Tailored Mesoporous Silicas: From Confinement Effects to Catalysis

Abstract

AbstractOrdered mesoporous silicas continue to find widespread use as supports for diverse applications such as catalysis, separations, and sensors. They provide a versatile platform for these studies because of their high surface area and the ability to control pore size, topology, and surface properties over wide ranges. Furthermore, there is a diverse array of synthetic methodologies for tailoring the pore surface with organic, organometallic, and inorganic functional groups. In this paper, we will discuss two examples of tailored mesoporous silicas and the resultant impact on chemical reactivity. First, we explore the impact of pore confinement on the thermochemical reactivity of phenethyl phenyl ether (PhCH2CH2OPh, PPE), which is a model of the dominant β-aryl ether linkage present in lignin derived from woody biomass. The influence of PPE surface immobilization, grafting density, silica pore diameter, and presence of a second surface-grafted inert “spacer” molecule on the product selectivity has been examined. We will show that the product selectivity can be substantially altered compared with the inherent gas-phase selectivity. Second, we have recently initiated an investigation of mesoporous silica supported, heterobimetallic oxide materials for photocatalytic conversion of carbon dioxide. Through surface organometallic chemistry, isolated M-O-M’ species can be generated on mesoporous silicas that, upon irradiation, form metal to metal charge transfer bands capable of converting CO2 into CO. Initial results from studies of Ti(IV)-O-Sn(II) on SBA-15 will be presented.