Adaptive Catalytic Nanointerfaces for Controlled Hydrogen Evolution: an in Situ Electrochemical Approach

Abstract Precious metal nanoparticles in electrocatalytic applications tend to be single‐use, becoming unusable afterward. Here, this is demonstrated that the electrocatalytic response of these nanoparticles, when confined at the step‐edges of corrugated carbon nanofibers interiors, can be switched...

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Main Authors: Carlos Herreros‐Lucas, Melanie Guillén‐Soler, Lucía Vizcaíno‐Anaya, Glen Murray, Mehtap Aygün, José Manuel Vila‐Fungueiriño, María del Carmen Giménez‐López
Format: Article
Language:English
Published: Wiley 2025-08-01
Series:Advanced Science
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Online Access:https://doi.org/10.1002/advs.202505104
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author Carlos Herreros‐Lucas
Melanie Guillén‐Soler
Lucía Vizcaíno‐Anaya
Glen Murray
Mehtap Aygün
José Manuel Vila‐Fungueiriño
María del Carmen Giménez‐López
author_facet Carlos Herreros‐Lucas
Melanie Guillén‐Soler
Lucía Vizcaíno‐Anaya
Glen Murray
Mehtap Aygün
José Manuel Vila‐Fungueiriño
María del Carmen Giménez‐López
author_sort Carlos Herreros‐Lucas
collection DOAJ
description Abstract Precious metal nanoparticles in electrocatalytic applications tend to be single‐use, becoming unusable afterward. Here, this is demonstrated that the electrocatalytic response of these nanoparticles, when confined at the step‐edges of corrugated carbon nanofibers interiors, can be switched on again at will by simply introducing sulfur as an inorganic mediator. To achieve this, an electrochemical methodology is developed that triggers the rapid surface reconfiguration of confined, deactivated nanoparticles (PdSx) involving the release of sulfur to yield highly active crystalline Pd(0) nanoparticles, confined polysulfides, and sulfur‐terminated carbon step‐edges. More importantly, the electrochemical performance can be systematically switched from a highly active mode, in which polysulfides enhance the hydrogen adsorption on palladium, to a much less active mode, called the resting mode, in which sulfur (formed by the oxidation of polysulfides) passivates the active Pd(0) nanoparticle surface. This discovery introduces a new protocol to control nanoparticle performance for catalytic reactions, and more crucially, to extend their lifespan.
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issn 2198-3844
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publishDate 2025-08-01
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series Advanced Science
spelling doaj-art-a345b99d945d4cc6aab879acd8233fa82025-08-20T11:56:11ZengWileyAdvanced Science2198-38442025-08-011230n/an/a10.1002/advs.202505104Adaptive Catalytic Nanointerfaces for Controlled Hydrogen Evolution: an in Situ Electrochemical ApproachCarlos Herreros‐Lucas0Melanie Guillén‐Soler1Lucía Vizcaíno‐Anaya2Glen Murray3Mehtap Aygün4José Manuel Vila‐Fungueiriño5María del Carmen Giménez‐López6Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) Universidade de Santiago de Compostela Santiago deCompostela 15782 SpainCentro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) Universidade de Santiago de Compostela Santiago deCompostela 15782 SpainCentro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) Universidade de Santiago de Compostela Santiago deCompostela 15782 SpainSchool of Chemistry The University of Nottingham University Park Nottingham NG7 2RD UKCentro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) Universidade de Santiago de Compostela Santiago deCompostela 15782 SpainCentro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) Universidade de Santiago de Compostela Santiago deCompostela 15782 SpainCentro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) Universidade de Santiago de Compostela Santiago deCompostela 15782 SpainAbstract Precious metal nanoparticles in electrocatalytic applications tend to be single‐use, becoming unusable afterward. Here, this is demonstrated that the electrocatalytic response of these nanoparticles, when confined at the step‐edges of corrugated carbon nanofibers interiors, can be switched on again at will by simply introducing sulfur as an inorganic mediator. To achieve this, an electrochemical methodology is developed that triggers the rapid surface reconfiguration of confined, deactivated nanoparticles (PdSx) involving the release of sulfur to yield highly active crystalline Pd(0) nanoparticles, confined polysulfides, and sulfur‐terminated carbon step‐edges. More importantly, the electrochemical performance can be systematically switched from a highly active mode, in which polysulfides enhance the hydrogen adsorption on palladium, to a much less active mode, called the resting mode, in which sulfur (formed by the oxidation of polysulfides) passivates the active Pd(0) nanoparticle surface. This discovery introduces a new protocol to control nanoparticle performance for catalytic reactions, and more crucially, to extend their lifespan.https://doi.org/10.1002/advs.202505104confined electrocatalystelectrochemical switchinghydrogen productionreconfigurable step‐edge
spellingShingle Carlos Herreros‐Lucas
Melanie Guillén‐Soler
Lucía Vizcaíno‐Anaya
Glen Murray
Mehtap Aygün
José Manuel Vila‐Fungueiriño
María del Carmen Giménez‐López
Adaptive Catalytic Nanointerfaces for Controlled Hydrogen Evolution: an in Situ Electrochemical Approach
Advanced Science
confined electrocatalyst
electrochemical switching
hydrogen production
reconfigurable step‐edge
title Adaptive Catalytic Nanointerfaces for Controlled Hydrogen Evolution: an in Situ Electrochemical Approach
title_full Adaptive Catalytic Nanointerfaces for Controlled Hydrogen Evolution: an in Situ Electrochemical Approach
title_fullStr Adaptive Catalytic Nanointerfaces for Controlled Hydrogen Evolution: an in Situ Electrochemical Approach
title_full_unstemmed Adaptive Catalytic Nanointerfaces for Controlled Hydrogen Evolution: an in Situ Electrochemical Approach
title_short Adaptive Catalytic Nanointerfaces for Controlled Hydrogen Evolution: an in Situ Electrochemical Approach
title_sort adaptive catalytic nanointerfaces for controlled hydrogen evolution an in situ electrochemical approach
topic confined electrocatalyst
electrochemical switching
hydrogen production
reconfigurable step‐edge
url https://doi.org/10.1002/advs.202505104
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