Molecular-scale insights into the electrical double layer at oxide-electrolyte interfaces

Abstract The electrical double layer (EDL) at metal oxide-electrolyte interfaces critically affects fundamental processes in water splitting, batteries, and corrosion. However, limitations in the microscopic-level understanding of the EDL have been a major bottleneck in controlling these interfacial...

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Main Authors: Chunyi Zhang, Marcos F. Calegari Andrade, Zachary K. Goldsmith, Abhinav S. Raman, Yifan Li, Pablo M. Piaggi, Xifan Wu, Roberto Car, Annabella Selloni
Format: Article
Language:English
Published: Nature Portfolio 2024-11-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-024-54631-1
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author Chunyi Zhang
Marcos F. Calegari Andrade
Zachary K. Goldsmith
Abhinav S. Raman
Yifan Li
Pablo M. Piaggi
Xifan Wu
Roberto Car
Annabella Selloni
author_facet Chunyi Zhang
Marcos F. Calegari Andrade
Zachary K. Goldsmith
Abhinav S. Raman
Yifan Li
Pablo M. Piaggi
Xifan Wu
Roberto Car
Annabella Selloni
author_sort Chunyi Zhang
collection DOAJ
description Abstract The electrical double layer (EDL) at metal oxide-electrolyte interfaces critically affects fundamental processes in water splitting, batteries, and corrosion. However, limitations in the microscopic-level understanding of the EDL have been a major bottleneck in controlling these interfacial processes. Herein, we use ab initio-based machine learning potential simulations incorporating long-range electrostatics to unravel the molecular-scale picture of the EDL at the prototypical anatase TiO2-electrolyte interface under various pH conditions. Our large-scale simulations, capable of capturing interfacial water dissociation/recombination reactions and electrolytic proton transport, provide unprecedented insights into the detailed structure of the EDL. Moreover, the larger capacitance of the EDL under basic relative to acidic conditions, originating from the higher affinity of the cations for the oxide surface, is found to give rise to distinct charging mechanisms on negative and positive surfaces. Our results are validated by the agreement between the computed EDL capacitance and experimental data.
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spelling doaj-art-bf3583097d4e4bf98ace5c11b2a820c82024-12-01T12:34:27ZengNature PortfolioNature Communications2041-17232024-11-011511910.1038/s41467-024-54631-1Molecular-scale insights into the electrical double layer at oxide-electrolyte interfacesChunyi Zhang0Marcos F. Calegari Andrade1Zachary K. Goldsmith2Abhinav S. Raman3Yifan Li4Pablo M. Piaggi5Xifan Wu6Roberto Car7Annabella Selloni8Department of Chemistry, Princeton UniversityMaterials Science Division, Lawrence Livermore National LaboratoryDepartment of Chemistry, Princeton UniversityDepartment of Chemistry, Princeton UniversityDepartment of Chemistry, Princeton UniversityDepartment of Chemistry, Princeton UniversityDepartment of Physics, Temple UniversityDepartment of Chemistry, Princeton UniversityDepartment of Chemistry, Princeton UniversityAbstract The electrical double layer (EDL) at metal oxide-electrolyte interfaces critically affects fundamental processes in water splitting, batteries, and corrosion. However, limitations in the microscopic-level understanding of the EDL have been a major bottleneck in controlling these interfacial processes. Herein, we use ab initio-based machine learning potential simulations incorporating long-range electrostatics to unravel the molecular-scale picture of the EDL at the prototypical anatase TiO2-electrolyte interface under various pH conditions. Our large-scale simulations, capable of capturing interfacial water dissociation/recombination reactions and electrolytic proton transport, provide unprecedented insights into the detailed structure of the EDL. Moreover, the larger capacitance of the EDL under basic relative to acidic conditions, originating from the higher affinity of the cations for the oxide surface, is found to give rise to distinct charging mechanisms on negative and positive surfaces. Our results are validated by the agreement between the computed EDL capacitance and experimental data.https://doi.org/10.1038/s41467-024-54631-1
spellingShingle Chunyi Zhang
Marcos F. Calegari Andrade
Zachary K. Goldsmith
Abhinav S. Raman
Yifan Li
Pablo M. Piaggi
Xifan Wu
Roberto Car
Annabella Selloni
Molecular-scale insights into the electrical double layer at oxide-electrolyte interfaces
Nature Communications
title Molecular-scale insights into the electrical double layer at oxide-electrolyte interfaces
title_full Molecular-scale insights into the electrical double layer at oxide-electrolyte interfaces
title_fullStr Molecular-scale insights into the electrical double layer at oxide-electrolyte interfaces
title_full_unstemmed Molecular-scale insights into the electrical double layer at oxide-electrolyte interfaces
title_short Molecular-scale insights into the electrical double layer at oxide-electrolyte interfaces
title_sort molecular scale insights into the electrical double layer at oxide electrolyte interfaces
url https://doi.org/10.1038/s41467-024-54631-1
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