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Highly Efficient Iron-Based Catalyst for Light-Driven Selective Hydrogenation of Nitroarenes

Jun Ma, Xin Mao, Canyu Hu, Xinyu Wang, Wanbing Gong, Dong Liu, Ran Long, Aijun Du, Huijun Zhao, Yujie Xiong

2023Journal of the American Chemical Society56 citationsDOI

Abstract

Light-driven hydrogenation of nitro compounds to functionalized amines is of great importance yet a challenge for practical applications, which calls for the development of high-performance, nonprecious photocatalysts and efficient catalytic systems. Herein, we report a high-efficiency Fe 3 O 4 @TiO 2 photocatalyst via a sol–gel and subsequent pyrolysis strategy, which exhibits desirable photothermal hydrogenation performance of nitro compounds to functionalized amines with the excellent selectivity of >90% exceeding those of the state-of-the-art heterogeneous photocatalysts. Our experimental results and theoretical calculations for the first time reveal that Fe 3 O 4 is the major active phase, and the strong metal–support interaction between Fe 3 O 4 and reducible TiO 2 further leads to performance improvement, taking advantage of the enhanced photothermal effect and the improved adsorption for the reactant and hydrazine hydrate. Notably, a variety of halonitrobenzenes and pharmaceutical intermediates can be completely converted to functionalized amines with high selectivities, even in gram-scale reactions. This work provides a new insight into the rational design of nonprecious photo/thermo-catalysts for other catalytic reactions.

Topics & Concepts

ChemistryCatalysisHydrazine (antidepressant)NitroCombinatorial chemistrySelectivityPhotocatalysisPhotothermal therapyHydrateRational designAdsorptionNanotechnologyOrganic chemistryMaterials scienceChromatographyAlkylNanomaterials for catalytic reactionsAdvanced Photocatalysis TechniquesCopper-based nanomaterials and applications