How
Does a Plasmon-Induced Hot Charge Carrier Break
a C–C Bond?
Hyun Huh
Hoa Duc Trinh
Dokyung Lee
Sangwoon Yoon
10.1021/acsami.9b05509.s001
https://acs.figshare.com/articles/journal_contribution/How_Does_a_Plasmon-Induced_Hot_Charge_Carrier_Break_a_C_C_Bond_/8321264
Hot-electron
chemistry at gold nanoparticle (AuNP) surfaces has
received much attention recently because its understanding provides
a basis for plasmonic photocatalysis and photovoltaics. Nonradiative
decay of excited surface plasmons produces energetic hot charge carriers
that transfer to adsorbate molecules and induce chemical reactions.
Such plasmon-driven reactions, however, have been limited to a few
systems, notably the dimerization of 4-aminobenzenethiol to 4,4′-dimercaptoazobenzene.
In this work, we explore a new class of plasmon-driven reactions associated
with a unimolecular bond cleavage process. We unveil the mechanism
of the decarboxylation reaction of 4-mercaptobenzoic acid and extend
the mechanism to account for the β-cleavage reaction of 4-mercaptobenzyl
alcohol. Combining the construction of well-controlled nanogap systems
and sensitive Raman spectroscopy with methodical changes of experimental
conditions (laser wavelengths, interface materials, pH, ambient gases,
etc.), we track the hot charge carriers from the formation to the
transfer to reactants, which provides insights into how plasmon excitation
eventually leads to the C–C bond cleavage of the molecules
in the nanogap.
2019-06-13 00:00:00
unimolecular bond cleavage process
4- mercaptobenzoic acid
charge carriers
Plasmon-Induced Hot Charge Carrier Break
4- mercaptobenzyl alcohol
transfer
Such plasmon-driven reactions
surface
mechanism
molecule
β- cleavage reaction
well-controlled nanogap systems