Probing Functionalities and Acidity of Calcined Phenylene-Bridged Periodic Mesoporous Organosilicates Using Dynamic Nuclear Polarization NMR, Diffuse Reflectance Infrared Fourier Transform Spectroscopy, and X-ray Photoelectron Spectroscopy

TL;DR

This study explores how calcination transforms phenylene-bridged mesoporous organosilicates, revealing oxidation and bond cleavage, and assesses their stability and functionalization potential for catalytic applications.

Contribution

It provides detailed insights into the chemical changes and stability of calcined PMO materials using advanced spectroscopic techniques, highlighting their potential for catalytic support.

Findings

Calcination at 450°C oxidizes phenylene bridges into (poly)phenols and carboxylic acids.

Calcined PMO retains ordered mesopores up to 600°C despite bond cleavage.

Phenol and carboxylic acid groups protonate amines but do not form covalent bonds.

Abstract

Owing to their high surface area, their high stability, and their hydrophobicity, periodic mesoporous organosilica (PMO) materials represent promising catalytic support for environmentally friendly chemical processes in water. We investigate here how the calcination of PMO material with benzene linkers (PMOB) allows its functionalization. Conventional and dynamic nuclear polarization (DNP)-enhanced NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray photoelectron spectroscopy prove that calcination at 450 {\deg}C results in the oxidation of phenylene bridges into (poly)phenols but also into carboxylic acids. Ketone, aldehyde, as well as allyl and aliphatic alcohol functionalities are also observed, but their amount is much lower than that of carboxylic acids. The calcination also cleaves the Si-C bonds. Nevertheless, N2 adsorption desorption measurements, powder X-ray diffraction, and transmission electron microscopy indicate that the PMOB materials calcined up to 600 {\deg}C still exhibit ordered mesopores. We show that the phenol and carboxylic acid functionalities of PMOB calcined at 450 {\deg}C protonate the NH2 group of 1-(3-aminopropyl)imidazole (API) in water at room temperature, but no formation of a covalent bond between API and the calcined PMOB functionalities has been detected.