Stable Ni(II) sites in Prussian blue analogue for selective, ampere-level ethylene glycol electrooxidation

Abstract The industrial implementation of coupled electrochemical hydrogen production systems necessitates high power density and high product selectivity for economic viability and safety. However, for organic nucleophiles (e.g., methanol, urea, and amine) electrooxidation in the anode, most cataly...

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Main Authors: Ji Kai Liu, Mengde Kang, Kai Huang, Hao Guan Xu, Yi Xiao Wu, Xin Yu Zhang, Yan Zhu, Hao Fan, Song Ru Fang, Yi Zhou, Cheng Lian, Peng Fei Liu, Hua Gui Yang
Format: Article
Language:English
Published: Nature Portfolio 2025-04-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-58203-9
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author Ji Kai Liu
Mengde Kang
Kai Huang
Hao Guan Xu
Yi Xiao Wu
Xin Yu Zhang
Yan Zhu
Hao Fan
Song Ru Fang
Yi Zhou
Cheng Lian
Peng Fei Liu
Hua Gui Yang
author_facet Ji Kai Liu
Mengde Kang
Kai Huang
Hao Guan Xu
Yi Xiao Wu
Xin Yu Zhang
Yan Zhu
Hao Fan
Song Ru Fang
Yi Zhou
Cheng Lian
Peng Fei Liu
Hua Gui Yang
author_sort Ji Kai Liu
collection DOAJ
description Abstract The industrial implementation of coupled electrochemical hydrogen production systems necessitates high power density and high product selectivity for economic viability and safety. However, for organic nucleophiles (e.g., methanol, urea, and amine) electrooxidation in the anode, most catalytic materials undergo unavoidable reconstruction to generate high-valent metal sites under harsh operation conditions, resulting in competition with oxygen evolution reaction. Here, we present unique Ni(II) sites in Prussian blue analogue (NiFe-sc-PBA) that serve as stable, efficient and selective active sites for ethylene glycol (EG) electrooxidation to formic acid, particularly at ampere-level current densities. Our in situ/operando characterizations demonstrate the robustness of Ni(II) sites during EG electrooxidation. Molecular dynamics simulations further illustrate that EG molecule tends to accumulate on the NiFe-sc-PBA surface, preventing hydroxyl-induced reconstruction in alkaline solutions. The stable Ni(II) sites in NiFe-sc-PBA anodes exhibit efficient and selective EG electrooxidation performance in a coupled electrochemical hydrogen production flow cell, producing high-value formic acid compared to traditional alkaline water splitting. The coupled system can continuously operate at stepwise ampere-level current densities (switchable 1.0 or 1.5 A cm−2) for over 500 hours without performance degradation.
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institution OA Journals
issn 2041-1723
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publishDate 2025-04-01
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spelling doaj-art-ecfc501042d24d0188895bd97797e3192025-08-20T02:12:02ZengNature PortfolioNature Communications2041-17232025-04-0116111310.1038/s41467-025-58203-9Stable Ni(II) sites in Prussian blue analogue for selective, ampere-level ethylene glycol electrooxidationJi Kai Liu0Mengde Kang1Kai Huang2Hao Guan Xu3Yi Xiao Wu4Xin Yu Zhang5Yan Zhu6Hao Fan7Song Ru Fang8Yi Zhou9Cheng Lian10Peng Fei Liu11Hua Gui Yang12Key Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and TechnologyState Key Laboratory of Chemical Engineering, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Chemistry and Molecular Engineering, East China University of Science and TechnologyState Key Laboratory of Chemical Engineering, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Chemistry and Molecular Engineering, East China University of Science and TechnologyKey Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and TechnologyKey Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and TechnologyDepartment of Energy and Chemical Engineering, School of Resources and Environmental Engineering, East China University of Science and TechnologyKey Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and TechnologyKey Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and TechnologyKey Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and TechnologyDepartment of Energy and Chemical Engineering, School of Resources and Environmental Engineering, East China University of Science and TechnologyState Key Laboratory of Chemical Engineering, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Chemistry and Molecular Engineering, East China University of Science and TechnologyKey Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and TechnologyKey Laboratory for Ultrafine Materials of Ministry of Education, Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and TechnologyAbstract The industrial implementation of coupled electrochemical hydrogen production systems necessitates high power density and high product selectivity for economic viability and safety. However, for organic nucleophiles (e.g., methanol, urea, and amine) electrooxidation in the anode, most catalytic materials undergo unavoidable reconstruction to generate high-valent metal sites under harsh operation conditions, resulting in competition with oxygen evolution reaction. Here, we present unique Ni(II) sites in Prussian blue analogue (NiFe-sc-PBA) that serve as stable, efficient and selective active sites for ethylene glycol (EG) electrooxidation to formic acid, particularly at ampere-level current densities. Our in situ/operando characterizations demonstrate the robustness of Ni(II) sites during EG electrooxidation. Molecular dynamics simulations further illustrate that EG molecule tends to accumulate on the NiFe-sc-PBA surface, preventing hydroxyl-induced reconstruction in alkaline solutions. The stable Ni(II) sites in NiFe-sc-PBA anodes exhibit efficient and selective EG electrooxidation performance in a coupled electrochemical hydrogen production flow cell, producing high-value formic acid compared to traditional alkaline water splitting. The coupled system can continuously operate at stepwise ampere-level current densities (switchable 1.0 or 1.5 A cm−2) for over 500 hours without performance degradation.https://doi.org/10.1038/s41467-025-58203-9
spellingShingle Ji Kai Liu
Mengde Kang
Kai Huang
Hao Guan Xu
Yi Xiao Wu
Xin Yu Zhang
Yan Zhu
Hao Fan
Song Ru Fang
Yi Zhou
Cheng Lian
Peng Fei Liu
Hua Gui Yang
Stable Ni(II) sites in Prussian blue analogue for selective, ampere-level ethylene glycol electrooxidation
Nature Communications
title Stable Ni(II) sites in Prussian blue analogue for selective, ampere-level ethylene glycol electrooxidation
title_full Stable Ni(II) sites in Prussian blue analogue for selective, ampere-level ethylene glycol electrooxidation
title_fullStr Stable Ni(II) sites in Prussian blue analogue for selective, ampere-level ethylene glycol electrooxidation
title_full_unstemmed Stable Ni(II) sites in Prussian blue analogue for selective, ampere-level ethylene glycol electrooxidation
title_short Stable Ni(II) sites in Prussian blue analogue for selective, ampere-level ethylene glycol electrooxidation
title_sort stable ni ii sites in prussian blue analogue for selective ampere level ethylene glycol electrooxidation
url https://doi.org/10.1038/s41467-025-58203-9
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