Atomically dispersed Ti-O clusters anchored on NH2-UiO-66(Zr) as efficient and deactivation-resistant photocatalyst for abatement of gaseous toluene under visible light

Photocatalytic oxidation (PCO) of volatile organic compounds (VOCs) over MOF-based photocatalysts is considerably impeded by the weak activation of reactant molecules on the catalyst surface and low charge carrier mobility. In this study, we demonstrate that atomically dispersed Ti species anchored on NH2-UiO-66(Zr) (AUiO-66(Zr/Ti)) exhibit high visible-light-responsive photocatalytic activity toward toluene vapor with an 83 % removal efficiency and 89 % CO2 selectivity. These results are markedly superior to those reported in the literature. More importantly, AUiO-66(Zr/Ti) exhibited excellent catalytic stability during a prolonged reaction, while its pristine AUiO-66(Zr) counterpart underwent rapid catalytic deactivation after a few hours. The optimized sample, AUiO-66(Zr/Ti)-4h, provided extended visible light absorption and enhanced charge carrier mobility due to ligand-to-linker metal charge transfer. Meanwhile, the defect-rich surface of AUiO-66(Zr/Ti)-4h facilitated the activation of H2O/toluene molecules into the critical intermediates of hydroxyl, benzoic acid, and maleic anhydride, which were effectively converted under visible light illumination. On the basis of the combined results of the PCO of toluene and material characterization, the structure − activity relationship and the related catalytic mechanism are discussed comprehensively.