Cooperativity in the Aldol Condensation Using Bifunctional Mesoporous Silica–Poly(styrene) MCM-41 Organic/Inorganic Hybrid Catalysts

Cleveland, Jacob W.; Choi, Ji Il; Sekiya, Ryoh-Suke; Cho, Jinwon; Moon, Hyun June; Jang, Seung Soon; Jones, Christopher W.

doi:10.1021/acsami.1c21738

Title: Cooperativity in the Aldol Condensation Using Bifunctional Mesoporous Silica–Poly(styrene) MCM-41 Organic/Inorganic Hybrid Catalysts

Journal Article · 28 February 2022 · ACS Applied Materials and Interfaces

DOI: https://doi.org/10.1021/acsami.1c21738 · OSTI ID:1865412

Cleveland, Jacob W. ^[1]; Choi, Ji Il ^[2]; Sekiya, Ryoh-Suke ^[2]; Cho, Jinwon ^[2]; Moon, Hyun June ^[3];

^[2];

^[2]

Georgia Institute of Technology, Atlanta, GA (United States); Georgia Institute of Technology
Georgia Institute of Technology, Atlanta, GA (United States)
School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Dr., Atlanta, Georgia 30332-0100, United States

This work explores the efficacy of silica/organic hybrid catalysts, where the organic component is built from linear aminopolymers appended to the silica support within the support mesopores. Specifically, the role of molecular weight and polymer chain composition in amine-bearing atom transfer radical polymerization-synthesized poly(styrene-co-2-(4-vinylbenzyl)isoindoline-1,3-dione) copolymers is probed in the aldol condensation of 4-nitrobenzaldehyde and acetone. Controlled polymerization produces protected amine-containing poly(styrene) chains of controlled molecular weight and dispersity, and a grafting-to thiol–ene coupling approach followed by a phthalimide deprotection step are used to covalently tether and activate the polymer hybrid catalysts prior to the catalytic reactions. Site-normalized batch kinetics are used to assess the role of polymer molecular weight and chain composition in the cooperative catalysis. Lower-molecular-weight copolymers are demonstrated to be more active than catalysts built from only molecular organic components or from higher-molecular-weight chains. Molecular dynamics simulations are used to probe the role of polymer flexibility and morphology, whereby it is determined that higher-molecular-weight hybrid structures result in congested pores that inhibit active site cooperativity and the diffusivity of reagents, thus resulting in lower rates during the reaction.

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Research Organization:: Georgia Institute of Technology, Atlanta, GA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-03ER15459

OSTI ID:: 1865412

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 9 Vol. 14; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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