Single-Atom-Based Vanadium Oxide Catalysts Supported on Metal–Organic Frameworks: Selective Alcohol Oxidation and Structure–Activity Relationship

We report the syntheses, structures,
and oxidation catalytic activities
of a single-atom-based vanadium oxide incorporated in two highly crystalline
MOFs, Hf-MOF-808 and Zr-NU-1000. These vanadium catalysts were introduced
by a postsynthetic metalation, and the resulting materials (Hf-MOF-808-V
and Zr-NU-1000-V) were thoroughly characterized through a combination
of analytic and spectroscopic techniques including single-crystal
X-ray crystallography. Their catalytic properties were investigated
using the oxidation of 4-methoxybenzyl alcohol under an oxygen atmosphere
as a model reaction. Crystallographic and variable-temperature spectroscopic
studies revealed that the incorporated vanadium in Hf-MOF-808-V changes
position with heat, which led to improved catalytic activity.