Synergetic Molecular Oxygen Activation and Catalytic Oxidation of Formaldehyde over Defective MIL-88B(Fe) Nanorods at Room Temperature

Defective MIL-88B­(Fe) nanorods are exploited as exemplary iron-bearing metal–organic framework (MOF) catalyst for molecular oxygen (O2) activation at ambient temperature, triggering effective catalytic oxidation of formaldehyde (HCHO), one of the major indoor air pollutants. Defective MIL-88B­(Fe) nanorods, growing along the [001] direction, expose abundant coordinatively unsaturated Fe-sites (Fe-CUSs) along extended hexagonal channels with a diameter of ca. 5 Å, larger enough for the diffusion of O2 (3.46 Å) and HCHO (2.7 Å). The Lewis acid–base interaction between Fe-CUSs and accessible HCHO accelerates the FeIII/FeII cycle, catalyzing Fenton-like O2 activation to produce reactive oxidative species (ROSs), including superoxide radicals (•O2 –), hydroxyl radicals (•OH), and singlet oxygen (1O2). Consequently, adsorbed HCHO can be oxidized into CO2 with a considerable mineralization efficiency (over 80%) and exceptional recyclability (4 runs, 48 h). Dioxymethylene (CH2OO), formate (HCOO–) species, and formyl radicals (•CHO) are recorded as the main reaction intermediates during HCHO oxidation. HCHO, H2O, and O2 are captured and activated by abundant FeIII/FeII-CUSs as acid/base and redox sites, triggering synergetic ROS generation and HCHO oxidation, involving cooperative acid–base and redox catalysis processes. This study will bring new insights into exploiting novel MOF catalysts for efficient O2 activation and reliable indoor air purification at ambient temperature.