jp8b07868_si_001.pdf (1.34 MB)
Targeted Deposition of Platinum onto Gold Nanorods by Plasmonic Hot Electrons
journal contribution
posted on 2018-11-16, 00:00 authored by Gregory T. Forcherio, David R. Baker, Jonathan Boltersdorf, Asher C. Leff, Joshua P. McClure, Kyle N. Grew, Cynthia A. LundgrenPhotocatalytic
assembly of heterometallic nanoarchitectures via
plasmonic hot electrons is demonstrated by liquid-phase, reductive
photodeposition of platinum (Pt) onto gold nanorods (AuNR) under longitudinal
surface plasmon (LSP) excitation. Nucleation of Pt0 from
PtCl62– was initiated by plasmonic hot
electrons at the Au surface. Sub-5 nm epitaxial overgrowth of Pt followed
a core–shell morphology. Measured 6.5 longitudinal:transversal
growth aspect ratio revealed longitudinal growth preferentiality that
was consistent with the LSP dipole polarity. In situ spectroscopic monitoring of the photocatalytic growth process permitted
real-time feedback into Au surface functionalization with PtCl62– according to 16 nm red-shift in its Cl–Pt
ligand-to-metal charge-transfer (LπMCT) band involving
ligand π orbitals. Subsequent Pt0 growth kinetics
were tracked using the LπMCT band. Discrete dipole
models elucidated evolving light-matter interactions of Pt-decorated
AuNR that were consistent with experimental characterization. These
studies provide a foundational mechanistic understanding toward guided
assembly of heterometallic nanoarchitectures at ambient conditions
via plasmonic hot electrons.