Understanding Relationships between Free Volume and Oxygen Absorption in Ionic Liquids

Wenny, Malia B.; Molinari, Nicola; Slavney, Adam H.; Thapa, Surendra; Lee, Byeongdu; Kozinsky, Boris; Mason, Jarad A.

doi:10.1021/acs.jpcb.2c00202

Title: Understanding Relationships between Free Volume and Oxygen Absorption in Ionic Liquids

Journal Article · 02 February 2022 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI: https://doi.org/10.1021/acs.jpcb.2c00202 · OSTI ID:1855602

Wenny, Malia B. ^[1];

^[1]; Slavney, Adam H. ^[1]; Thapa, Surendra ^[1];

^[2];

^[1];

^[1]

Harvard Univ., Cambridge, MA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

In this report understanding the factors that govern gas absorption in ionic liquids is critical to the development of high-capacity solvents for catalysis, electrochemistry, and gas separations. Here, we report experimental probes of liquid structure that provide insights into how free volume impacts the O₂ absorption properties of ionic liquids. Specifically, we establish that isothermal compressibility - measured rapidly and accurately through small-angle X-ray scattering - reports on the size distribution of transient voids within a representative series of ionic liquids and is correlated with O₂ absorption capacity. Additionally, O₂ absorption capacities are correlated with thermal expansion coefficients, reflecting the beneficial effect of weak intermolecular interactions in ionic liquids on free volume and gas absorption capacity. Molecular dynamics simulations show that the void size distribution - in particular, the probability of forming larger voids within an ionic liquid - has a greater impact on O₂ absorption than the total free volume. These results establish relationships between the ionic liquid structure and gas absorption properties that offer design strategies for ionic liquids with high gas solubilities.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: Arnold and Mabel Beckman Foundation; Office of Naval Research (ONR); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357; FG02-97ER25308

OSTI ID:: 1855602

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry Journal Issue: 6 Vol. 126; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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