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Optimizing Hydrogen Binding on Ru Sites with RuCo Alloy Nanosheets for Efficient Alkaline Hydrogen Evolution

Ruthenium (Ru)‐based catalysts, with considerable performance and desirable cost, are becoming highly interesting candidates to replace platinum (Pt) in the alkaline hydrogen evolution reaction (HER). The hydrogen binding at Ru sites (Ru−H) is an important factor limiting the HER activity. Herein, d...

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Autores principales: Cai, Chao, Liu, Kang, Zhu, Yuanmin, Li, Pengcheng, Wang, Qiyou, Liu, Bao, Chen, Shanyong, Li, Huangjingwei, Zhu, Li, Li, Hongmei, Fu, Junwei, Chen, Yu, Pensa, Evangelina, Hu, Junhua, Lu, Ying‐Rui, Chan, Ting‐Shan, Cortés, Emiliano, Liu, Min
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9300137/
https://www.ncbi.nlm.nih.gov/pubmed/34822728
http://dx.doi.org/10.1002/anie.202113664
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author Cai, Chao
Liu, Kang
Zhu, Yuanmin
Li, Pengcheng
Wang, Qiyou
Liu, Bao
Chen, Shanyong
Li, Huangjingwei
Zhu, Li
Li, Hongmei
Fu, Junwei
Chen, Yu
Pensa, Evangelina
Hu, Junhua
Lu, Ying‐Rui
Chan, Ting‐Shan
Cortés, Emiliano
Liu, Min
author_facet Cai, Chao
Liu, Kang
Zhu, Yuanmin
Li, Pengcheng
Wang, Qiyou
Liu, Bao
Chen, Shanyong
Li, Huangjingwei
Zhu, Li
Li, Hongmei
Fu, Junwei
Chen, Yu
Pensa, Evangelina
Hu, Junhua
Lu, Ying‐Rui
Chan, Ting‐Shan
Cortés, Emiliano
Liu, Min
author_sort Cai, Chao
collection PubMed
description Ruthenium (Ru)‐based catalysts, with considerable performance and desirable cost, are becoming highly interesting candidates to replace platinum (Pt) in the alkaline hydrogen evolution reaction (HER). The hydrogen binding at Ru sites (Ru−H) is an important factor limiting the HER activity. Herein, density functional theory (DFT) simulations show that the essence of Ru−H binding energy is the strong interaction between the [Formula: see text] orbital of Ru and the 1s orbital of H. The charge transfer between Ru sites and substrates (Co and Ni) causes the appropriate downward shift of the [Formula: see text] ‐band center of Ru, which results in a Gibbs free energy of 0.022 eV for H* in the RuCo system, much lower than the 0.133 eV in the pure Ru system. This theoretical prediction has been experimentally confirmed using RuCo alloy‐nanosheets (RuCo ANSs). They were prepared via a fast co‐precipitation method followed with a mild electrochemical reduction. Structure characterizations reveal that the Ru atoms are embedded into the Co substrate as isolated active sites with a planar symmetric and Z‐direction asymmetric coordination structure, obtaining an optimal [Formula: see text] modulated electronic structure. Hydrogen sensor and temperature program desorption (TPD) tests demonstrate the enhanced Ru−H interactions in RuCo ANSs compared to those in pure Ru nanoparticles. As a result, the RuCo ANSs reach an ultra‐low overpotential of 10 mV at 10 mA cm(−2) and a Tafel slope of 20.6 mV dec(−1) in 1 M KOH, outperforming that of the commercial Pt/C. This holistic work provides a new insight to promote alkaline HER by optimizing the metal‐H binding energy of active sites.
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spelling pubmed-93001372022-07-21 Optimizing Hydrogen Binding on Ru Sites with RuCo Alloy Nanosheets for Efficient Alkaline Hydrogen Evolution Cai, Chao Liu, Kang Zhu, Yuanmin Li, Pengcheng Wang, Qiyou Liu, Bao Chen, Shanyong Li, Huangjingwei Zhu, Li Li, Hongmei Fu, Junwei Chen, Yu Pensa, Evangelina Hu, Junhua Lu, Ying‐Rui Chan, Ting‐Shan Cortés, Emiliano Liu, Min Angew Chem Int Ed Engl Communications Ruthenium (Ru)‐based catalysts, with considerable performance and desirable cost, are becoming highly interesting candidates to replace platinum (Pt) in the alkaline hydrogen evolution reaction (HER). The hydrogen binding at Ru sites (Ru−H) is an important factor limiting the HER activity. Herein, density functional theory (DFT) simulations show that the essence of Ru−H binding energy is the strong interaction between the [Formula: see text] orbital of Ru and the 1s orbital of H. The charge transfer between Ru sites and substrates (Co and Ni) causes the appropriate downward shift of the [Formula: see text] ‐band center of Ru, which results in a Gibbs free energy of 0.022 eV for H* in the RuCo system, much lower than the 0.133 eV in the pure Ru system. This theoretical prediction has been experimentally confirmed using RuCo alloy‐nanosheets (RuCo ANSs). They were prepared via a fast co‐precipitation method followed with a mild electrochemical reduction. Structure characterizations reveal that the Ru atoms are embedded into the Co substrate as isolated active sites with a planar symmetric and Z‐direction asymmetric coordination structure, obtaining an optimal [Formula: see text] modulated electronic structure. Hydrogen sensor and temperature program desorption (TPD) tests demonstrate the enhanced Ru−H interactions in RuCo ANSs compared to those in pure Ru nanoparticles. As a result, the RuCo ANSs reach an ultra‐low overpotential of 10 mV at 10 mA cm(−2) and a Tafel slope of 20.6 mV dec(−1) in 1 M KOH, outperforming that of the commercial Pt/C. This holistic work provides a new insight to promote alkaline HER by optimizing the metal‐H binding energy of active sites. John Wiley and Sons Inc. 2021-12-07 2022-01-21 /pmc/articles/PMC9300137/ /pubmed/34822728 http://dx.doi.org/10.1002/anie.202113664 Text en © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Communications
Cai, Chao
Liu, Kang
Zhu, Yuanmin
Li, Pengcheng
Wang, Qiyou
Liu, Bao
Chen, Shanyong
Li, Huangjingwei
Zhu, Li
Li, Hongmei
Fu, Junwei
Chen, Yu
Pensa, Evangelina
Hu, Junhua
Lu, Ying‐Rui
Chan, Ting‐Shan
Cortés, Emiliano
Liu, Min
Optimizing Hydrogen Binding on Ru Sites with RuCo Alloy Nanosheets for Efficient Alkaline Hydrogen Evolution
title Optimizing Hydrogen Binding on Ru Sites with RuCo Alloy Nanosheets for Efficient Alkaline Hydrogen Evolution
title_full Optimizing Hydrogen Binding on Ru Sites with RuCo Alloy Nanosheets for Efficient Alkaline Hydrogen Evolution
title_fullStr Optimizing Hydrogen Binding on Ru Sites with RuCo Alloy Nanosheets for Efficient Alkaline Hydrogen Evolution
title_full_unstemmed Optimizing Hydrogen Binding on Ru Sites with RuCo Alloy Nanosheets for Efficient Alkaline Hydrogen Evolution
title_short Optimizing Hydrogen Binding on Ru Sites with RuCo Alloy Nanosheets for Efficient Alkaline Hydrogen Evolution
title_sort optimizing hydrogen binding on ru sites with ruco alloy nanosheets for efficient alkaline hydrogen evolution
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9300137/
https://www.ncbi.nlm.nih.gov/pubmed/34822728
http://dx.doi.org/10.1002/anie.202113664
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