Abstract

Efficient and stable photocatalysts for selective oxidative coupling of

amines to imines are crucial to the conversion of sustainable solar energy
to value-added chemical energy. In this work, UiO-66-
NH2@Au@COF core–shell nanocomposites with intercalated Au
nanoparticles between the UiO-66-NH2 core and the covalent-organic
framework (COF) shell have been demonstrated to exhibit enhanced
activity and stability for visible-light-driven aerobic selective oxidation of
amines to imines. With optimized Au and two-dimensional π-conjugated
COF content, the obtained UiO-66-NH2@Au0.5@COF1 photocatalyst
exhibited the highest conversion of benzylamine with an imine yield of
66.9% for at least five cycles. It is revealed that the introduction of
appropriate Au and COF could not only broaden the visible-light
absorption band but also promote the separation of photoinduced charge
carriers and enhance the photocatalytic performance. Furthermore, a
rational mechanism was explored to elucidate the process of
photocatalytic reaction. The intercalated Au nanoparticles with the
localized surface plasmon resonance (LSPR) effect act as generators of
hot electrons and also transfer channels for the photo-generated
electrons from the COF shell to the UiO-66-NH2 core. Importantly,
the MOF@metal@COF photocatalysts might provide a promising
strategy to construct photocatalysts with desirable activity and stability
under visible-light illumination.