Adsorption, Ordering, and Local Environments of Surfactant-Encapsulated Polyoxometalate Ions Probed at the Air–Water Interface

Doughty, Benjamin; Yin, Panchao; Ma, Ying-Zhong

doi:10.1021/acs.langmuir.6b01643

Title: Adsorption, Ordering, and Local Environments of Surfactant-Encapsulated Polyoxometalate Ions Probed at the Air–Water Interface

Journal Article · Sat Jul 23 00:00:00 EDT 2016 · Langmuir

DOI:https://doi.org/10.1021/acs.langmuir.6b01643· OSTI ID:1324104

Doughty, Benjamin ^[1]; Yin, Panchao ^[2]; Ma, Ying-Zhong ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division and Shull Wollan Center, Neutron Sciences Directorate

The continued development and application of surfactant-encapsulated polyoxometalates (SEPs) relies on understanding the ordering and organization of species at their interface and how these are impacted by the various local environments to which they are exposed. In this paper, we report on the equilibrium properties of two common SEPs adsorbed to the air–water interface and probed with surface-specific vibrational sum-frequency generation (SFG) spectroscopy. These results reveal clear shifts in vibrational band positions, the magnitude of which scales with the charge of the SEP core, which is indicative of a static field effect on the surfactant coating and the associated local chemical environment. This static field also induces ordering in surrounding water molecules that is mediated by charge screening via the surface-bound surfactants. From these SFG measurements, we are able to show that Mo₁₃₂-based SEPs are more polar than Mo₇₂V₃₀ SEPs. Disorder in the surfactant chain packing at the highly curved SEP surfaces is attributed to large conic volumes that can be sampled without interactions with neighboring chains. Measurements of adsorption isotherms yield free energies of adsorption to the air–water interface of -46.8 ± 0.4 and -44.8 ± 1.2 kJ/mol for the Mo₁₃₂ and Mo₇₂V₃₀ SEPs, respectively, indicating a strong propensity for the fluid surface. Finally, the influence of intermolecular interactions on the surface adsorption energies is 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)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1324104

Journal Information:: Langmuir, Vol. 32, Issue 32; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 21 works

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