TY - JOUR
T1 - Single-Particle Insights into Plasmonic Hot Carrier Separation Augmenting Photoelectrochemical Ethanol Oxidation with Photocatalytically Synthesized Pd-Au Bimetallic Nanorods
AU - Forcherio, Gregory T.
AU - Ostovar, Behnaz
AU - Boltersdorf, Jonathan
AU - Cai, Yi Yu
AU - Leff, Asher C.
AU - Grew, Kyle N.
AU - Lundgren, Cynthia A.
AU - Link, Stephan
AU - Baker, David R.
N1 - This work was sponsored by the U.S. Army Combat Capabilities Development Command - Army Research Laboratory and was accomplished in part under USARL Cooperative Agreement No. W911NF-17-2-0057 (awarded to G.T.F.). G.T.F. also acknowledges support from the Office of Naval Research Code 312 and the Naval Innovative Science & Engineering Program. S.L. thanks the Robert A. Welch Foundation for support through the Charles W. Duncan, Jr.–Welch Chair in Chemistry (C-0002) and acknowledges financial support from the U.S. Department of Energy, Office of Science, Basic Energy Sciences, CPIMS Program, under Award No. DE-339SC0016534, which for this work supported S.L. who oversaw the single-particle measurements and analysis and final manuscript preparation. We thank Dr. Stephen A. Lee and Alexander Al-Zubeidi for useful discussions. The views and conclusions contained in this document are those of the authors and should not be interpreted as representing official policies, either expressed or implied, of the U.S. Government. The U.S. Government is authorized to reproduce and distribute reprints for Government purposes notwithstanding any copyright notation herein.
PY - 2022/8/23
Y1 - 2022/8/23
N2 - 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 Pd0shell was reductively grown onto colloidal Au nanorods via hot carriers generated from surface plasmon resonance excitation in the presence of [PdCl4]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.
AB - 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 Pd0shell was reductively grown onto colloidal Au nanorods via hot carriers generated from surface plasmon resonance excitation in the presence of [PdCl4]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.
KW - nanocatalysts
KW - photoelectrochemistry
KW - photoluminescence spectroscopy
KW - single-particle spectroscopy
KW - surface plasmon resonance
UR - https://www.scopus.com/pages/publications/85136153249
UR - https://www.scopus.com/pages/publications/85136153249#tab=citedBy
U2 - 10.1021/acsnano.2c03549
DO - 10.1021/acsnano.2c03549
M3 - Article
C2 - 35894585
AN - SCOPUS:85136153249
SN - 1936-0851
VL - 16
SP - 12377
EP - 12389
JO - ACS Nano
JF - ACS Nano
IS - 8
ER -