TY  - JOUR
A1  - Bald, Ilko
A1  - Schürmann, Robin Mathis
A1  - Ebel, Kenny
A1  - Nicolas, Christophe
A1  - Milosavljevic, Aleksandar R.
T1  - Role of valence band states and plasmonic enhancement in electron-transfer-induced transformation of nitrothiophenol
JF  - The Journal of Physical Chemistry Letters
N2  - Hot-electron-induced reactions are more and more recognized as a critical and ubiquitous reaction in heterogeneous catalysis. However, the kinetics of these reactions is still poorly understood, which is also due to the complexity of plasmonic nanostructures. We determined the reaction rates of the hot-electron-mediated reaction of 4-nitrothiophenol (NTP) on gold nanoparticles (AuNPs) using fractal kinetics as a function of the laser wavelength and compared them with the plasmonic enhancement of the system. The reaction rates can be only partially explained by the plasmonic response of the NPs. Hence, synchrotron X-ray photoelectron spectroscopy (XPS) measurements of isolated NTP-capped AuNP clusters have been performed for the first time. In this way, it was possible to determine the work function and the accessible valence band states of the NP systems. The results show that besides the plasmonic enhancement, the reaction rates are strongly influenced by the local density of the available electronic states of the system.
Y1  - 2019
UR  - https://pubs.acs.org/doi/10.1021/acs.jpclett.9b00848
U6  - https://doi.org/10.1021/acs.jpclett.9b00848
SN  - 1948-7185
VL  - 10
SP  - 3153
EP  - 3158
PB  - American Chemical Society
CY  - Washington
ER  -