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 k_BT, 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.