文献类型：期刊文献

英文题名：Enhanced Biphasic Reactions in Amphiphilic Silica Mesopores

作者：Zhao, Guolin[1,2];Li, Yao[1,2];Zhen, Wen[3];Gao, Jie[1];Gu, Yunjiao[1];Hong, Bing[1];Han, Xia[2];Zhao, Shuangliang[2,3];Pera-Titus, Marc[1,4]

机构：[1]UMI 3464 CNRS Solvay, Ecoefficient Prod & Proc Lab E2P2L, UMI 3464, Shanghai 201108, Peoples R China;[2]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[3]Guangxi Univ, Sch Chem & Chem Engn, Nanning 530004, Peoples R China;[4]Cardiff Univ, Cardiff Catalysis Inst, Sch Chem, Cardiff CF10 3AT, Wales

年份：2024

卷号：128

期号：4

起止页码：1644

外文期刊名：JOURNAL OF PHYSICAL CHEMISTRY C

收录：;EI(收录号：20240515464062);WOS:【SCI-EXPANDED(收录号:WOS:001156041200001)】；

基金：This study was funded by the ERC grant Micheangelo (contract number #771586) and Solvay.

语种：英文

外文关键词：Ethylene - Intelligent systems - Light scattering - Monte Carlo methods - Organic solvents - Ostwald ripening - Particle size analysis - Silica - Surface reactions - Thermogravimetric analysis - Titration

摘要：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 cm(3)center dot 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.