Structure and self-diffusivity of mixed-cation electrolytes between neutral and charged graphene sheets

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F67985858%3A_____%2F24%3A00583500" target="_blank" >RIV/67985858:_____/24:00583500 - isvavai.cz</a>

Alternative codes found

RIV/60076658:12310/24:43908292 RIV/44555601:13440/24:43898358

Result on the web

<a href="https://hdl.handle.net/11104/0351469" target="_blank" >https://hdl.handle.net/11104/0351469</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1063/5.0188104" target="_blank" >10.1063/5.0188104</a>

Result language

angličtina

Original language name

Structure and self-diffusivity of mixed-cation electrolytes between neutral and charged graphene sheets

Original language description

Graphene-based applications, such as supercapacitors or capacitive deionization, take place in an aqueous environment, and they benefit from molecular-level insights into the behavior of aqueous electrolyte solutions in single-digit graphene nanopores with a size comparable to a few molecular diameters. Under single-digit graphene nanoconfinement (smallest dimension <2 nm), water and ions behave drastically different than in the bulk. Most aqueous electrolytes in the graphene-based applications as well as in nature contain a mix of electrolytes. We study several prototypical aqueous mixed alkali-chloride electrolytes containing an equimolar fraction of Li/Na, Li/K, or Na/K cations confined between neutral and positively or negatively charged parallel graphene sheets. The strong hydration shell of small Li+ vs a larger Na+ or large K+ with weaker or weak hydration shells affects the interplay between the ions’s propensity to hydrate or dehydrate under the graphene nanoconfinement and the strength of the ion–graphene interactions mediated by confinement-induced layered water. We perform molecular dynamics simulations of the confined mixed-cation electrolytes using the effectively polarizable force field for electrolyte–graphene systems and focused on a relation between the electrochemical adsorption and structural properties of the water molecules and ions and their diffusion behavior. The simulations show that the one-layer nanoslits have the biggest impact on the ions’ adsorption and the water and ions’ diffusion. The positively charged one-layer nanoslits only allow for Cl− adsorption and strengthen the intermolecular bonding, which along with the ultrathin confinement substantially reduces the water and Cl− diffusion. In contrast, the negatively charged one-layer nanoslits only allow for adsorption of weakly hydrated Na+ or K+ and substantially break up the non-covalent bond network, which leads to the enhancement of the water and Na+ or K+ diffusion up to or even above the bulk diffusion. In wider nanoslits, cations adsorb closer to the graphene surfaces than Cl−’s with preferential adsorption of a weakly hydrated cation over a strongly hydrated cation. The positive graphene charge has an intuitive effect on the adsorption of weakly hydrated Na+’s or K+’s and Cl−’s and a counterintuitive effect on the adsorption of strongly hydrated Li+’s. On the other hand, the negative surface charge has an intuitive effect on the adsorption of both types of cations and only mild intuitive or counterintuitive effects on the Cl− adsorption. The diffusion of water molecules and ions confined in the wider nanoslits is reduced with respect to the bulk diffusion, more for the positive graphene charge, which strengthened the intermolecular bonding, and less for the negative surface charge, which weakened the non-covalent bond network.

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/GA21-27338S" target="_blank" >GA21-27338S: Capacitive Deionisation: Insights from Molecular Modelling</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2024

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Chemical Physics

ISSN

0021-9606

e-ISSN

1089-7690

Volume of the periodical

160

Issue of the periodical within the volume

9

Country of publishing house

US - UNITED STATES

Number of pages

17

Pages from-to

094701

UT code for WoS article

001178860800009

EID of the result in the Scopus database

2-s2.0-85186319693