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In this study, we report the fabrication of mesoporous assemblies of silver and TiO₂ nanoparticles (Ag/MTA) and demonstrate their catalytic efficiency for the selective reduction of nitroarenes. The Ag/TiO₂ assemblies, which show large surface areas (119-128 m²·g -1 ) and narrow-sized mesopores ( ca. 7.1-7.4 nm), perform as highly active catalysts for the reduction of nitroarenes, giving the corresponding aryl amines and N -aryl hydroxylamines with NaBH₄ and ammonia-borane (NH₃BH₃), respectively, in moderate to high yields, even in large scale reactions (up to 5 mmol). Kinetic studies indicate that nitroarenes substituted with electron-withdrawing groups reduced faster than those with electron-donating groups. The measured positive ρ values from the formal Hammett-type kinetic analysis of X -substituted nitroarenes are consistent with the proposed mechanism that include the formation of possible [Ag]-H hybrid species, which are responsible for the reduction process. Because of the high observed chemo selectivities and the clean reaction processes, the present catalytic systems, i.e. , Ag/MTA-NaBH₄ and Ag/MTA-NH₃BH₃, show promise for the efficient synthesis of aryl amines and N -aryl hydroxylamines at industrial levels.

Reduction of Nitroarenes into Aryl Amines and N-Aryl hydroxylamines via Activation of NaBH4 and Ammonia-Borane Complexes by Ag/TiO2 Catalyst