Charge Density Overcomes Steric Hindrance of Ferrocene Surfactant in Switchable Oil-in-Dispersion Emulsions

Angew Chem Int Ed Engl. 2023 Jan 26;62(5):e202210050. doi: 10.1002/anie.202210050. Epub 2022 Dec 19.

Abstract

A ferrocene surfactant can be switched between single and double head form (FcN+ C12 /Fc+ N+ C12 ) triggered by redox reaction. FcN+ C12 can neither stabilize an O/W emulsion alone nor an oil-in-dispersion emulsion in combination with alumina nanoparticles due to the steric hindrance of the ferrocene group. However, such steric hindrance can be overcome by increasing the charge density in Fc+ N+ C12 , so that oil-in-dispersion emulsions can be co-stabilized by Fc+ N+ C12 and alumina nanoparticles at very low concentrations (1×10-7 M (≈50 ppb) and 0.001 wt %, respectively). Not only can reversible formation/destabilization of oil-in-dispersion emulsions be achieved by redox reaction, but also reversible transformation between oil-in-dispersion emulsions and Pickering emulsions can be obtained through reversing the charge of alumina particles by adjusting the pH. The results provide a new protocol for the design of surfactants for stabilization of smart oil-in-dispersion emulsions.

Keywords: Alumina Nanoparticles; Charge Density; Emulsion; Ferrocene Surfactant; Steric Hindrance.