Liquid-Liquid Interface Can Promote Micro-Scale Thermal Marangoni Convection in Liquid Binary Mixtures

Liquid-liquid phase separation, a physical transition in which a homogeneous solution spontaneously demixes into two coexisting liquid phases, has been a key topic in the thermodynamics of two-component systems and may find applications in separation, drug delivery, and protein crystallization. Here we applied a microscale temperature gradient using optothermal heating of a gold nanoparticle to overcome the experimental difficulties inherent in homogeneous heating: we aimed at highlighting precise structural development by avoiding randomly nucleating/growing microdomains. In response to laser illumination, a single gold nanoparticle immersed in a binary mixture of aqueous 2,6-dimethylpiridine (lutidine) and N-isopropylpropionamide (NiPPA) was clearly sensitive to the phase transition of the surrounding liquid as demonstrated by light scattering signals, spectral red-shifts and bright-spot images. The local phase separation encapsulating the gold nanoparticle resulted in immediate formation and growth of an organic-rich droplet which was confirmed by Raman spectroscopy. Remarkably, the droplet was stable under a non-equilibrium steady-state heating condition because of strong thermal confinement. Microdroplet growth was ascribed to thermocapillary flow induced by a newly formed liquid-liquid interface around the hot gold nanoparticle. Based upon a tracer experiment and numerical simulation, it is deduced that the transport of solute to the high temperature area is driven by this thermocapillary flow. This study enhances our understanding of phase separation in binary mixtures induced by microscale temperature confinement.

This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpcc.9b09208.