Identifying a Universal Activity Descriptor and a Unifying Mechanism Concept on Perovskite Oxides for Green Hydrogen Production

Producing indispensable hydrogen and oxygen for social development via water electrolysis shows more prospects than other technologies. Although electrocatalysts have been explored for centuries, a universal activity descriptor for both hydrogen-evolution reaction (HER) and oxygen-evolution reaction...

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Main Authors: Guan, D., Xu, Hengyue, Zhang, Q., Huang, Y.C., Shi, C., Chang, Y.C., Xu, Xiaomin, Tang, Jiayi, Gu, Y., Pao, C.W., Haw, S.C., Chen, J.M., Hu, Z., Ni, M., Shao, Zongping
Format: Journal Article
Language:English
Published: 2023
Subjects:
Online Access:http://purl.org/au-research/grants/arc/DP200103315
http://hdl.handle.net/20.500.11937/94762
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author Guan, D.
Xu, Hengyue
Zhang, Q.
Huang, Y.C.
Shi, C.
Chang, Y.C.
Xu, Xiaomin
Tang, Jiayi
Gu, Y.
Pao, C.W.
Haw, S.C.
Chen, J.M.
Hu, Z.
Ni, M.
Shao, Zongping
author_facet Guan, D.
Xu, Hengyue
Zhang, Q.
Huang, Y.C.
Shi, C.
Chang, Y.C.
Xu, Xiaomin
Tang, Jiayi
Gu, Y.
Pao, C.W.
Haw, S.C.
Chen, J.M.
Hu, Z.
Ni, M.
Shao, Zongping
author_sort Guan, D.
building Curtin Institutional Repository
collection Online Access
description Producing indispensable hydrogen and oxygen for social development via water electrolysis shows more prospects than other technologies. Although electrocatalysts have been explored for centuries, a universal activity descriptor for both hydrogen-evolution reaction (HER) and oxygen-evolution reaction (OER) is not yet developed. Moreover, a unifying concept is not yet established to simultaneously understand HER/OER mechanisms. Here, the relationships between HER/OER activities in three common electrolytes and over ten representative material properties on 12 3d-metal-based model oxides are rationally bridged through statistical methodologies. The orbital charge-transfer energy (Δ) can serve as an ideal universal descriptor, where a neither too large nor too small Δ (≈1 eV) with optimal electron-cloud density around Fermi level affords the best activities, fulfilling Sabatier's principle. Systematic experiments and computations unravel that pristine oxide with Δ ≈ 1 eV possesses metal-like high-valence configurations and active lattice-oxygen sites to help adsorb key protons in HER and induce lattice-oxygen participation in the OER, respectively. After reactions, partially generated metals in the HER and high-valence hydroxides in the OER dominate proton adsorption and couple with pristine lattice-oxygen activation, respectively. These can be successfully rationalized by the unifying orbital charge-transfer theory. This work provides the foundation of rational material design and mechanism understanding for many potential applications.
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institution Curtin University Malaysia
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publishDate 2023
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spelling curtin-20.500.11937-947622024-04-17T08:16:01Z Identifying a Universal Activity Descriptor and a Unifying Mechanism Concept on Perovskite Oxides for Green Hydrogen Production Guan, D. Xu, Hengyue Zhang, Q. Huang, Y.C. Shi, C. Chang, Y.C. Xu, Xiaomin Tang, Jiayi Gu, Y. Pao, C.W. Haw, S.C. Chen, J.M. Hu, Z. Ni, M. Shao, Zongping green hydrogen production orbital charge-transfer theory property-activity relationships unifying mechanism concept universal activity descriptors Producing indispensable hydrogen and oxygen for social development via water electrolysis shows more prospects than other technologies. Although electrocatalysts have been explored for centuries, a universal activity descriptor for both hydrogen-evolution reaction (HER) and oxygen-evolution reaction (OER) is not yet developed. Moreover, a unifying concept is not yet established to simultaneously understand HER/OER mechanisms. Here, the relationships between HER/OER activities in three common electrolytes and over ten representative material properties on 12 3d-metal-based model oxides are rationally bridged through statistical methodologies. The orbital charge-transfer energy (Δ) can serve as an ideal universal descriptor, where a neither too large nor too small Δ (≈1 eV) with optimal electron-cloud density around Fermi level affords the best activities, fulfilling Sabatier's principle. Systematic experiments and computations unravel that pristine oxide with Δ ≈ 1 eV possesses metal-like high-valence configurations and active lattice-oxygen sites to help adsorb key protons in HER and induce lattice-oxygen participation in the OER, respectively. After reactions, partially generated metals in the HER and high-valence hydroxides in the OER dominate proton adsorption and couple with pristine lattice-oxygen activation, respectively. These can be successfully rationalized by the unifying orbital charge-transfer theory. This work provides the foundation of rational material design and mechanism understanding for many potential applications. 2023 Journal Article http://hdl.handle.net/20.500.11937/94762 10.1002/adma.202305074 eng http://purl.org/au-research/grants/arc/DP200103315 http://purl.org/au-research/grants/arc/DP200103332 http://creativecommons.org/licenses/by/4.0/ fulltext
spellingShingle green hydrogen production
orbital charge-transfer theory
property-activity relationships
unifying mechanism concept
universal activity descriptors
Guan, D.
Xu, Hengyue
Zhang, Q.
Huang, Y.C.
Shi, C.
Chang, Y.C.
Xu, Xiaomin
Tang, Jiayi
Gu, Y.
Pao, C.W.
Haw, S.C.
Chen, J.M.
Hu, Z.
Ni, M.
Shao, Zongping
Identifying a Universal Activity Descriptor and a Unifying Mechanism Concept on Perovskite Oxides for Green Hydrogen Production
title Identifying a Universal Activity Descriptor and a Unifying Mechanism Concept on Perovskite Oxides for Green Hydrogen Production
title_full Identifying a Universal Activity Descriptor and a Unifying Mechanism Concept on Perovskite Oxides for Green Hydrogen Production
title_fullStr Identifying a Universal Activity Descriptor and a Unifying Mechanism Concept on Perovskite Oxides for Green Hydrogen Production
title_full_unstemmed Identifying a Universal Activity Descriptor and a Unifying Mechanism Concept on Perovskite Oxides for Green Hydrogen Production
title_short Identifying a Universal Activity Descriptor and a Unifying Mechanism Concept on Perovskite Oxides for Green Hydrogen Production
title_sort identifying a universal activity descriptor and a unifying mechanism concept on perovskite oxides for green hydrogen production
topic green hydrogen production
orbital charge-transfer theory
property-activity relationships
unifying mechanism concept
universal activity descriptors
url http://purl.org/au-research/grants/arc/DP200103315
http://purl.org/au-research/grants/arc/DP200103315
http://hdl.handle.net/20.500.11937/94762