Insights into the pH effect on hydrogen electrocatalysis

Hydrogen electrocatalytic reactions, including the hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR), play a crucial role in a wide range of energy conversion and storage technologies. However, the HER and HOR display anomalous non-Nernstian pH dependent kinetics, showing t...

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Published inChemical Society reviews Vol. 53; no. 2; pp. 1253 - 1311
Main Authors Cui, Wen-Gang, Gao, Fan, Na, Guoquan, Wang, Xingqiang, Li, Zhenglong, Yang, Yaxiong, Niu, Zhiqiang, Qu, Yongquan, Wang, Dingsheng, Pan, Hongge
Format Journal Article
LanguageEnglish
Published England Royal Society of Chemistry 14.10.2024
Subjects
Acidic oxides
Anion exchanging
Catalysts
Design optimization
Electrocatalysis
Electrolysis
Electrolytes
Electrolytic cells
Energy conversion
Fuel cells
Hydrogen
Hydrogen evolution reactions
Kinetics
Oxidation
Reaction kinetics
Online AccessGet full text
ISSN0306-0012
1460-4744
1460-4744
DOI10.1039/d4cs00370e

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Abstract Hydrogen electrocatalytic reactions, including the hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR), play a crucial role in a wide range of energy conversion and storage technologies. However, the HER and HOR display anomalous non-Nernstian pH dependent kinetics, showing two to three orders of magnitude sluggish kinetics in alkaline media compared to that in acidic media. Fundamental understanding of the origins of the intrinsic pH effect has attracted substantial interest from the electrocatalysis community. More critically, a fundamental molecular level understanding of this effect is still debatable, but is essential for developing active, stable, and affordable fuel cells and water electrolysis technologies. Against this backdrop, in this review, we provide a comprehensive overview of the intrinsic pH effect on hydrogen electrocatalysis, covering the experimental observations, underlying principles, and strategies for catalyst design. We discuss the strengths and shortcomings of various activity descriptors, including hydrogen binding energy (HBE) theory, bifunctional theory, potential of zero free charge (pzfc) theory, 2B theory and other theories, across different electrolytes and catalyst surfaces, and outline their interrelations where possible. Additionally, we highlight the design principles and research progress in improving the alkaline HER/HOR kinetics by catalyst design and electrolyte optimization employing the aforementioned theories. Finally, the remaining controversies about the pH effects on HER/HOR kinetics as well as the challenges and possible research directions in this field are also put forward. This review aims to provide researchers with a comprehensive understanding of the intrinsic pH effect and inspire the development of more cost-effective and durable alkaline water electrolyzers (AWEs) and anion exchange membrane fuel cells (AMFCs) for a sustainable energy future. This review systematically provides various insights into the pH effect on hydrogen electrocatalysis, and thus providing a reference for future development of hydrogen electrocatalysis based on these insights.
AbstractList Hydrogen electrocatalytic reactions, including the hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR), play a crucial role in a wide range of energy conversion and storage technologies. However, the HER and HOR display anomalous non-Nernstian pH dependent kinetics, showing two to three orders of magnitude sluggish kinetics in alkaline media compared to that in acidic media. Fundamental understanding of the origins of the intrinsic pH effect has attracted substantial interest from the electrocatalysis community. More critically, a fundamental molecular level understanding of this effect is still debatable, but is essential for developing active, stable, and affordable fuel cells and water electrolysis technologies. Against this backdrop, in this review, we provide a comprehensive overview of the intrinsic pH effect on hydrogen electrocatalysis, covering the experimental observations, underlying principles, and strategies for catalyst design. We discuss the strengths and shortcomings of various activity descriptors, including hydrogen binding energy (HBE) theory, bifunctional theory, potential of zero free charge (pzfc) theory, 2B theory and other theories, across different electrolytes and catalyst surfaces, and outline their interrelations where possible. Additionally, we highlight the design principles and research progress in improving the alkaline HER/HOR kinetics by catalyst design and electrolyte optimization employing the aforementioned theories. Finally, the remaining controversies about the pH effects on HER/HOR kinetics as well as the challenges and possible research directions in this field are also put forward. This review aims to provide researchers with a comprehensive understanding of the intrinsic pH effect and inspire the development of more cost-effective and durable alkaline water electrolyzers (AWEs) and anion exchange membrane fuel cells (AMFCs) for a sustainable energy future.
Hydrogen electrocatalytic reactions, including the hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR), play a crucial role in a wide range of energy conversion and storage technologies. However, the HER and HOR display anomalous non-Nernstian pH dependent kinetics, showing two to three orders of magnitude sluggish kinetics in alkaline media compared to that in acidic media. Fundamental understanding of the origins of the intrinsic pH effect has attracted substantial interest from the electrocatalysis community. More critically, a fundamental molecular level understanding of this effect is still debatable, but is essential for developing active, stable, and affordable fuel cells and water electrolysis technologies. Against this backdrop, in this review, we provide a comprehensive overview of the intrinsic pH effect on hydrogen electrocatalysis, covering the experimental observations, underlying principles, and strategies for catalyst design. We discuss the strengths and shortcomings of various activity descriptors, including hydrogen binding energy (HBE) theory, bifunctional theory, potential of zero free charge (pzfc) theory, 2B theory and other theories, across different electrolytes and catalyst surfaces, and outline their interrelations where possible. Additionally, we highlight the design principles and research progress in improving the alkaline HER/HOR kinetics by catalyst design and electrolyte optimization employing the aforementioned theories. Finally, the remaining controversies about the pH effects on HER/HOR kinetics as well as the challenges and possible research directions in this field are also put forward. This review aims to provide researchers with a comprehensive understanding of the intrinsic pH effect and inspire the development of more cost-effective and durable alkaline water electrolyzers (AWEs) and anion exchange membrane fuel cells (AMFCs) for a sustainable energy future. This review systematically provides various insights into the pH effect on hydrogen electrocatalysis, and thus providing a reference for future development of hydrogen electrocatalysis based on these insights.
Hydrogen electrocatalytic reactions, including the hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR), play a crucial role in a wide range of energy conversion and storage technologies. However, the HER and HOR display anomalous non-Nernstian pH dependent kinetics, showing two to three orders of magnitude sluggish kinetics in alkaline media compared to that in acidic media. Fundamental understanding of the origins of the intrinsic pH effect has attracted substantial interest from the electrocatalysis community. More critically, a fundamental molecular level understanding of this effect is still debatable, but is essential for developing active, stable, and affordable fuel cells and water electrolysis technologies. Against this backdrop, in this review, we provide a comprehensive overview of the intrinsic pH effect on hydrogen electrocatalysis, covering the experimental observations, underlying principles, and strategies for catalyst design. We discuss the strengths and shortcomings of various activity descriptors, including hydrogen binding energy (HBE) theory, bifunctional theory, potential of zero free charge (pzfc) theory, 2B theory and other theories, across different electrolytes and catalyst surfaces, and outline their interrelations where possible. Additionally, we highlight the design principles and research progress in improving the alkaline HER/HOR kinetics by catalyst design and electrolyte optimization employing the aforementioned theories. Finally, the remaining controversies about the pH effects on HER/HOR kinetics as well as the challenges and possible research directions in this field are also put forward. This review aims to provide researchers with a comprehensive understanding of the intrinsic pH effect and inspire the development of more cost-effective and durable alkaline water electrolyzers (AWEs) and anion exchange membrane fuel cells (AMFCs) for a sustainable energy future.Hydrogen electrocatalytic reactions, including the hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR), play a crucial role in a wide range of energy conversion and storage technologies. However, the HER and HOR display anomalous non-Nernstian pH dependent kinetics, showing two to three orders of magnitude sluggish kinetics in alkaline media compared to that in acidic media. Fundamental understanding of the origins of the intrinsic pH effect has attracted substantial interest from the electrocatalysis community. More critically, a fundamental molecular level understanding of this effect is still debatable, but is essential for developing active, stable, and affordable fuel cells and water electrolysis technologies. Against this backdrop, in this review, we provide a comprehensive overview of the intrinsic pH effect on hydrogen electrocatalysis, covering the experimental observations, underlying principles, and strategies for catalyst design. We discuss the strengths and shortcomings of various activity descriptors, including hydrogen binding energy (HBE) theory, bifunctional theory, potential of zero free charge (pzfc) theory, 2B theory and other theories, across different electrolytes and catalyst surfaces, and outline their interrelations where possible. Additionally, we highlight the design principles and research progress in improving the alkaline HER/HOR kinetics by catalyst design and electrolyte optimization employing the aforementioned theories. Finally, the remaining controversies about the pH effects on HER/HOR kinetics as well as the challenges and possible research directions in this field are also put forward. This review aims to provide researchers with a comprehensive understanding of the intrinsic pH effect and inspire the development of more cost-effective and durable alkaline water electrolyzers (AWEs) and anion exchange membrane fuel cells (AMFCs) for a sustainable energy future.
Author Niu, Zhiqiang
Qu, Yongquan
Pan, Hongge
Na, Guoquan
Wang, Xingqiang
Wang, Dingsheng
Cui, Wen-Gang
Li, Zhenglong
Yang, Yaxiong
Gao, Fan
AuthorAffiliation Department of Chemistry
Nankai University
Tsinghua University
School of Materials Science and Engineering
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education)
Northwestern Polytechnical University
Xi'an Technological University
School of Chemistry and Chemical Engineering
Zhejiang University
Institute of Science and Technology for New Energy
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  name: Institute of Science and Technology for New Energy
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  name: Xi'an Technological University
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BackLink https://www.ncbi.nlm.nih.gov/pubmed/39239864$$D View this record in MEDLINE/PubMed
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Notes Zhiqiang Niu is a Professor at the College of Chemistry, Nankai University. He received his PhD degree from the Institute of Physics, Chinese Academy of Sciences in 2010 under the supervision of Prof. Sishen Xie. After his postdoctoral research in the School of Materials Science and Engineering, Nanyang Technological University (Singapore, co-supervisor: Prof. Xiaodong Chen), he started his independent research career under the Hundred Young Academic Leaders Program of Nankai University in 2014. He was awarded the National Youth Thousand Talents of China (2015). His research interests include nanocarbon materials and advanced energy storage devices.
Yongquan Qu is currently a professor at the School of Chemistry and Chemical Engineering, Northwestern Polytechnical University. He received his BS in Materials Science and Engineering from Nanjing University in 2001, MS in Chemistry from the Dalian Institute of Chemical Physics in 2004, and PhD in Chemistry from the University of California, Davis, in 2009. He worked as a postdoctoral research fellow in the University of California, Los Angeles, from 2009 to 2011. His research interests focus on heterogeneous catalysis in the areas of organic synthesis, clean energy production and environmental remediation.
Hongge Pan is a professor and director of the Institute of Science and Technology for New Energy, Xi'an Technological University. He received his PhD in materials science and engineering from Zhejiang University in 1996 under a joint program between Zhejiang University and the Institute of Physics, Chinese Academy of Science. Later that year he joined Zhejiang University and became a professor in 1999. He is a recipient of the Changjiang Distinguished Professorship by the Ministry of Education (2014) and the National Outstanding Doctoral Dissertation Award (2000). His research is focused on energy materials for solid-state hydrogen storage, lithium ion batteries, electrocatalysis, and photocatalysis. Now he serves as a co-editor-in-chief of Journal of Alloys and Compounds.
Dingsheng Wang received his BS degree from the Department of Chemistry and Physics at the University of Science and Technology of China in 2004 and PhD degree from the Department of Chemistry at Tsinghua University in 2009 under the supervision of Prof. Yadong Li. He conducted his postdoctoral research in Prof. Shoushan Fan's group at the Department of Physics, Tsinghua University. He joined the faculty of the Department of Chemistry, Tsinghua University, in 2012. His research interests are focused on the synthesis and applications of nanomaterials, clusters, and atomically dispersed materials.
Wen-Gang Cui is currently an associate professor at the Institute of Science and Technology for New Energy, Xi'an Technological University. He received his PhD in Chemistry from Nankai University in 2021. His research interests focus on heterogeneous catalysis for energy storage and conversion applications.
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Snippet Hydrogen electrocatalytic reactions, including the hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR), play a crucial role in a wide...
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SubjectTerms Acidic oxides
Anion exchanging
Catalysts
Design optimization
Electrocatalysis
Electrolysis
Electrolytes
Electrolytic cells
Energy conversion
Fuel cells
Hydrogen
Hydrogen evolution reactions
Kinetics
Oxidation
Reaction kinetics
Title Insights into the pH effect on hydrogen electrocatalysis
URI https://www.ncbi.nlm.nih.gov/pubmed/39239864
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