Room-temperature hydrogenation of halogenated nitrobenzenes over metal–organic-framework-derived ultra-dispersed Ni stabilized by N-doped carbon nanoneedles

Abstract

Ultra-dispersed Ni nanoparticles (7.5 nm) on nitrogen-doped carbon nanoneedles (Ni@NCNs) were prepared by simple pyrolysis of Ni-based metal–organic-framework for selective hydrogenation of halogenated nitrobenzenes to corresponding anilines. Two different crystallization methods (stirring and static) were compared and the optimal pyrolysis temperature was explored. Ni@NCNs were systematically characterized by wide analytical techniques. In the hydrogenation of p-chloronitrobenzene, Ni@NCNs-600 (pyrolyzed at 600 °C) exhibited extraordinarily high performance with 77.9 h^–1 catalytic productivity and > 99% p-chloroaniline selectivity at full p-chloronitrobenzene conversion under mild conditions (90 °C, 1.5 MPa H₂), showing obvious superiority compared with reported Ni-based catalysts. Notably, the reaction smoothly proceeded at room temperature with full conversion and > 99% selectivity. Moreover, Ni@NCNs-600 afforded good tolerance to various nitroarenes substituted by sensitive groups (halogen, nitrile, keto, carboxylic, etc.), and could be easily recycled by magnetic separation and reused for 5 times without deactivation. The adsorption tests showed that the preferential adsorption of –NO₂ on the catalyst can restrain the dehalogenation of p-chloronitrobenzene, thus achieving high p-chloroaniline selectivity. While the high activity can be attributed to high Ni dispersion, special morphology, and rich pore structure of the catalyst.

Graphical abstract

Keywords

halogenated nitrobenzenes / room-temperature hydrogenation / Ni nanoparticles / nitrogen-doped carbon nanoneedles / metal–organic-framework

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Acknowledgements

This work was supported by the National Key R&D Program of China (Grant No. 2021YFC2103704), the National Natural Science Foundation of China (Grant Nos. 21878266 and 22078288), the Science and Technology Research Project of Henan Province (Grant No. 222300420527), and Program of Processing and Efficient Utilization of Biomass Resources of Henan Center for Outstanding Overseas Scientists (Grant No. GZS2022007).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at http://dx.doi.org/10.1007/s11705-022-2220-9 and is accessible for authorized users.

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