Rights statement: This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.jpclett.2c02260
Accepted author manuscript, 610 KB, PDF document
Available under license: CC BY-NC: Creative Commons Attribution-NonCommercial 4.0 International License
Final published version
Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
}
TY - JOUR
T1 - Understanding the Chemical Shifts of Aqueous Electrolyte Species Adsorbed in Carbon Nanopores
AU - Sasikumar, Anagha
AU - Griffin, John M
AU - Merlet, Céline
N1 - This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.jpclett.2c02260
PY - 2022/9/29
Y1 - 2022/9/29
N2 - Interfaces between aqueous electrolytes and nanoporous carbons are involved in a number of technological applications such as energy storage and capacitive deionization. Nuclear magnetic spectroscopy is a very useful tool to characterize ion adsorption in such systems thanks to its nuclei specificity and the ability to distinguish between ions in the bulk and in pores. We use complementary methods (density functional theory, molecular dynamics simulations, and a mesoscopic model) to investigate the relative importance of various effects on the chemical shifts of adsorbed species: ring currents, ion organization in pores of various sizes, specific ion-carbon interactions, and hydration. We show that ring currents and ion organization are predominant for the determination of chemical shifts in the case of Li ions and hydrogen atoms of water. For the large Rb and Cs ions, the additional effect of the hydration shell should be considered to predict chemical shifts in agreement with experiments.
AB - Interfaces between aqueous electrolytes and nanoporous carbons are involved in a number of technological applications such as energy storage and capacitive deionization. Nuclear magnetic spectroscopy is a very useful tool to characterize ion adsorption in such systems thanks to its nuclei specificity and the ability to distinguish between ions in the bulk and in pores. We use complementary methods (density functional theory, molecular dynamics simulations, and a mesoscopic model) to investigate the relative importance of various effects on the chemical shifts of adsorbed species: ring currents, ion organization in pores of various sizes, specific ion-carbon interactions, and hydration. We show that ring currents and ion organization are predominant for the determination of chemical shifts in the case of Li ions and hydrogen atoms of water. For the large Rb and Cs ions, the additional effect of the hydration shell should be considered to predict chemical shifts in agreement with experiments.
U2 - 10.1021/acs.jpclett.2c02260
DO - 10.1021/acs.jpclett.2c02260
M3 - Journal article
C2 - 36135796
VL - 13
SP - 8953
EP - 8962
JO - The Journal of Physical Chemistry Letters
JF - The Journal of Physical Chemistry Letters
SN - 1948-7185
IS - 38
ER -