Metal-Organic Framework-Supported Mono Bipyridyl-Iron Hydroxyl Catalyst for Selective Benzene Hydroxylation into Phenol.

Direct hydroxylation of benzene to phenol is more appealing in the industry for the economic and environmentally friendly phenol synthesis than the conventional cumene process. We have developed a UiO-metal-organic framework (MOF)-supported mono bipyridyl-Iron(II) hydroxyl catalyst [bpy-UiO-Fe(OH)2] for the selective benzene hydroxylation into phenol using H2O2 as the oxidant. The heterogeneous bpy-UiO-Fe(OH)2 catalyst showed high activity and remarkable phenol selectivity of 99%, giving the phenol mass-specific activity up to 1261 mmolPhOHgFe-1 h-1 at 60 °C. Bpy-UiO-Fe(OH)2 is significantly more active and selective than its homogeneous counterpart, bipyridine-Fe(OH)2. This enhanced catalytic activity of bpy-UiO-Fe(OH)2 over its homogeneous control is attributed to the active site isolation of the bpy-Fe(OH)2 moiety by the solid MOF that prevents intermolecular decomposition. Moreover, the exceptional selectivity of bpy-UiO-Fe(OH)2 in benzene to phenol conversion is originated via shape-selective catalysis, where the confined reaction space within the porous UiO-MOF prevents the formation of larger overoxidized products such as hydroquinone or benzoquinone, leading to the formation of only smaller-sized phenol after monohydroxylation of benzene. Spectroscopic and controlled experiments and theoretical calculations elucidated the reaction pathway, in which the in situ generated •OH radical mediated by bpy-UiO-FeII(OH)2 is the key species for benzene hydroxylation. This work underscores the significance of MOF-supported earth-abundant metal catalysts for sustainable production of fine chemicals.