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Isotope Effects in Plasmonic Photosynthesis
Author(s) -
Yu Sungju,
Jain Prashant K.
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202011805
Subject(s) - plasmon , photoexcitation , kinetic isotope effect , chemistry , photosynthesis , photochemistry , bond cleavage , plasmonic nanoparticles , chemical physics , materials science , physics , optoelectronics , atomic physics , organic chemistry , catalysis , biochemistry , deuterium , excited state
The photoexcitation of plasmonic nanoparticles has been shown to drive multistep, multicarrier transformations, such as the conversion of CO 2 into hydrocarbons. But for such plasmon‐driven chemistry to be precisely understood and modeled, the critical photoinitiation step in the reaction cascade must be identified. We meet this goal by measuring H/D and 12 C/ 13 C kinetic isotope effects (KIEs) in plasmonic photosynthesis. In particular, we found that the substitution of H 2 O with D 2 O slows hydrocarbon production by a factor of 5–8. This primary H/D KIE leads to the inference that hole‐driven scission of the O−H bond in H 2 O is a critical, limiting step in plasmonic photosynthesis. This study advances mechanistic understanding of light‐driven chemical reactions on plasmonic nanoparticles.