Herein, a highly stable, porous, multifunctional and metal-free catalyst was developed, which exhibited significant catalytic performance in the oxidation of amines and the transfer hydrogenation of nitriles under mild conditions.
The selective oxidation of aniline to metastable and valuable azoxybenzene,a zobenzene or nitrosobenzene has important practical significance in organic synthesis.However, uncontrollable selectivity and laborious synthesis of the expensive required catalysts severely hinders the uptake of these reactions in industrial settings.Herein, we have pioneered the discovery of Zr(OH) 4 as an efficient heterogeneous catalyst capable of the selective oxidation of aniline,u sing either peroxideo rO 2 as oxidant, to selectively obtain various azoxybenzenes,s ymmetric/unsymmetric azobenzenes,a sw ell as nitrosobenzenes,b ys imply regulating the reaction solvent, without the need for additives.M echanistic experiments and DFT calculations demonstrate that the activation of H 2 O 2 and O 2 is primarily achieved by the bridging hydroxyl and terminal hydroxyl groups of Zr(OH) 4 ,r espectively.T he present work provides an economical and environmentally friendly strategy for the selective oxidation of aniline in industrial applications.
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