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Plasmonic Switching of the Reaction Pathway: Visible‐Light Irradiation Varies the Reactant Concentration at the Solid–Solution Interface of a Gold–Cobalt Catalyst
Author(s) -
Peiris Erandi,
Sarina Sarina,
Waclawik Eric R.,
Ayoko Godwin A.,
Han Pengfei,
Jia Jianfeng,
Zhu HuaiYong
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201904452
Subject(s) - aniline , catalysis , photochemistry , alkyne , materials science , selectivity , imine , irradiation , chemistry , organic chemistry , physics , nuclear physics
Product selectivity of alkyne hydroamination over catalytic Au 2 Co alloy nanoparticles (NPs) can be made switchable by a light‐on/light‐off process, yielding imine (cross‐coupling product of aniline and alkyne) under visible‐light irradiation, but 1,4‐diphenylbutadiyne in the dark. The low‐flux light irradiation concentrates aniline on the catalyst, accelerating the catalytic cross‐coupling by several orders of magnitude even at a very low overall aniline concentrations (1.0×10 −3 mol L −1 ). A tentative mechanism is that Au 2 Co NPs absorb light, generating an intense fringing electromagnetic field and hot electrons. The sharp field‐gradient (plasmonic optical force) can selectively enhance adsorption of light‐polarizable aniline molecules on the catalyst. The light irradiation thereby alters the aniline/alkyne ratio at the NPs surface, switching product selectivity. This represents a new paradigm to modify a catalysis process by light.