Nanoscale organization of thiol and arylsulfonic acid on silica leads to a highly active and selective bifunctional, heterogeneous catalyst

Ordered mesoporous silicas functionalized with alkylsulfonic acid and thiol group pairs have been shown to catalyze the synthesis of bisphenols from the condensation of phenol and various ketones, with activity and selectivity highly dependent on the distance between the acid and thiol. Here, a new route to thiol/sulfonic acid paired catalysts is reported. A bis-silane precursor molecule containing both a disulfide and a sulfonate ester bond is grafted onto the surface of ordered mesoporous silica, SBA-15, followed by simultaneous disulfide reduction and sulfonate ester hydrolysis. The resulting catalyst, containing organized pairs of arylsulfonic acid and thiol groups, is significantly more active than the alkylsulfonic acid/thiol paired catalyst in the synthesis of bisphenol A and Z, and this increase in activity does not lead to a loss of regioselectivity. The paired catalyst has activity similar to that of a randomly bifunctionalized arylsulfonic acid/thiol catalyst in the bisphenol A reaction but exhibits greater activity and selectivity than the randomly bifunctionalized catalyst in the bisphenol Z reaction.     

Cooperative catalysis by silica-supported organic functional groups

Hybrid inorganic-organic materials comprising organic functional groups tethered from silica surfaces are versatile, heterogeneous catalysts. Recent advances have led to the preparation of silica materials containing multiple, different functional groups that can show cooperative catalysis; that is, these functional groups can act together to provide catalytic activity and selectivity superior to what can be obtained from either monofunctional materials or homogeneous catalysts. This tutorial review discusses cooperative catalysis of silica-based catalytic materials, focusing on the cooperative action of acid-base, acid-thiol, amine-urea, and imidazole-alcohol-carboxylate groups. Particular attention is given to the effect of the spatial arrangement of these organic groups and recent developments in the spatial organization of multiple groups on the silica surface.     

A wave field synthesis approach to reproduction of spatially correlated sound fields

This article discusses an open-loop wave field synthesis (WFS) approach for the reproduction of spatially correlated sound fields. The main application concerns laboratory reproduction of turbulent boundary layer wall pressure on aircraft fuselages and measurement of their sound transmission loss. The problem configuration involves reconstruction of random sound pressure distributions on a planar reproduction surface using a planar array of reproduction monopoles parallel to the reproduction plane. In this paper, the WFS formulation is extended to sound fields with imposed time and spatial correlation properties (or equivalently imposed cross-spectral density in the frequency and wave number domains). Numerical examples are presented for the reproduction of a propagating plane wave, diffuse acoustic field and wall pressure in subsonic or supersonic turbulent boundary layers. The reproduction accuracy is examined in terms of the size of the source plane and reproduction plane, their separation, and the number of reproduction sources required per acoustic wavelength. While the reproduction approach cannot reconstruct sub-wavelength correlation scales of subsonic turbulent boundary layers, it effectively reconstructs correlation scales larger than the acoustic wavelength, making it appropriate for diffuse acoustic field and supersonic turbulent layers.