Bulk Anion Recognition Kinetically Holds Back Interfacial Adsorption

Sun, Pan; Bhattacharjee, Nabarupa; Einkauf, Jeffrey D.; Doughty, Benjamin

doi:10.1021/acs.jpclett.4c03551

Title: Bulk Anion Recognition Kinetically Holds Back Interfacial Adsorption

Journal Article · Thu Feb 20 00:00:00 UTC 2025 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.4c03551 · OSTI ID:2538180

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Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Ames Laboratory, and Iowa State University, Ames, IA (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

The competition between bulk and interfacial phenomena underlies many key processes in complex chemical phenomena and transport. While competitive processes are often framed in a thermodynamic context, opportunities to leverage transient species found away from equilibrium can provide a kinetic handle to achieve unconventional reaction outcomes. In this work, we outfit an iminoguanidinium headgroup capable of selective SO₄^2– complexation with alkyl tails of varying complexity to probe competitive bulk and interfacial reaction pathways and tune kinetic pathways for selective chemical separations. Using sum frequency generation (SFG) vibrational spectroscopy we unexpectedly find that adsorption of ligands to the air–aqueous interface was dramatically slowed down for species with increasingly hydrophobic tails. Underlying this phenomenon, we show that the formation of bulk colloidal species with differing propensities for SO₄^2– inhibited surface adsorption via a kinetic bottleneck in the exchange of molecular extractants with colloidal aggregates. This kinetic effect could open up avenues to access unconventional selectivity via complexation of strongly coordinating species in the bulk phase, allowing for more weakly coordinating species to transport via interfacial mechanisms. Furthermore, this work broadly probes nonequilibrium phenomena in chemical separations that arise through unexpected interfacial events that are neglected in traditional equilibrium descriptions.

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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:: 2538180

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 8 Vol. 16; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Adsorption
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Title: Bulk Anion Recognition Kinetically Holds Back Interfacial Adsorption

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