Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 122, Issue 50, Pages 28901-28909Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.8b07868
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Funding
- Army Research Laboratory [W911NF-17-2-0057, W911NF-16-2-0059]
- U.S. Army Research Laboratory
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Photocatalytic 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 Pt from PtCl62- was initiated by plasmonic hot electrons at the Au surface. Sub-5 rim 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 (L pi MCT) band involving ligand pi orbitals. Subsequent Pt-0 growth kinetics were tracked using the L pi MCT 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.
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