TY - JOUR
T1 - Quantifying the ultrafast and steady-state molecular reduction potential of a plasmonic photocatalyst
AU - Warkentin, Christopher L.
AU - Frontiera, Renee R.
N1 - Publisher Copyright:
© 2023 National Academy of Sciences. All rights reserved.
PY - 2023
Y1 - 2023
N2 - Plasmonic materials are promising photocatalysts as they are well suited to convert light into hot carriers and heat. Hot electron transfer is suggested as the driving force in many plasmon-driven reactions. However, to date, there are no direct molecular measures of the rate and yield of plasmon-To-molecule electron transfer or energy of these electrons on the timescale of plasmon decay. Here, we use ultrafast and spectroelectrochemical surface-enhanced Raman spectroscopy to quantify electron transfer from a plasmonic substrate to adsorbed methyl viologen molecules. We observe a reduction yield of 2.4 to 3.5% on the picosecond timescale, with plasmon-induced potentials ranging from 3.1 to 4.5 mV. Excitingly, some of these reduced species are stabilized and persist for tens of minutes. This work provides concrete metrics toward optimizing material molecule interactions for efficient plasmon-driven photocatalysis.
AB - Plasmonic materials are promising photocatalysts as they are well suited to convert light into hot carriers and heat. Hot electron transfer is suggested as the driving force in many plasmon-driven reactions. However, to date, there are no direct molecular measures of the rate and yield of plasmon-To-molecule electron transfer or energy of these electrons on the timescale of plasmon decay. Here, we use ultrafast and spectroelectrochemical surface-enhanced Raman spectroscopy to quantify electron transfer from a plasmonic substrate to adsorbed methyl viologen molecules. We observe a reduction yield of 2.4 to 3.5% on the picosecond timescale, with plasmon-induced potentials ranging from 3.1 to 4.5 mV. Excitingly, some of these reduced species are stabilized and persist for tens of minutes. This work provides concrete metrics toward optimizing material molecule interactions for efficient plasmon-driven photocatalysis.
UR - http://www.scopus.com/inward/record.url?scp=85175584770&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85175584770&partnerID=8YFLogxK
U2 - 10.1073/pnas.2305932120
DO - 10.1073/pnas.2305932120
M3 - Article
C2 - 37874859
AN - SCOPUS:85175584770
SN - 0027-8424
VL - 120
JO - Proceedings of the National Academy of Sciences of the United States of America
JF - Proceedings of the National Academy of Sciences of the United States of America
IS - 44
M1 - e2305932120
ER -