Unveiling the mechanism of methylcellulose-templated synthesis of Al2O3 microspheres with organic solvents as swelling agents in microchannel

Abstract

Herein, we report a systematic investigation of the preparation of large-pore-volume Al2O3 microspheres using a complex synthesis system with methylcellulose (MC) as the template and gelation initiator and organic solvents as the swelling agent and carrier medium under the flow characteristics of a coaxial microchannel. The adsorption of MC micelles on boehmite colloidal nanoparticles (NPs) was proven and determined by interfacial tension measurements, dynamic light scattering, and cryogenic transmission electron microscopy. Isothermal titration calorimetry demonstrated that the adsorption process was caused by nonspecific hydrophobicity; one binding site was involved, and the affinity constant was 1060 M−1. When the MC:NPs mass ratio exceeded 0.1, the template–NP bridged each other to form large aggregates, thereby forming large mesopores and enhancing the gelation speed. Alkanes, alcohols, and amines were applied to further enhance the porosity, and the swelling capacities were investigated experimentally and theoretically. Amines were efficient swelling agents owing to their excellent ability to swell MC micelles and insert into the acid colloid network. The coaxial microchannel was subjected to molding; this process significantly influenced the morphology and textural properties owing to the internal circulation during droplet formation. When trihexylamine with suitable steric hindrance, alkalinity, and polarity was used as the swelling agent, the microspheres exhibited an optimal specific surface area of 403 m2/g and a pore volume of 1.85 cm3/g.