Energetically Preferred Bilayered Coacervation of Oppositely Charged ZrHP Nanoplatelets.

A platform is introduced for bilayered coacervation of oppositely charged nanoplatelets (NPLs) at the oil-water interface. To this end, we synthesized two types of zirconium hydrogen phosphate (ZrHP) NPLs, cationically charged NPLs (CNPLs), and anionically charged NPLs (ANPLs) by conducting surface-initiated atom transfer radical polymerization. Taking advantage of the platelet geometry and controlled wettability, we demonstrated that ANPLs and CNPLs coacervate themselves to form a bilayered NPL membrane at the interface, which was directly confirmed by confocal laser scanning microscopy. Via theoretical consideration using the hit-and-miss Monte Carlo method, we determined that electrostatic attraction-driven coacervation of ANPLs and CNPLs at the interface shows a minimum attachment energy of ∼ -106 kBT, which is comparable to the cases where NPLs charged with the same type of ions are attached. Finally, this unique and novel interfacial coacervation behavior allowed us to develop a pH-responsive smart Pickering emulsion system.