The action of molecular catalysts comprises multiple microscopic kinetic steps whose nature is of central importance in determining catalyst activity and selectivity. Single-molecule microscopy enables the direct examination of these steps, including elucidation of molecule-to-molecule variability. Such molecular diversity is particularly important for the behavior of molecular catalysts supported at surfaces. We present the first combined investigation of the initiation dynamics of an operational palladium cross-coupling catalyst at the bulk and single-molecule levels, including under turnover conditions. Base-initiated kinetics reveal highly heterogeneous behavior indicative of diverse catalyst population. Unexpectedly, this distribution becomes more heterogeneous at increasing base concentration. We model this behavior with a two-step saturation mechanism and identify specific microscopic steps where chemical variability must exist in order to yield observed behavior. Critically, we reveal how structural diversity at a surface translates into heterogeneity in catalyst behavior, while demonstrating how single-molecule experiments can contribute to understanding of molecular catalysts.

Direct tracking of lithium ions with time and spatial resolution can provide an important diagnostic tool for understanding mechanisms in lithium ion batteries. A fluorescent indicator of lithium ions, 2-(2-hydroxyphenyl)naphthoxazole, was synthesized and used for real-time tracking of lithium ions via widefield fluorescence microscopy. The fluorophore can be excited with visible light and was shown to enable quantitative determination of the lithium ion diffusion constant in a microfluidic model system for a plasticized polymer electrolyte lithium battery. The use of widefield fluorescence microscopy for in situ tracking of lithium ions in batteries is discussed.

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.