Surface Charge Regulation of MIL-100(Fe) by Anion Exchange for Demulsifying the Cationic Surfactant-Stabilized O/W Emulsion.

Demulsifying ionic surfactant-stabilized emulsions remains an emerging issue due to the stringent electrostatic barriers. In this work, a phosphate-mediated anion exchange strategy was proposed to fabricate a metal-organic framework, MIL-100(Fe), with adjustable surface charge for effective demulsification toward a cationic surfactant-stabilized emulsion. By adjusting the pH of the phosphate precursor solution, the surface charge of MIL-100(Fe) can be fine-tuned. At pH 3.0, the phosphate-exchanged MIL-100(Fe) with the zeta potential decreasing from 21.4 to 6.1 mV exhibited a significant enhancement of the demulsification efficiency (DE) from 35 to 91%. Further elevating the pH to 9.0 results in the zeta potential of the phosphate-exchanged MIL-100(Fe) to be reversed to -2.0 mV, and the DE can be optimized to 96% within 5 min. The demulsification mechanism was systematically explored based on the zeta potential, distribution of the surfactant, viscoelastic modulus evaluation, and morphological characterization of the emulsion in combination with monitoring of the dynamics process of demulsification. It was found that the phosphate-exchanged MIL-100(Fe) captured by the emulsion can lead to the release of the surfactant and heterogenization of the interfacial film, causing the elasticity of the emulsion to decrease and the irreversible deformation of emulsion droplets. Consequently, the destabilized emulsion could be subjected to the effective demulsification either by the fusion pathway mediated by the phosphate-exchanged MIL-100(Fe) or direct rupture. This work emphasized a facile and promising approach to deal with the cationic surfactant-emulsified oily wastewater and disclosed the fundamental demulsification process.