Dynamics of a Room Temperature Ionic Liquid in Supported Ionic Liquid Membranes vs the Bulk Liquid: 2D IR and Polarized IR Pump–Probe Experiments

Shin, Jae Yoon; Yamada, Steven A.; Fayer, Michael D.

doi:10.1021/jacs.6b10695

Title: Dynamics of a Room Temperature Ionic Liquid in Supported Ionic Liquid Membranes vs the Bulk Liquid: 2D IR and Polarized IR Pump–Probe Experiments

Journal Article · Wed Dec 14 00:00:00 EST 2016 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.6b10695· OSTI ID:1797779

Shin, Jae Yoon ^[1]; Yamada, Steven A. ^[1];

^[1]

Stanford Univ., CA (United States)

Supported ionic liquid membranes (SILMs) are membranes that have ionic liquids impregnated in their pores. SILMs have been proposed for advanced carbon capture materials. Two-dimensional infrared (2D IR) and polarization selective IR pump-probe (PSPP) techniques were used to investigate the dynamics of reorientation and spectral diffusion of the linear triatomic anion, SeCN^–, in polyethersulfone (PES) membranes and room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf₂). The dynamics in the bulk EmimNTf₂ were compared to its dynamics in the SILM samples. Two PES membranes, PES200 and PES30, have pores with average sizes, ~300 nm and ~100 nm, respectively. Despite the relatively large pore sizes, the measurements reveal that the reorientation of SeCN^– and the RTIL structural fluctuations are substantially slower in the SILMs than in the bulk liquid. The complete orientational randomization, slows from 136 ps in the bulk to 513 ps in the PES30. 2D IR measurements yield three time scales for structural spectral diffusion (SSD), that is, the time evolution of the liquid structure. The slowest decay constant increases from 140 ps in the bulk to 504 ps in the PES200 and increases further to 1660 ps in the PES30. The results suggest that changes at the interface propagate out and influence the RTIL structural dynamics even more than a hundred nanometers from the polymer surface. Furthermore, the differences between the IL dynamics in the bulk and in the membranes suggest that studies of bulk RTIL properties may be poor guides to their use in SILMs in carbon capture applications.

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Research Organization:: Stanford Univ., CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: FG02-84ER13251

OSTI ID:: 1797779

Journal Information:: Journal of the American Chemical Society, Vol. 139, Issue 1; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Dynamics of a Room Temperature Ionic Liquid in Supported Ionic Liquid Membranes vs the Bulk Liquid: 2D IR and Polarized IR Pump–Probe Experiments

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