Harnessing Hot Electrons from Near IR Light for Hydrogen Production Using Pt-End-Capped-AuNRs.

Gold nanorods show great potential in harvesting natural sunlight and generating hot charge carriers that can be employed to produce electrical or chemical energies. We show that photochemical reduction of Pt(IV) to Pt metal mainly takes place at the ends of gold nanorods (AuNRs), suggesting photon-induced hot electrons are localized in a time-averaged manner at AuNR ends. To use these hot electrons efficiently, a novel synthetic method to selectively overgrow Pt at the ends of AuNRs has been developed. These Pt-end-capped AuNRs show relatively high activity for the production of hydrogen gas using artificial white light, natural sunlight, and more importantly, near IR light at 976 nm. Tuning of the surface plasmon resonance (SPR) wavelength of AuNRs changes the hydrogen gas production rate, indicating that SPR is involved in hot electron generation and photoreduction of hydrogen ions. This study shows that gold nanorods are excellent for converting low-energy photons into high-energy hot electrons, which can be used to drive chemical reactions at their surfaces.

Microscopic Movement of Slow-Diffusing Nanoparticles in Cylindrical Nanopores Studied with Three-Dimensional Tracking.

To study slow mass transport in confined environments, we developed a three-dimensional (3D) single-particle localization technique to track their microscopic movements in cylindrical nanopores. Under two model conditions, particles are retained much longer inside the pores: (1) increased solvent viscosity, which slows down the particle throughout the whole pore, and (2) increased pore wall affinity, which slows down the particle only at the wall. In viscous solvents, the particle steps decrease proportionally to the increment of the viscosity, leading to macroscopically slow diffusion. As a contrast, the particles in sticky pores are microscopically active by showing limited reduction of step sizes. A restricted diffusion mode, possibly caused by the heterogeneous environment in sticky pores, is the main reason for macroscopically slow diffusion. This study shows that it is possible to differentiate slow diffusion in confined environments caused by different mechanisms.