Boosting Reaction Kinetics with Viscous Nanowire Dispersions

Abstract

Higher viscosity typically slows chemical reactions by restricting molecular movement, while stirring accelerates reactions by enhancing reactant diffusion and collisions. However, in this study, we reveal that reaction rates in nanowire dispersions─with microscopic viscosity ∼300 times that of decane, can be enhanced by over an order of magnitude. Counterintuitively, stirring slows the reaction with higher stirring rates causing even greater deceleration. This phenomenon is observed in both photo- and thermally activated cyclic reactions. Molecular dynamics simulations and confocal laser scanning microscopy suggest that aliphatic chains grafted onto nanowires interact with anisotropic molecules, increasing their local concentrations near the nanowires. Notably, azobenzene photoisomerization is completely inhibited in the nanowire dispersion, despite completing within 30 s in the absence of nanowires. We propose that the aliphatic chains align reactive molecules directionally, while the confined space prevents bulky cis-isomer formation. These findings show that nanowires not only harvest and orient reactive molecules but also exclude bulky products, significantly enhancing the reaction kinetics in confined systems.