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Reaction Pathway Dependence in Plasmonic Catalysis: Hydrogenation as a Model Molecular Transformation
Author(s) -
Barbosa Eduardo C. M.,
Fiorio Jhonatan L.,
Mou Tong,
Wang Bin,
Rossi Liane M.,
Camargo Pedro H. C.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201705749
Subject(s) - nanomaterial based catalyst , plasmon , catalysis , surface plasmon resonance , nanoparticle , density functional theory , nanotechnology , materials science , plasmonic nanoparticles , chemical physics , chemistry , photochemistry , computational chemistry , optoelectronics , organic chemistry
The localized surface plasmon resonance (LSPR) excitation in plasmonic nanoparticles can enhance or mediate chemical transformations. Increased reaction rates for several reactions have been reported due to this phenomenon; however, the fundamental understanding of mechanisms and factors that affect activities remains limited. Here, by investigating hydrogenation reactions as a model transformation and employing different reducing agents, H 2 and NaBH 4 , which led to different hydrogenation reaction pathways, we observed that plasmonic excitation of Au nanoparticle catalysts can lead to negative effects over the activities. The underlying physical reason was explored using density functional theory calculations. We observed that positive versus negative effects on the plasmonic catalytic activity is reaction‐pathway dependent. These results shed important insights on our current understanding of plasmonic catalysis, demonstrating reaction pathways must be taken into account for the design of plasmonic nanocatalysts.