| Autor: |
Forcherio GT; U.S. Army Combat Capabilities Development Command - Army Research Laboratory, Adelphi, Maryland 20783 United States.; Electro-Optic Technology Division, Naval Surface Warfare Center, Crane, Indiana 47522 United States., Ostovar B, Boltersdorf J; U.S. Army Combat Capabilities Development Command - Army Research Laboratory, Adelphi, Maryland 20783 United States., Cai YY, Leff AC; U.S. Army Combat Capabilities Development Command - Army Research Laboratory, Adelphi, Maryland 20783 United States.; General Technical Services, Adelphi, Maryland 20783, United States., Grew KN; U.S. Army Combat Capabilities Development Command - Army Research Laboratory, Adelphi, Maryland 20783 United States., Lundgren CA; U.S. Army Combat Capabilities Development Command - Army Research Laboratory, Adelphi, Maryland 20783 United States., Link S, Baker DR; U.S. Army Combat Capabilities Development Command - Army Research Laboratory, Adelphi, Maryland 20783 United States. |
| Abstrakt: |
Understanding the nature of hot carrier pathways following surface plasmon excitation of heterometallic nanostructures and their mechanistic prevalence during photoelectrochemical oxidation of complex hydrocarbons, such as ethanol, remains challenging. This work studies the fate of carriers from Au nanorods before and after the presence of reductively photodeposited Pd at the single-particle level using scattering and emission spectroscopy, along with ensemble photoelectrochemical methods. A sub-2 nm epitaxial Pd 0 shell was reductively grown onto colloidal Au nanorods via hot carriers generated from surface plasmon resonance excitation in the presence of [PdCl 4 ] 2- . These bimetallic Pd-Au nanorod architectures exhibited 14% quenched emission quantum yields and 9% augmented plasmon damping determined from their scattering spectra compared to the bare Au nanorods, consistent with injection/separation of intraband hot carriers into the Pd. Absorbed photon-to-current efficiency in photoelectrochemical ethanol oxidation was enhanced 50× from 0.00034% to 0.017% due to the photodeposited Pd. Photocurrent during ethanol oxidation improved 13× under solar-simulated AM1.5G and 40× for surface plasmon resonance-targeted irradiation conditions after photodepositing Pd, consistent with enhanced participation of intraband-excited sp -band holes and desorption of ethanol oxidation reaction intermediates owing to photothermal effects. |
