Proton, Electron, and Hydrogen-Atom Transfer Thermodynamics of the Metal–Organic Framework, Ti-MIL-125, are Intrinsically Correlated to the Structural Disorder

Interfacial charge transfer reactions involving protons and/or electrons are fundamental to heterogeneous catalysis and many other reactions relevant to energy, chemical, and biological sectors. Metal–organic frameworks (MOFs) with redox-active metal-oxo nodes have emerged as candidate materials to examine these reactions with near-atomic-level precision, given their crystalline nature. Here, we employed a colloidally stable, Ti-based MOF, Ti-MIL-125, with different crystal sizes to examine the thermodynamics of proton-coupled electron transfer (PCET) reactions. The Ti8(μ2-O)8(μ2-OH)4 nodes structurally mimic TiO2, which have shown some PCET reactivity towards reactions of H2, O2, and others. In this report, we have demonstrated that a change in crystal size induces different amounts of structural disorder to the Ti-oxo node, further changing the thermodynamics of proton/electron/hydrogen-atom transfer reactions. Using electrochemical open-circuit potential (EOCP) measurements, we have determined that all crystallites undergo a 1H+/1e- redox reaction, which, given the stoichiometry, can be considered as a net H-atom transfer (HAT) reaction. The thermodynamics of this HAT reaction, the Ti3+O–H bond dissociation free energy (BDFE), was dependent on the crystal size of the MOF, as the decrease in crystal size induces more structural disorder. Our computational calculations have indicated that this difference in BDFE is due to a local change in the geometry of Ti cations, rather than the commonly invoked defects, such as the ‘missing-linker’ defect sites. Individual proton/electron transfer (PT/ET) thermodynamics were also highly dependent on the crystal sizes. These were probed using pKa or band gaps (Eg), respectively. These findings suggest that, particularly when MOFs are nanosized with a large amount of structural disorder, they should no longer be considered ‘true’ single-site catalysts; this is an implicit, but widespread assumption within the MOF-based catalysis field. Implications of these findings will be contrasted with structurally similar metal oxides like TiO2 and other redox-active MOFs.