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Ultrafast Reaction Mechanisms in Perovskite Based Photocatalytic C–C Coupling
journal contribution
posted on 2020-01-24, 22:03 authored by Kang Wang, Haipeng Lu, Xiaolin Zhu, Yixiong Lin, Matthew C. Beard, Yong Yan, Xihan ChenSolar
driven carbon–carbon (C–C) bond formation is
a new direction in solar energy utilization. Earth abundant nanocrystal
based photocatalysts are highly sought after as they can potentially
eliminate expensive noble metal catalysts. A detailed understanding
of the underlying reaction mechanisms could provide guidance in designing
new systems that can activate a larger class of small molecules. Here,
we employ transient absorption spectroscopy to study a model C–C
bond formation reaction, i.e., α-alkylation of aldehydes catalyzed
by colloidal CsPbBr3 nanocrystals (NCs). We find that both
electrons and holes undergo ultrafast charge transfer (∼50
ps) from photoexcited perovskite NCs to reactant molecules. A charge
separated state lives for more than 0.8 μs, enabling a radical
mechanism to form the C–C bonds. We discuss the differences
between the NCs photoredox catalysts and the molecular catalyst.