Theoretical Examination of the Hydroxide Transport in Cobaltocenium-Containing Polyelectrolytes

Wickramasinghe, Sachith; Hoehn, Alexandria; Wetthasinghe, Shehani T.; Lin, Huina; Wang, Qi; Jakowski, Jacek; Rassolov, Vitaly; Tang, Chuanbing; Garashchuk, Sophya

doi:10.1021/acs.jpcb.3c04118

Title: Theoretical Examination of the Hydroxide Transport in Cobaltocenium-Containing Polyelectrolytes

Journal Article · Thu Nov 16 00:00:00 EST 2023 · Journal of Physical Chemistry. B

DOI:https://doi.org/10.1021/acs.jpcb.3c04118· OSTI ID:2234363

Wickramasinghe, Sachith ^[1];

^[1]; Wetthasinghe, Shehani T. ^[1];

^[1]; Wang, Qi ^[1];

^[2];

^[1];

^[1]

University of South Carolina, Columbia, SC (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Polymers incorporating cobaltocenium groups have received attention as promising components of anion-exchange membranes (AEMs), exhibiting a good balance of chemical stability and high ionic conductivity. In this work, we analyze the hydroxide diffusion in the presence of cobaltocenium cations in an aqueous environment based on the molecular dynamics of model systems confined in one dimension to mimic the AEM channels. In order to describe the proton hopping mechanism, the forces are obtained from the electronic structure computed at the density-functional tight-binding level. We find that the hydroxide diffusion depends on the channel size, modulation of the electrostatic interactions by the solvation shell, and its rearrangement ability. Hydroxide diffusion proceeds via both the vehicular and structural diffusion mechanisms with the latter playing a larger role at low diffusion coefficients. The highest diffusion coefficient is observed under moderate water densities (around half the density of liquid water) when there are enough water molecules to form the solvation shell, reducing the electrostatic interaction between ions, yet there is enough space for the water rearrangements during the proton hopping. Furthermore, the effects of cobaltocenium separation, orientation, chemical modifications, and the role of nuclear quantum effects are also discussed.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC05-00OR22725; OIA-1655740; CHE-1955768; CHE-2308922

OSTI ID:: 2234363

Journal Information:: Journal of Physical Chemistry. B, Vol. 127, Issue 47; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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