Enhanced biphasic reactions in amphiphilic silica mesopores

Zhao, Guolin, Li, Yao, Zhen, Wen, Gao, Jie, Gu, Yunjiao, Hong, Bing, Han, Xia, Zhao, Shuangliang and Pera-Titus, Marc 2024. Enhanced biphasic reactions in amphiphilic silica mesopores. Journal of Physical Chemistry C 128 , pp. 1644-1653. 10.1021/acs.jpcc.3c07477

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Abstract

In this study, we investigated the effect of the pore volume and mesopore size of surface-active catalytic organosilicas on the genesis of particle-stabilized (Pickering) emulsions for the dodecanal/ethylene glycol system and their reactivity for the acid-catalyzed biphasic acetalization reaction. To this aim, we functionalized a series of fumed silica superparticles (size 100–300 nm) displaying an average mesopore size in the range of 11–14 nm and variable mesopore volume, with a similar surface density of octyl and propylsulfonic acid groups. The modified silica superparticles were characterized in detail using different techniques, including acid–base titration, thermogravimetric analysis, TEM, and dynamic light scattering. The pore volume of the particles impacts their self-assembly and coverage at the dodecanal/ethylene glycol (DA/EG) interface. This affects the stability and the average droplet size of emulsions and conditions of the available interfacial surface area for reaction. The maximum DA-EG productivity is observed for A200 super-SiNPs with a pore volume of 0.39 cm3·g–1 with an interfacial coverage by particles lower than 1 (i.e., submonolayer). Using dissipative particle dynamics and all-atom grand canonical Monte Carlo simulations, we unveil a stabilizing role of the pore volume of porous silica superparticles for generating emulsions and local micromixing of immiscible dodecanal and ethylene glycol, allowing fast and efficient solvent-free acetalization in the presence of Pickering emulsions. The micromixing level is interrelated to the adsorption energy of self-assembled particles at the DA/EG interface.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry Cardiff Catalysis Institute (CCI)
Publisher:	American Chemical Society
ISSN:	1932-7447
Funders:	ERC grant Micheangelo (contract number #771586) and Solvay.
Date of First Compliant Deposit:	23 January 2024
Date of Acceptance:	2 January 2024
Last Modified:	07 Mar 2024 14:05
URI:	https://orca.cardiff.ac.uk/id/eprint/165758

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