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Title: Specific ion effects at graphitic interfaces

Abstract

Improved understanding of aqueous solutions at graphitic interfaces is critical for energy storage and water desalination. However, many mechanistic details remain unclear, including how interfacial structure and response are dictated by intrinsic properties of solvated ions under applied voltage. In this work, we combine hybrid first-principles/continuum simulations with electrochemical measurements to investigate adsorption of several alkali-metal cations at the interface with graphene and within graphene slit-pores. We confirm that adsorption energy increases with ionic radius, while being highly dependent on the pore size. In addition, in contrast with conventional electrochemical models, we find that interfacial charge transfer contributes non-negligibly to this interaction and can be further enhanced by confinement. We conclude that the measured interfacial capacitance trends result from a complex interplay between voltage, confinement, and specific ion effects-including ion hydration and charge transfer.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2];  [1];  [1];  [1]; ORCiD logo [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan)
Publication Date:
Research Org.:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1633023
Report Number(s):
LLNL-JRNL-778780
Journal ID: ISSN 2041-1723; 968664
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Materials science; Energy storage; Electrochemistry; Graphene; Porous materials; Two-dimensional materials

Citation Formats

Zhan, Cheng, Cerón, Maira R., Hawks, Steven A., Otani, Minoru, Wood, Brandon C., Pham, Tuan Anh, Stadermann, Michael, and Campbell, Patrick G. Specific ion effects at graphitic interfaces. United States: N. p., 2019. Web. doi:10.1038/s41467-019-12854-7.
Zhan, Cheng, Cerón, Maira R., Hawks, Steven A., Otani, Minoru, Wood, Brandon C., Pham, Tuan Anh, Stadermann, Michael, & Campbell, Patrick G. Specific ion effects at graphitic interfaces. United States. https://doi.org/10.1038/s41467-019-12854-7
Zhan, Cheng, Cerón, Maira R., Hawks, Steven A., Otani, Minoru, Wood, Brandon C., Pham, Tuan Anh, Stadermann, Michael, and Campbell, Patrick G. Thu . "Specific ion effects at graphitic interfaces". United States. https://doi.org/10.1038/s41467-019-12854-7. https://www.osti.gov/servlets/purl/1633023.
@article{osti_1633023,
title = {Specific ion effects at graphitic interfaces},
author = {Zhan, Cheng and Cerón, Maira R. and Hawks, Steven A. and Otani, Minoru and Wood, Brandon C. and Pham, Tuan Anh and Stadermann, Michael and Campbell, Patrick G.},
abstractNote = {Improved understanding of aqueous solutions at graphitic interfaces is critical for energy storage and water desalination. However, many mechanistic details remain unclear, including how interfacial structure and response are dictated by intrinsic properties of solvated ions under applied voltage. In this work, we combine hybrid first-principles/continuum simulations with electrochemical measurements to investigate adsorption of several alkali-metal cations at the interface with graphene and within graphene slit-pores. We confirm that adsorption energy increases with ionic radius, while being highly dependent on the pore size. In addition, in contrast with conventional electrochemical models, we find that interfacial charge transfer contributes non-negligibly to this interaction and can be further enhanced by confinement. We conclude that the measured interfacial capacitance trends result from a complex interplay between voltage, confinement, and specific ion effects-including ion hydration and charge transfer.},
doi = {10.1038/s41467-019-12854-7},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {10}
}

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Cited by: 55 works
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Figures / Tables:

Fig. 1 Fig. 1: Interaction between alkali-metal cations with graphene. a Potential energy surface of the cation adsorption on the graphene surface with a total excess charge of qgrp = −0.5e in 1 M LiCl, NaCl, KCl and CsCl aqueous electrolytes. Inset represents the cation-graphene system, where the green-yellow circles represent amore » hydrated alkali cation. b Ionic charge of the cations at different qgrp and adsorption locations. Inset: interfacial charge transfer between Cs+ and the graphene electrode as an example, where the cyan and yellow isosurfaces indicate charge depletion and accumulation regions, respectively. c Schematic description of the charge transfer (CT) effect on the potential response of charged graphene electrode. d The overall charge transfer obtained by integrating the charge transfer per ion, shown in b, and local cation density (inset). The isosurface is set to be 10−4 and 1.6−4 a.u. for the oxygen density in the ion solvation shell (in a) and electronic density difference (in b), respectively.« less

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Translocation of Single-Stranded DNA Through Single-Walled Carbon Nanotubes
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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.