The
embedding of molecular metal oxides, or polyoxometalates (POMs),
in metal–organic frameworks (MOFs) opens new research avenues
in catalysis and beyond. This review explores the host–guest
chemistry of POMs embedded in MOF hosts and discusses the synergism
of the resulting composites for heterogeneous catalysis. The review
focuses on well-established and well-studied classes of POMs, such
as Keggin and Wells–Dawson anions, and well-researched MOFs,
including the MIL, UiO, and NENU families. Outstanding examples of
synergistic catalytic activity between the POM and MOF are described,
and key performance parameters, including POM localization, pore size
and pore structure, as well as particle size effects are described
for technologically important catalytic processes. In addition to
thermal catalysis, we discuss the use of POM@MOF composites for electro-
and photocatalysis with an emphasis on energy conversion systems.
Finally, we provide an outlook on emerging areas where POM@MOF composites
could lead to new catalytic reactivity.
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