Cargando…

Cationic Vacancy Defects in Iron Phosphide: A Promising Route toward Efficient and Stable Hydrogen Evolution by Electrochemical Water Splitting

Engineering the electronic properties of transition metal phosphides has shown great effectiveness in improving their intrinsic catalytic activity for the hydrogen evolution reaction (HER) in water splitting applications. Herein, we report for the first time, the creation of Fe vacancies as an appro...

Descripción completa

Detalles Bibliográficos
Autores principales: Kwong, Wai Ling, Gracia‐Espino, Eduardo, Lee, Cheng Choo, Sandström, Robin, Wågberg, Thomas, Messinger, Johannes
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5725677/
https://www.ncbi.nlm.nih.gov/pubmed/28980427
http://dx.doi.org/10.1002/cssc.201701565
_version_ 1783285580854984704
author Kwong, Wai Ling
Gracia‐Espino, Eduardo
Lee, Cheng Choo
Sandström, Robin
Wågberg, Thomas
Messinger, Johannes
author_facet Kwong, Wai Ling
Gracia‐Espino, Eduardo
Lee, Cheng Choo
Sandström, Robin
Wågberg, Thomas
Messinger, Johannes
author_sort Kwong, Wai Ling
collection PubMed
description Engineering the electronic properties of transition metal phosphides has shown great effectiveness in improving their intrinsic catalytic activity for the hydrogen evolution reaction (HER) in water splitting applications. Herein, we report for the first time, the creation of Fe vacancies as an approach to modulate the electronic structure of iron phosphide (FeP). The Fe vacancies were produced by chemical leaching of Mg that was introduced into FeP as “sacrificial dopant”. The obtained Fevacancy‐rich FeP nanoparticulate films, which were deposited on Ti foil, show excellent HER activity compared to pristine FeP and Mg‐doped FeP, achieving a current density of 10 mA cm(−2) at overpotentials of 108 mV in 1 m KOH and 65 mV in 0.5 m H(2)SO(4), with a near‐100 % Faradaic efficiency. Our theoretical and experimental analyses reveal that the improved HER activity originates from the presence of Fe vacancies, which lead to a synergistic modulation of the structural and electronic properties that result in a near‐optimal hydrogen adsorption free energy and enhanced proton trapping. The success in catalytic improvement through the introduction of cationic vacancy defects has not only demonstrated the potential of Fe‐vacancy‐rich FeP as highly efficient, earth abundant HER catalyst, but also opens up an exciting pathway for activating other promising catalysts for electrochemical water splitting.
format Online
Article
Text
id pubmed-5725677
institution National Center for Biotechnology Information
language English
publishDate 2017
publisher John Wiley and Sons Inc.
record_format MEDLINE/PubMed
spelling pubmed-57256772017-12-12 Cationic Vacancy Defects in Iron Phosphide: A Promising Route toward Efficient and Stable Hydrogen Evolution by Electrochemical Water Splitting Kwong, Wai Ling Gracia‐Espino, Eduardo Lee, Cheng Choo Sandström, Robin Wågberg, Thomas Messinger, Johannes ChemSusChem Full Papers Engineering the electronic properties of transition metal phosphides has shown great effectiveness in improving their intrinsic catalytic activity for the hydrogen evolution reaction (HER) in water splitting applications. Herein, we report for the first time, the creation of Fe vacancies as an approach to modulate the electronic structure of iron phosphide (FeP). The Fe vacancies were produced by chemical leaching of Mg that was introduced into FeP as “sacrificial dopant”. The obtained Fevacancy‐rich FeP nanoparticulate films, which were deposited on Ti foil, show excellent HER activity compared to pristine FeP and Mg‐doped FeP, achieving a current density of 10 mA cm(−2) at overpotentials of 108 mV in 1 m KOH and 65 mV in 0.5 m H(2)SO(4), with a near‐100 % Faradaic efficiency. Our theoretical and experimental analyses reveal that the improved HER activity originates from the presence of Fe vacancies, which lead to a synergistic modulation of the structural and electronic properties that result in a near‐optimal hydrogen adsorption free energy and enhanced proton trapping. The success in catalytic improvement through the introduction of cationic vacancy defects has not only demonstrated the potential of Fe‐vacancy‐rich FeP as highly efficient, earth abundant HER catalyst, but also opens up an exciting pathway for activating other promising catalysts for electrochemical water splitting. John Wiley and Sons Inc. 2017-10-27 2017-11-23 /pmc/articles/PMC5725677/ /pubmed/28980427 http://dx.doi.org/10.1002/cssc.201701565 Text en © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution‐NonCommercial‐NoDerivs (http://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Full Papers
Kwong, Wai Ling
Gracia‐Espino, Eduardo
Lee, Cheng Choo
Sandström, Robin
Wågberg, Thomas
Messinger, Johannes
Cationic Vacancy Defects in Iron Phosphide: A Promising Route toward Efficient and Stable Hydrogen Evolution by Electrochemical Water Splitting
title Cationic Vacancy Defects in Iron Phosphide: A Promising Route toward Efficient and Stable Hydrogen Evolution by Electrochemical Water Splitting
title_full Cationic Vacancy Defects in Iron Phosphide: A Promising Route toward Efficient and Stable Hydrogen Evolution by Electrochemical Water Splitting
title_fullStr Cationic Vacancy Defects in Iron Phosphide: A Promising Route toward Efficient and Stable Hydrogen Evolution by Electrochemical Water Splitting
title_full_unstemmed Cationic Vacancy Defects in Iron Phosphide: A Promising Route toward Efficient and Stable Hydrogen Evolution by Electrochemical Water Splitting
title_short Cationic Vacancy Defects in Iron Phosphide: A Promising Route toward Efficient and Stable Hydrogen Evolution by Electrochemical Water Splitting
title_sort cationic vacancy defects in iron phosphide: a promising route toward efficient and stable hydrogen evolution by electrochemical water splitting
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5725677/
https://www.ncbi.nlm.nih.gov/pubmed/28980427
http://dx.doi.org/10.1002/cssc.201701565
work_keys_str_mv AT kwongwailing cationicvacancydefectsinironphosphideapromisingroutetowardefficientandstablehydrogenevolutionbyelectrochemicalwatersplitting
AT graciaespinoeduardo cationicvacancydefectsinironphosphideapromisingroutetowardefficientandstablehydrogenevolutionbyelectrochemicalwatersplitting
AT leechengchoo cationicvacancydefectsinironphosphideapromisingroutetowardefficientandstablehydrogenevolutionbyelectrochemicalwatersplitting
AT sandstromrobin cationicvacancydefectsinironphosphideapromisingroutetowardefficientandstablehydrogenevolutionbyelectrochemicalwatersplitting
AT wagbergthomas cationicvacancydefectsinironphosphideapromisingroutetowardefficientandstablehydrogenevolutionbyelectrochemicalwatersplitting
AT messingerjohannes cationicvacancydefectsinironphosphideapromisingroutetowardefficientandstablehydrogenevolutionbyelectrochemicalwatersplitting