High-Valence Metal Modulating Lattice Oxygen in High-Entropy Layered Double Hydroxides for Enhanced Oxygen Evolution Reaction

Xiahua Zhong; Hong Yi Wang; Chen Zhang; Wenhu Wang; Christopher T. Nelson; Xiaoqing He; Qingqing Sun; Benjamine G. Gibson; Manish Neupane; Baolin Deng; Mingjie Liu; Yingchao Yang

doi:10.1002/adfm.202518240

High-Valence Metal Modulating Lattice Oxygen in High-Entropy Layered Double Hydroxides for Enhanced Oxygen Evolution Reaction

Xiahua Zhong
, Hong Yi Wang
, Chen Zhang
, Wenhu Wang
, Christopher T. Nelson
, Xiaoqing He
, Qingqing Sun
, Benjamine G. Gibson
, Manish Neupane
, Baolin Deng
, Mingjie Liu
, Yingchao Yang

electron Microscopy and Microanalysis

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

The oxygen evolution reaction (OER) is hindered by sluggish kinetics due to its complex four-electron, proton-coupled mechanism. While noble metal oxides like IrO₂ and RuO₂ are effective OER catalysts, their high cost and unsatisfactory stability limit large-scale applications. High-entropy layered double hydroxides (HE-LDHs) offer a promising alternative by enabling multi-metallic site tuning and entropy-driven phase stabilization. Herein, VCoNiCuZn and MoCoNiCuZn HE-LDHs respectively modulated by high-valence V⁴⁺/V⁵⁺ and Mo⁶⁺ are hydrothermally synthesized on Ni foam. The MoCoNiCuZn HE-LDH achieved an overpotential of 186 mV at 10 mA cm⁻², which is significantly lower than that of 306 mV obtained from CoNiCuZn LDH. The strong M-O covalency induced by high-valence metals facilitates charge redistribution and d-p orbital overlap, activating lattice oxygen and promoting the lattice oxygen mechanism (LOM). The resulting OER performance surpasses most reported multi-principal element materials and rivals noble-metal-doped LDHs. Moreover, high-entropy stabilization presents excellent structural durability and long-term electrochemical stability, highlighting the promise of noble-metal-free HE-LDHs for water splitting.

Original language	English
Article number	e18240
Journal	Advanced Functional Materials
Volume	35
Issue number	47
DOIs	https://doi.org/10.1002/adfm.202518240
State	Published - Nov 19 2025

Funding

X.Z. and H.W. contributed equally to this work. Y.Y. gratefully acknowledge financial support by the U.S. National Science Foundation, Faculty Early Career Development Program (CAREER), under award number 2420622. Y.Y. also thanks to the Center for Nanophase Materials Sciences (CNMS) at Oak Ridge National Laboratory (ORNL) for the characterization support under user proposal CNMS2023-B-02166. M.L and H.W. acknowledge the University of Florida Research Computing for providing computational resources and support that have contributed to the research results reported in this publication. X.Z. and H.W. contributed equally to this work. Y.Y. gratefully acknowledge financial support by the U.S. National Science Foundation, Faculty Early Career Development Program (CAREER), under award number 2420622. Y.Y. also thanks to the Center for Nanophase Materials Sciences (CNMS) at Oak Ridge National Laboratory (ORNL) for the characterization support under user proposal CNMS2023‐B‐02166. M.L and H.W. acknowledge the University of Florida Research Computing for providing computational resources and support that have contributed to the research results reported in this publication.

Keywords

high-entropy
high-valence metals
lattice oxygen
layered double hydroxides
oxygen evolution reaction

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10.1002/adfm.202518240

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title = "High-Valence Metal Modulating Lattice Oxygen in High-Entropy Layered Double Hydroxides for Enhanced Oxygen Evolution Reaction",

abstract = "The oxygen evolution reaction (OER) is hindered by sluggish kinetics due to its complex four-electron, proton-coupled mechanism. While noble metal oxides like IrO2 and RuO2 are effective OER catalysts, their high cost and unsatisfactory stability limit large-scale applications. High-entropy layered double hydroxides (HE-LDHs) offer a promising alternative by enabling multi-metallic site tuning and entropy-driven phase stabilization. Herein, VCoNiCuZn and MoCoNiCuZn HE-LDHs respectively modulated by high-valence V4+/V5+ and Mo6+ are hydrothermally synthesized on Ni foam. The MoCoNiCuZn HE-LDH achieved an overpotential of 186 mV at 10 mA cm−2, which is significantly lower than that of 306 mV obtained from CoNiCuZn LDH. The strong M-O covalency induced by high-valence metals facilitates charge redistribution and d-p orbital overlap, activating lattice oxygen and promoting the lattice oxygen mechanism (LOM). The resulting OER performance surpasses most reported multi-principal element materials and rivals noble-metal-doped LDHs. Moreover, high-entropy stabilization presents excellent structural durability and long-term electrochemical stability, highlighting the promise of noble-metal-free HE-LDHs for water splitting.",

keywords = "high-entropy, high-valence metals, lattice oxygen, layered double hydroxides, oxygen evolution reaction",

author = "Xiahua Zhong and Wang, \{Hong Yi\} and Chen Zhang and Wenhu Wang and Nelson, \{Christopher T.\} and Xiaoqing He and Qingqing Sun and Gibson, \{Benjamine G.\} and Manish Neupane and Baolin Deng and Mingjie Liu and Yingchao Yang",

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doi = "10.1002/adfm.202518240",

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T1 - High-Valence Metal Modulating Lattice Oxygen in High-Entropy Layered Double Hydroxides for Enhanced Oxygen Evolution Reaction

AU - Zhong, Xiahua

AU - Wang, Hong Yi

AU - Zhang, Chen

AU - Wang, Wenhu

AU - Nelson, Christopher T.

AU - He, Xiaoqing

AU - Sun, Qingqing

AU - Gibson, Benjamine G.

AU - Neupane, Manish

AU - Deng, Baolin

AU - Liu, Mingjie

AU - Yang, Yingchao

PY - 2025/11/19

Y1 - 2025/11/19

N2 - The oxygen evolution reaction (OER) is hindered by sluggish kinetics due to its complex four-electron, proton-coupled mechanism. While noble metal oxides like IrO2 and RuO2 are effective OER catalysts, their high cost and unsatisfactory stability limit large-scale applications. High-entropy layered double hydroxides (HE-LDHs) offer a promising alternative by enabling multi-metallic site tuning and entropy-driven phase stabilization. Herein, VCoNiCuZn and MoCoNiCuZn HE-LDHs respectively modulated by high-valence V4+/V5+ and Mo6+ are hydrothermally synthesized on Ni foam. The MoCoNiCuZn HE-LDH achieved an overpotential of 186 mV at 10 mA cm−2, which is significantly lower than that of 306 mV obtained from CoNiCuZn LDH. The strong M-O covalency induced by high-valence metals facilitates charge redistribution and d-p orbital overlap, activating lattice oxygen and promoting the lattice oxygen mechanism (LOM). The resulting OER performance surpasses most reported multi-principal element materials and rivals noble-metal-doped LDHs. Moreover, high-entropy stabilization presents excellent structural durability and long-term electrochemical stability, highlighting the promise of noble-metal-free HE-LDHs for water splitting.

AB - The oxygen evolution reaction (OER) is hindered by sluggish kinetics due to its complex four-electron, proton-coupled mechanism. While noble metal oxides like IrO2 and RuO2 are effective OER catalysts, their high cost and unsatisfactory stability limit large-scale applications. High-entropy layered double hydroxides (HE-LDHs) offer a promising alternative by enabling multi-metallic site tuning and entropy-driven phase stabilization. Herein, VCoNiCuZn and MoCoNiCuZn HE-LDHs respectively modulated by high-valence V4+/V5+ and Mo6+ are hydrothermally synthesized on Ni foam. The MoCoNiCuZn HE-LDH achieved an overpotential of 186 mV at 10 mA cm−2, which is significantly lower than that of 306 mV obtained from CoNiCuZn LDH. The strong M-O covalency induced by high-valence metals facilitates charge redistribution and d-p orbital overlap, activating lattice oxygen and promoting the lattice oxygen mechanism (LOM). The resulting OER performance surpasses most reported multi-principal element materials and rivals noble-metal-doped LDHs. Moreover, high-entropy stabilization presents excellent structural durability and long-term electrochemical stability, highlighting the promise of noble-metal-free HE-LDHs for water splitting.

KW - high-entropy

KW - high-valence metals

KW - lattice oxygen

KW - layered double hydroxides

KW - oxygen evolution reaction

UR - https://www.scopus.com/pages/publications/105018489000

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DO - 10.1002/adfm.202518240

M3 - Article

AN - SCOPUS:105018489000

SN - 1616-301X

VL - 35

JO - Advanced Functional Materials

JF - Advanced Functional Materials

IS - 47

M1 - e18240

ER -

High-Valence Metal Modulating Lattice Oxygen in High-Entropy Layered Double Hydroxides for Enhanced Oxygen Evolution Reaction

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Keywords

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