Metal-organic frameworks (MOFs) based on titania secondary building units are porous crystals that exhibit exceptional photoredox activity. MOFs like MIL-125—the prototypical titanium MOF photocatalyst—has shown limited substrate uptake and limited photocatalytic activity, attributed to small pore windows. Here, we present the design, synthesis, and photocatalytic activity of a library of photoredox active titania MOFs based on a hex rod-packed net of titania nanowires connected through oligo-p-phenylene dicarboxylate links (UCFMOF-n, where n = # of phenyl rings). UCFMOFs with formula Ti6O9[MTVlinks]3 contain one-dimensional pores that increase in size, and electron donating group (EDG) functionalization. We show that UCFMOFs feature increased substrate uptake which, in combination with decreased optical bandgaps, results in superior visible light driven catalysis benzyl alcohol. Specifically, UCFMOF-4 with an MTV composition of 30% EDG links results in a 25% increase in substrate uptake and almost 20x photocatalytic rates with respect to MIL-125. This work emphasizes the roles of pore size, composition, and electronic structure on the photoredox catalysis in titania MOFs and how these parameters should be addressed when designing new MOF photocatalysts.

Designing titania metal-organic framework photocatalysts using the principles of reticular chemistry

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