Monitoring Mechanical, Electronic, and Catalytic Trends in a Titanium Metal Organic Framework Under the Influence of Guest-Molecule Encapsulation Using Density Functional Theory

In this study, we conduct a density functional theory investigation to study the mechanical stability of a titanium-based metal organic framework (MOF-901), which was hypothetically assumed to possess 2D characteristics. It is systematically found that the encapsulation of methanol enhances the mechanical stability of MOF-901 as the elastic tensors C(ij) of MOF-901∙nMeOH are higher than the corresponding C(ij) quantities reported for solvent-free MOF-901. Moreover, the 2D characteristics of MOF-901 is confirmed by verifying the negative values of C(33). At the same time, the band gap of MOF-901 is observed to be solvent-dependent. In its pure form, MOF-901 possesses a direct gap (E(g)) of 2.07 eV, with the valence and conduction bands mainly constituted by electrons of 4-aminobenzoate linkers. Introducing methanol into MOF-901 causes distortion to the 4-aminobenzoate geometry, thereby induces electronic degeneracy to the conduction bands. Consequently, E(g) is narrowed to 1.84 eV with 5.7 wt% MeOH or 1.63 eV with 11.4 wt% MeOH. Hence, it is possible to tailor the band gap of MOF-901 by controlling methanol guest, which only acquires van der Waals interaction to the framework. In addition, our theoretical prediction shows a Ti(IV) site can undergo electronic hopping to become Ti(III) under the effect of visible light (~440–443 nm). Then, Ti(III) is capable of breaking the C-Br bond in ethyl α-bromophenylacetate spontaneously, which in turn activates the polymerization of methyl methacrylate with an energy barrier of 0.30 eV.