title: Probing Heterogeneity and Bonding at Silica Surfaces through Single-Molecule Investigation of Base-Mediated Linkage Failure.
abstract: The nature of silica surfaces is relevant to many chemical systems, including heterogeneous catalysis and chromatographies utilizing functionalized-silica stationary phases. Surface linkages must be robust to achieve wide and reliable applicability. However, silyl ether-silica support linkages are known to be susceptible to detachment when exposed to basic conditions. We use single-molecule spectroscopy to examine the rate of surface linkage failure upon exposure to base at a variety of deposition conditions. Kinetic analysis elucidates the role of thermal annealing and addition of blocking layers in increasing stability. Critically, it was found that successful surface modification strategies alter the rate at which base molecules approach the silica surface as opposed to reducing surface linkage reactivity. Our results also demonstrate that the innate structural diversity of the silica surface is likely the cause of observed heterogeneity in surface-linkage disruption kinetics.
authors.affiliation: Department of Chemistry, The University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: Katherine M
authors.initials: KM
authors.lastname: Lupo
authors.affiliation: Department of Chemistry, The University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: Daniel A
authors.initials: DA
authors.lastname: Hinton
authors.affiliation: Department of Chemistry, The University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: James D
authors.initials: JD
authors.lastname: Ng
authors.affiliation: Department of Chemistry, The University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: Nicolas A
authors.initials: NA
authors.lastname: Padilla
authors.affiliation: Department of Chemistry, The University of Wisconsin-Madison , 1101 University Avenue, Madison, Wisconsin 53706, United States.
authors.forename: Randall H
authors.initials: RH
authors.lastname: Goldsmith