Electronic structure-dependent water-dissociation pathways of ruthenium-based catalysts in alkaline H2-Evolution

Chengdong Yang; Zihe Wu; Zhenyang Zhao; Yun Gao; Tian Ma; Chao He; Changzhu Wu; Xikui Liu; Xianglin Luo; Shuang Li; Chong Cheng; Changsheng Zhao

doi:10.1002/smll.202206949

Electronic structure-dependent water-dissociation pathways of ruthenium-based catalysts in alkaline H₂-Evolution

Chengdong Yang, Zihe Wu, Zhenyang Zhao, Yun Gao, Tian Ma, Chao He, Changzhu Wu, Xikui Liu, Xianglin Luo, Shuang Li^*, Chong Cheng^*, Changsheng Zhao^*

^*Kontaktforfatter

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review

26 Downloads (Pure)

Abstract

Ruthenium (Ru)-based catalysts have displayed compelling hydrogen evolution activities, which hold the promising potential to substitute platinum in alkaline H₂-evolution. In the challenging alkaline electrolytes, the water-dissociation process involves multistep reactions, while the profound origin and intrinsic factors of diverse Ru species on water-dissociation pathways and reaction principles remain ambiguous. Here the fundamental origin of water-dissociation pathways of Ru-based catalysts in alkaline media to be from their unique electronic structures in complex coordination environments are disclosed. These theoretical results validate that the modulated electronic structures with delocalization-localization coexistence at their boundaries between the Ru nanocluster and single-atom site have a profound influence on water-dissociation pathways, which push H₂O* migration and binding orientation during the splitting process, thus enhancing the dissociation kinetics. By creating Ru catalysts with well-defined nanocluster, single-atom site, and also complex site, the electrocatalytic data shows that both the nanocluster and single-atom play essential roles in water-dissociation, while the complex site possesses synergistically enhanced roles in alkaline electrolytes. This study discloses a new electronic structure-dependent water-dissociation pathway and reaction principle in Ru-based catalysts, thus offering new inspiration to design efficient and durable catalysts for the practical production of H₂ in alkaline electrolytes.

Originalsprog	Engelsk
Artikelnummer	2206949
Tidsskrift	Small
Vol/bind	19
Udgave nummer	14
Antal sider	10
ISSN	1613-6810
DOI	https://doi.org/10.1002/smll.202206949
Status	Udgivet - 5. apr. 2023

Bibliografisk note

Funding Information:
This work was financially supported by the National Key R&D Program of China (2021YFE0205000, 2019YFA0110600, and 2019YFA0110601), National Natural Science Foundation of China (Nos. 52161145402, 52173133, and 51803134), the Sichuan Science and Technology Program (Nos. 2022YFH0088, 2021YFH0087, 2021YFH0135, and 2021YFH0180), the 1·3·5 Project for Disciplines of Excellence, West China Hospital, Sichuan University (No. ZYJC21047), the innovation project of Med‐X Center for Materials, Sichuan University (No. MCM202102). C.C. acknowledges the financial support of the State Key Laboratory of Polymer Materials Engineering (Grant No. sklpme2021‐4‐02) and Fundamental Research Funds for the Central Universities. C.H. thanks the China Scholarship Council (CSC) for financial support. The authors gratefully acknowledge Dr. Mi Zhou and Dr. Minghua Zhang for their analytical support. The authors thank the Ceshigo Research Service for the technical support on XAS. The authors also thank Zhongkebaice Technology Service Co. Ltd. for the technical support on high‐resolution HAADF‐STEM.

Publisher Copyright:
© 2023 Wiley-VCH GmbH.

Dokumenter og links

10.1002/smll.202206949

Open Access VersionAccepteret manuskript, 2,91 MB

Citationsformater

@article{ce27559fd64f47589fc2e793ddffaff2,

title = "Electronic structure-dependent water-dissociation pathways of ruthenium-based catalysts in alkaline H2-Evolution",

abstract = "Ruthenium (Ru)-based catalysts have displayed compelling hydrogen evolution activities, which hold the promising potential to substitute platinum in alkaline H2-evolution. In the challenging alkaline electrolytes, the water-dissociation process involves multistep reactions, while the profound origin and intrinsic factors of diverse Ru species on water-dissociation pathways and reaction principles remain ambiguous. Here the fundamental origin of water-dissociation pathways of Ru-based catalysts in alkaline media to be from their unique electronic structures in complex coordination environments are disclosed. These theoretical results validate that the modulated electronic structures with delocalization-localization coexistence at their boundaries between the Ru nanocluster and single-atom site have a profound influence on water-dissociation pathways, which push H2O* migration and binding orientation during the splitting process, thus enhancing the dissociation kinetics. By creating Ru catalysts with well-defined nanocluster, single-atom site, and also complex site, the electrocatalytic data shows that both the nanocluster and single-atom play essential roles in water-dissociation, while the complex site possesses synergistically enhanced roles in alkaline electrolytes. This study discloses a new electronic structure-dependent water-dissociation pathway and reaction principle in Ru-based catalysts, thus offering new inspiration to design efficient and durable catalysts for the practical production of H2 in alkaline electrolytes.",

keywords = "electrocatalysts, hydrogen production, ruthenium materials, seawater electrolysis, water-dissociation",

author = "Chengdong Yang and Zihe Wu and Zhenyang Zhao and Yun Gao and Tian Ma and Chao He and Changzhu Wu and Xikui Liu and Xianglin Luo and Shuang Li and Chong Cheng and Changsheng Zhao",

note = "Funding Information: This work was financially supported by the National Key R&D Program of China (2021YFE0205000, 2019YFA0110600, and 2019YFA0110601), National Natural Science Foundation of China (Nos. 52161145402, 52173133, and 51803134), the Sichuan Science and Technology Program (Nos. 2022YFH0088, 2021YFH0087, 2021YFH0135, and 2021YFH0180), the 1·3·5 Project for Disciplines of Excellence, West China Hospital, Sichuan University (No. ZYJC21047), the innovation project of Med‐X Center for Materials, Sichuan University (No. MCM202102). C.C. acknowledges the financial support of the State Key Laboratory of Polymer Materials Engineering (Grant No. sklpme2021‐4‐02) and Fundamental Research Funds for the Central Universities. C.H. thanks the China Scholarship Council (CSC) for financial support. The authors gratefully acknowledge Dr. Mi Zhou and Dr. Minghua Zhang for their analytical support. The authors thank the Ceshigo Research Service for the technical support on XAS. The authors also thank Zhongkebaice Technology Service Co. Ltd. for the technical support on high‐resolution HAADF‐STEM. Publisher Copyright: {\textcopyright} 2023 Wiley-VCH GmbH.",

year = "2023",

month = apr,

day = "5",

doi = "10.1002/smll.202206949",

language = "English",

volume = "19",

journal = "Small",

issn = "1613-6810",

publisher = "Wiley - V C H Verlag GmbH & Co. KGaA",

number = "14",

}

TY - JOUR

T1 - Electronic structure-dependent water-dissociation pathways of ruthenium-based catalysts in alkaline H2-Evolution

AU - Yang, Chengdong

AU - Wu, Zihe

AU - Zhao, Zhenyang

AU - Gao, Yun

AU - Ma, Tian

AU - He, Chao

AU - Wu, Changzhu

AU - Liu, Xikui

AU - Luo, Xianglin

AU - Li, Shuang

AU - Cheng, Chong

AU - Zhao, Changsheng

N1 - Funding Information: This work was financially supported by the National Key R&D Program of China (2021YFE0205000, 2019YFA0110600, and 2019YFA0110601), National Natural Science Foundation of China (Nos. 52161145402, 52173133, and 51803134), the Sichuan Science and Technology Program (Nos. 2022YFH0088, 2021YFH0087, 2021YFH0135, and 2021YFH0180), the 1·3·5 Project for Disciplines of Excellence, West China Hospital, Sichuan University (No. ZYJC21047), the innovation project of Med‐X Center for Materials, Sichuan University (No. MCM202102). C.C. acknowledges the financial support of the State Key Laboratory of Polymer Materials Engineering (Grant No. sklpme2021‐4‐02) and Fundamental Research Funds for the Central Universities. C.H. thanks the China Scholarship Council (CSC) for financial support. The authors gratefully acknowledge Dr. Mi Zhou and Dr. Minghua Zhang for their analytical support. The authors thank the Ceshigo Research Service for the technical support on XAS. The authors also thank Zhongkebaice Technology Service Co. Ltd. for the technical support on high‐resolution HAADF‐STEM. Publisher Copyright: © 2023 Wiley-VCH GmbH.

PY - 2023/4/5

Y1 - 2023/4/5

N2 - Ruthenium (Ru)-based catalysts have displayed compelling hydrogen evolution activities, which hold the promising potential to substitute platinum in alkaline H2-evolution. In the challenging alkaline electrolytes, the water-dissociation process involves multistep reactions, while the profound origin and intrinsic factors of diverse Ru species on water-dissociation pathways and reaction principles remain ambiguous. Here the fundamental origin of water-dissociation pathways of Ru-based catalysts in alkaline media to be from their unique electronic structures in complex coordination environments are disclosed. These theoretical results validate that the modulated electronic structures with delocalization-localization coexistence at their boundaries between the Ru nanocluster and single-atom site have a profound influence on water-dissociation pathways, which push H2O* migration and binding orientation during the splitting process, thus enhancing the dissociation kinetics. By creating Ru catalysts with well-defined nanocluster, single-atom site, and also complex site, the electrocatalytic data shows that both the nanocluster and single-atom play essential roles in water-dissociation, while the complex site possesses synergistically enhanced roles in alkaline electrolytes. This study discloses a new electronic structure-dependent water-dissociation pathway and reaction principle in Ru-based catalysts, thus offering new inspiration to design efficient and durable catalysts for the practical production of H2 in alkaline electrolytes.

AB - Ruthenium (Ru)-based catalysts have displayed compelling hydrogen evolution activities, which hold the promising potential to substitute platinum in alkaline H2-evolution. In the challenging alkaline electrolytes, the water-dissociation process involves multistep reactions, while the profound origin and intrinsic factors of diverse Ru species on water-dissociation pathways and reaction principles remain ambiguous. Here the fundamental origin of water-dissociation pathways of Ru-based catalysts in alkaline media to be from their unique electronic structures in complex coordination environments are disclosed. These theoretical results validate that the modulated electronic structures with delocalization-localization coexistence at their boundaries between the Ru nanocluster and single-atom site have a profound influence on water-dissociation pathways, which push H2O* migration and binding orientation during the splitting process, thus enhancing the dissociation kinetics. By creating Ru catalysts with well-defined nanocluster, single-atom site, and also complex site, the electrocatalytic data shows that both the nanocluster and single-atom play essential roles in water-dissociation, while the complex site possesses synergistically enhanced roles in alkaline electrolytes. This study discloses a new electronic structure-dependent water-dissociation pathway and reaction principle in Ru-based catalysts, thus offering new inspiration to design efficient and durable catalysts for the practical production of H2 in alkaline electrolytes.

KW - electrocatalysts

KW - hydrogen production

KW - ruthenium materials

KW - seawater electrolysis

KW - water-dissociation

U2 - 10.1002/smll.202206949

DO - 10.1002/smll.202206949

M3 - Journal article

C2 - 36599619

AN - SCOPUS:85145690875

SN - 1613-6810

VL - 19

JO - Small

JF - Small

IS - 14

M1 - 2206949

ER -