Liquid/liquid (L/L) interfaces play a key, yet poorly
understood,
role in a range of complex chemical phenomena where time-evolving
interfacial structures and transient supramolecular assemblies act
as gatekeepers to function. Here, we employ surface-specific vibrational
sum frequency generation combined with neutron and X-ray scattering
methods to track the transport of dioctyl phosphoric acid (DOP) and
di-(2-ethylhexyl) phosphoric acid (DEHPA) ligands used in solvent
extraction at buried oil/aqueous interfaces away from equilibrium.
Our results show evidence for a dynamic interfacial restructuring
at low ligand concentrations in contrast to expectation. These time-varying
interfaces arise from the transport of sparingly soluble interfacial
ligands into the neighboring aqueous phase. These results support
a proposed “antagonistic” role of ligand complexation
in the aqueous phase that could serve as a holdback mechanism in kinetic
liquid extractions. These findings provide new insights into interfacially
controlled chemical transport at L/L interfaces and how these interfaces
vary chemically, structurally, and temporally in a concentration-dependent
manner and present potential avenues to design selective kinetic separations.