2020 Journal Article Sun, Y., Liao, H., Wang, J., Chen, B., Sun, S., Ong, S. J. H., Xi, S., Diao, C., Du, Y., Wang, J., Breese, M. B. H., Li, S., Zhang, H. & Xu, J. Z. (2020). Covalency competition dominates the water oxidation structure-activity relationship on spinel oxides. Nature Catalysis, 3, 554-563. https://dx.doi.org/10.1038/s41929-020-0465-6 2520-1158 https://hdl.handle.net/10356/148451 10.1038/s41929-020-0465-6 3 554 563 en MOE2018-T2-2-027 Nature Catalysis © 2020 The Author(s), under exclusive licence to Springer Nature Limited. All rights reserved. This paper was published in Nature Catalysis and is made available with permission of The Author(s). application/pdf