  Metal-organic frameworks (MOFs) are an attractive substrate for catalytic
reactions due to the high area density of reaction sites and the ability to
tailor an array of material attributes. This study focuses on a thermally
stable crystalline UiO-66(Zr) MOF structure and the modulation of the
electronic structure using two strategies to improve the catalytic conversion
and selectivity of benzene alcohol to benzedehyate. Those two strategies
include the functionalization of the organic struts with branched ligands and
manually creating structural defects with unsaturated organic linkers. A
combination of computational and experimental results provide evidence of
improved catalytic activity of MOFs via these two approaches. Functional groups
attached to the main organic strut modify the electronic environment of the
photoactive aromatic carbon and thereby decrease the optical band gap by 1eV.
Whereas the introduction of structural defects due to the organic linker
desaturation provided a shift in the HUMO as a result of the decrease in strut
coordination with the inorganic knots.
