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First-principles study of vanadium carbides as electrocatalysts for hydrogen and oxygen evolution reactions

Vanadium carbides have attracted much attention as highly active catalysts in both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), while a satisfactory understanding of the underlying mechanisms still remains a challenge. Herein we apply first-principles calculations to sy...

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Autores principales: Wan, Jing, Wang, Congcong, Tang, Qian, Gu, Xiao, He, Mingquan
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9075541/
https://www.ncbi.nlm.nih.gov/pubmed/35542271
http://dx.doi.org/10.1039/c9ra06539c
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author Wan, Jing
Wang, Congcong
Tang, Qian
Gu, Xiao
He, Mingquan
author_facet Wan, Jing
Wang, Congcong
Tang, Qian
Gu, Xiao
He, Mingquan
author_sort Wan, Jing
collection PubMed
description Vanadium carbides have attracted much attention as highly active catalysts in both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), while a satisfactory understanding of the underlying mechanisms still remains a challenge. Herein we apply first-principles calculations to systematically analyze the crystal structures, electronic properties, free energies during the HER and OER processes, surface energies and crystal formation energies of the three types of vanadium carbides, i.e., V(4)C(3), V(8)C(7) and VC. We show that all these vanadium carbides are metallic, which enables efficient electron transport from the bulk to the surface of the catalysts. All these vanadium carbides exhibit excellent HER performance but show poor OER catalytic activity. In particular, the V(8)C(7) (110) surface shows the best catalytic performance for its relatively small |ΔG(H*)| value (−0.114 eV) for HER. Emergence of natural carbon vacancies gives rise to large surface energy, proper hydrogen adsorption energy, low crystal formation energy and weak bond strength in V(8)V(7), which guarantees its leading position among the three vanadium carbides. In addition, a remarkable resemblance between VC/V(8)C(7) and Pt in their electronic structures on (110) and (111) surfaces are found, which indicates a Pt-like HER mechanism in these vanadium carbides. Our results thus bring new insights to the theoretical understanding of the excellent HER performance of vanadium carbides.
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spelling pubmed-90755412022-05-09 First-principles study of vanadium carbides as electrocatalysts for hydrogen and oxygen evolution reactions Wan, Jing Wang, Congcong Tang, Qian Gu, Xiao He, Mingquan RSC Adv Chemistry Vanadium carbides have attracted much attention as highly active catalysts in both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), while a satisfactory understanding of the underlying mechanisms still remains a challenge. Herein we apply first-principles calculations to systematically analyze the crystal structures, electronic properties, free energies during the HER and OER processes, surface energies and crystal formation energies of the three types of vanadium carbides, i.e., V(4)C(3), V(8)C(7) and VC. We show that all these vanadium carbides are metallic, which enables efficient electron transport from the bulk to the surface of the catalysts. All these vanadium carbides exhibit excellent HER performance but show poor OER catalytic activity. In particular, the V(8)C(7) (110) surface shows the best catalytic performance for its relatively small |ΔG(H*)| value (−0.114 eV) for HER. Emergence of natural carbon vacancies gives rise to large surface energy, proper hydrogen adsorption energy, low crystal formation energy and weak bond strength in V(8)V(7), which guarantees its leading position among the three vanadium carbides. In addition, a remarkable resemblance between VC/V(8)C(7) and Pt in their electronic structures on (110) and (111) surfaces are found, which indicates a Pt-like HER mechanism in these vanadium carbides. Our results thus bring new insights to the theoretical understanding of the excellent HER performance of vanadium carbides. The Royal Society of Chemistry 2019-11-15 /pmc/articles/PMC9075541/ /pubmed/35542271 http://dx.doi.org/10.1039/c9ra06539c Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Wan, Jing
Wang, Congcong
Tang, Qian
Gu, Xiao
He, Mingquan
First-principles study of vanadium carbides as electrocatalysts for hydrogen and oxygen evolution reactions
title First-principles study of vanadium carbides as electrocatalysts for hydrogen and oxygen evolution reactions
title_full First-principles study of vanadium carbides as electrocatalysts for hydrogen and oxygen evolution reactions
title_fullStr First-principles study of vanadium carbides as electrocatalysts for hydrogen and oxygen evolution reactions
title_full_unstemmed First-principles study of vanadium carbides as electrocatalysts for hydrogen and oxygen evolution reactions
title_short First-principles study of vanadium carbides as electrocatalysts for hydrogen and oxygen evolution reactions
title_sort first-principles study of vanadium carbides as electrocatalysts for hydrogen and oxygen evolution reactions
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9075541/
https://www.ncbi.nlm.nih.gov/pubmed/35542271
http://dx.doi.org/10.1039/c9ra06539c
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