Tunable Band Gaps in MUV-10(M): A Family of Photoredox-Active MOFs with Earth-Abundant Open Metal Sites

Abstract

<div> <div> <p>Titanium-based metal—organic frameworks (Ti-MOFs) attract intense research attention because they can store charges in the form of Ti3+ and they serve as photosensitizers for co-catalysts through heterogeneous photoredox reactions at the MOF-liquid interface. Both charge storage and charge transfer depend on redox potentials of the MOF and the molecular substrate, but the factors controlling these energetic aspects are not well understood. Additionally, photocatalysis involving Ti-MOFs relies on co-catalysts rather than the intrinsic Ti reactivity in part because Ti-MOFs with open metal sites are rare. Here, we report that the class of Ti-MOFs known as MUV-10 can be synthetically modified to include a range of redox-inactive ions with flexible coordination environments that control the energies of the photoactive orbitals. Lewis acidic cations installed in the MOF cluster (Cd, Sr , and Ba ) or introduced to the pores (H, Li, Na, K) tune the electronic structure and band gaps of the MOFs. Through use of optical redox indicators, we report the first direct measurement of the Fermi levels (redox potentials) of photoexcited MOFs in situ. Taken together, these results explain the ability of Ti-MOFs to store charges and provide design principles for achieving heterogeneous photoredox chemistry with electrostatic control.</p> </div> </div>

Dynamic metal-linker bonds in metal-organic frameworks

“…Early evidence of this effect was observed by VT diffuse-reflectance UV-Vis spectroscopy (VT-DRUVVis) of MUV-10(Ca), Ti3Ca3(μ3-O)2(1,3,5-benzenetricarboxylate)4(H2O)6. 57 Upon heating the material, absorption tails emerged as far as 2.0 eV below the low-temperature optical gap. Despite such a large effect, these tails disappeared upon cooling, thereby ruling out irreversible thermal degradation.…”