TY - JOUR
T1 - d-Band Holes React at the Tips of Gold Nanorods
AU - Al-Zubeidi, Alexander
AU - Wang, Yufei
AU - Lin, Jiamu
AU - Flatebo, Charlotte
AU - Landes, Christy F.
AU - Ren, Hang
AU - Link, Stephan
N1 - This work was supported by the Army Research Office under fund numbers W911NF1910363 and W911NF2210295, awarded to C.F.L. and S.L. S.L thanks the Robert A. Welch Foundation for support through the Charles W. Duncan, Jr.-Welch Chair in Chemistry (C-0002). C.F.L. acknowledges funding from the Robert A. Welch Foundation (C-1787) and support through the Kenneth S. Pitzer-Schlumberger Chair in Chemistry. Y.W. and H.R. acknowledge research support sponsored by the Defense Advanced Research Project Agency (DARPA) and the Army Research Office under Grant Number W911NF-20-1-0304. The views and conclusions contained in this document are those of the authors and should not be interpreted as representing the official policies, either expressed or implied, of the Defense Advanced Research Project Agency (DARPA) and the Army Research Office or the U.S. Government. The U.S. Government is authorized to reproduce and distribute reprints for Government purposes notwithstanding any copyright notation herein. This work was conducted in part using resources of the Shared Equipment Authority at Rice University.
PY - 2023/6/2
Y1 - 2023/6/2
N2 - Reactive hot spots on plasmonic nanoparticles have attracted attention for photocatalysis as they allow for efficient catalyst design. While sharp tips have been identified as optimal features for field enhancement and hot electron generation, the locations of catalytically promising d-band holes are less clear. Here we exploit d-band hole-enhanced dissolution of gold nanorods as a model reaction to locate reactive hot spots produced from direct interband transitions, while the role of the plasmon is to follow the reaction optically in real time. Using a combination of single-particle electrochemistry and single-particle spectroscopy, we determine that d-band holes increase the rate of gold nanorod electrodissolution at their tips. While nanorods dissolve isotropically in the dark, the same nanoparticles switch to tip-enhanced dissolution upon illimitation with 488 nm light. Electron microscopy confirms that dissolution enhancement is exclusively at the tips of the nanorods, consistent with previous theoretical work that predicts the location of d-band holes. We, therefore, conclude that d-band holes drive reactions selectively at the nanorod tips.
AB - Reactive hot spots on plasmonic nanoparticles have attracted attention for photocatalysis as they allow for efficient catalyst design. While sharp tips have been identified as optimal features for field enhancement and hot electron generation, the locations of catalytically promising d-band holes are less clear. Here we exploit d-band hole-enhanced dissolution of gold nanorods as a model reaction to locate reactive hot spots produced from direct interband transitions, while the role of the plasmon is to follow the reaction optically in real time. Using a combination of single-particle electrochemistry and single-particle spectroscopy, we determine that d-band holes increase the rate of gold nanorod electrodissolution at their tips. While nanorods dissolve isotropically in the dark, the same nanoparticles switch to tip-enhanced dissolution upon illimitation with 488 nm light. Electron microscopy confirms that dissolution enhancement is exclusively at the tips of the nanorods, consistent with previous theoretical work that predicts the location of d-band holes. We, therefore, conclude that d-band holes drive reactions selectively at the nanorod tips.
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U2 - 10.1021/acs.jpclett.3c00997
DO - 10.1021/acs.jpclett.3c00997
M3 - Article
C2 - 37267074
AN - SCOPUS:85162931766
SN - 1948-7185
VL - 14
SP - 5297
EP - 5304
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 23
ER -