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Main Authors: Wang, Peiyao, Jiang, Gengping, Yan, Yuan, Qu, Longbing, Du, Xiaoyang, Li, Dan, Liu, Jefferson Zhe
Format: Preprint
Published: 2024
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Online Access:https://arxiv.org/abs/2411.13747
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author Wang, Peiyao
Jiang, Gengping
Yan, Yuan
Qu, Longbing
Du, Xiaoyang
Li, Dan
Liu, Jefferson Zhe
author_facet Wang, Peiyao
Jiang, Gengping
Yan, Yuan
Qu, Longbing
Du, Xiaoyang
Li, Dan
Liu, Jefferson Zhe
contents Water molecules are traditionally regarded as passive dielectric media in electrochemical systems. In this work, we challenge this conventional perspective using molecular dynamics simulations and theoretical analysis. We show that interfacial water is polarized differently from bulk water and effectively screens the electrostatic potential between ions and the surface. This goes beyond the classic electric double layer (EDL) model, which treated water as merely a passive dielectric. The observed overscreening occurs because a significant portion of water polarization directly responds to the graphene surface, in addition to screening the electrostatic interactions between ions and charged surfaces. Furthermore, we reveal that this surface-induced polarization of interfacial water governs the electric potential distribution and EDL capacitance, and can even invert the electrode surface potential polarity, overriding the contribution of ions. These molecular-level insights lead to a revised EDL model that more accurately describes the electric and chemical potential distributions in the interfacial EDL regions.
format Preprint
id arxiv_https___arxiv_org_abs_2411_13747
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Beyond Dielectrics: Interfacial Water Polarization Governs Graphene-Based Electrochemical Interfaces
Wang, Peiyao
Jiang, Gengping
Yan, Yuan
Qu, Longbing
Du, Xiaoyang
Li, Dan
Liu, Jefferson Zhe
Chemical Physics
Water molecules are traditionally regarded as passive dielectric media in electrochemical systems. In this work, we challenge this conventional perspective using molecular dynamics simulations and theoretical analysis. We show that interfacial water is polarized differently from bulk water and effectively screens the electrostatic potential between ions and the surface. This goes beyond the classic electric double layer (EDL) model, which treated water as merely a passive dielectric. The observed overscreening occurs because a significant portion of water polarization directly responds to the graphene surface, in addition to screening the electrostatic interactions between ions and charged surfaces. Furthermore, we reveal that this surface-induced polarization of interfacial water governs the electric potential distribution and EDL capacitance, and can even invert the electrode surface potential polarity, overriding the contribution of ions. These molecular-level insights lead to a revised EDL model that more accurately describes the electric and chemical potential distributions in the interfacial EDL regions.
title Beyond Dielectrics: Interfacial Water Polarization Governs Graphene-Based Electrochemical Interfaces
topic Chemical Physics
url https://arxiv.org/abs/2411.13747