气候变化领域集成服务门户(CCPortal): Size dependence of hydrophobic hydration at electrified gold/water interfaces

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DOI	10.1073/pnas.2023867118
	Size dependence of hydrophobic hydration at electrified gold/water interfaces
	Serva A.; Salanne M.; Havenith M.; Pezzotti S.
发表日期	2021
ISSN	00278424
卷号	118 期号:15
英文摘要	Hydrophobic hydration at metal/water interfaces actively contributes to the energetics of electrochemical reactions, e.g. CO2 and N2 reduction, where small hydrophobic molecules are involved. In this work, constant applied potential molecular dynamics is employed to study hydrophobic hydration at a gold/water interface. We propose an adaptation of the Lum-Chandler-Weeks (LCW) theory to describe the free energy of hydrophobic hydration at the interface as a function of solute size and applied voltage. Based on this model we are able to predict the free energy cost of cavity formation at the interface directly from the free energy cost in the bulk plus an interface-dependent correction term. The interfacial water network contributes significantly to the free energy, yielding a preference for outer-sphere adsorption at the gold surface for ideal hydrophobes. We predict an accumulation of small hydrophobic solutes of sizes comparable to CO or N2, while the free energy cost to hydrate larger hydrophobes, above 2.5-Å radius, is shown to be greater at the interface than in the bulk. Interestingly, the transition from the volume dominated to the surface dominated regimes predicted by the LCW theory in the bulk is also found to take place for hydrophobes at the Au/water interface but occurs at smaller cavity radii. By applying the adapted LCW theory to a simple model addition reaction, we illustrate some implications of our findings for electrochemical reactions. © 2021 National Academy of Sciences. All rights reserved.
英文关键词	Electrochemistry; Gold/water interface; Hydrophobic hydration; Lum-Chandler-Weeks theory; Molecular dynamics
语种	英语
来源期刊	Proceedings of the National Academy of Sciences of the United States of America
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/179871
作者单位	Sorbonne Université, CNRS, Physico-chimie des Electrolytes et Nanosystèmes Interfaciaux, PHENIX, Paris, F-75005, France; Institut Universitaire de France, Paris Cedex 05, 75231, France; Department of Physical Chemistry II, Ruhr University Bochum, Bochum, 44780, Germany; Department of Physics, Technische Universität Dortmund, Dortmund, 44227, Germany
推荐引用方式 GB/T 7714	Serva A.,Salanne M.,Havenith M.,et al. Size dependence of hydrophobic hydration at electrified gold/water interfaces[J],2021,118(15).
APA	Serva A.,Salanne M.,Havenith M.,&Pezzotti S..(2021).Size dependence of hydrophobic hydration at electrified gold/water interfaces.Proceedings of the National Academy of Sciences of the United States of America,118(15).
MLA	Serva A.,et al."Size dependence of hydrophobic hydration at electrified gold/water interfaces".Proceedings of the National Academy of Sciences of the United States of America 118.15(2021).