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

doi:10.1007/s11705-022-2220-9

Front. Chem. Sci. Eng.

2022, Vol. 16

Issue (12) : 1782-1792 https://doi.org/10.1007/s11705-022-2220-9

RESEARCH ARTICLE

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

Yuemin Lin¹, Yuanyuan Zhang¹, Renfeng Nie²(

), Kai Zhou¹, Yao Ma¹, Mingjie Liu¹, Dan Lu¹, Zongbi Bao^1,³, Qiwei Yang^1,³, Yiwen Yang^1,³, Qilong Ren^1,³, Zhiguo Zhang^1,³(

)

¹. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China
². School of Chemical Engineering, Henan Center for Outstanding Overseas Scientists, Zhengzhou University, Zhengzhou 450001, China
³. Institute of Zhejiang University—Quzhou, Quzhou 324000, China

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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.

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

Corresponding Author(s): Renfeng Nie,Zhiguo Zhang

Online First Date: 03 November 2022 Issue Date: 19 December 2022

Cite this article:

Yuemin Lin,Yuanyuan Zhang,Renfeng Nie, et al. Room-temperature hydrogenation of halogenated nitrobenzenes over metal–organic-framework-derived ultra-dispersed Ni stabilized by N-doped carbon nanoneedles[J]. Front. Chem. Sci. Eng., 2022, 16(12): 1782-1792.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-022-2220-9
https://academic.hep.com.cn/fcse/EN/Y2022/V16/I12/1782

Fig.1 (a) Illustration for preparation of Ni@NCNs-T; (b) PXRD patterns of Ni-MOFs by different preparation methods.

Fig.2 SEM images of Ni-MOFs prepared by (a, b) stirring-crystallization and (c, d) static-crystallization.

Fig.3 (a) PXRD patterns, (b) Raman spectra, (c) N 1s and (d) Ni 2p XPS spectra of Ni@NCNs.

Fig.4 (a, b, c) SEM images of Ni@NCNs-600 at different nanoscales; (d, e) TEM images; (f) high resolution TEM image and SEAD patterns; (g) elemental mapping images of Ni@NCNs-600; (h, i) TEM images of Ni@NCNs-600-static. The insets in (e) and (i) show the size distributions of Ni nanoparticles.

Fig.5 (a) Proposed reaction routes for the hydrogenation of p-chloronitrobenzene. (b) Catalytic results of different catalysts for the selective hydrogenation of p-chloronitrobenzene to p-chloroaniline (reaction conditions: 53 mg p-chloronitrobenzene, 2.8 wt % equiv. catalyst, 2 mL ethanol, 80 °C, 2.0 MPa H₂, 60 min. * 787 mg p-chloronitrobenzene, 10 mg Ni@NCNs-600 catalyst, ethanol/H₂O (8/2, 10 mL), 90 °C, 1.5 MPa H₂, 60 min). (c) Saturated adsorption capacity of different substrates with Ni@NCNs-600. (d) Activity comparison of reported Ni-based catalysts for p-chloronitrobenzene hydrogenation to p-chloroaniline, the catalytic productivity is defined as the mole of converted p-chloronitrobenzene per mole of Ni per hour.

Fig.6 (a) Effect of water on the hydrogenation of p-chloronitrobenzene (reaction conditions: 53 mg p-chloronitrobenzene, 2.8 wt % equiv. Ni@NCNs-600 catalyst, 2 mL solvent, 80 °C, 2.0 MPa H₂, 30 min). (b) Effect of reaction temperature on the hydrogenation of p-chloronitrobenzene (reaction conditions: 53 mg p-chloronitrobenzene, 2.8 wt % equiv. Ni@NCNs-600 catalyst, 2 mL solvent (ethanol/H₂O = 8/2), 2.0 MPa H₂, 20 min). (c) Effect of hydrogen pressure on the hydrogenation of p-chloronitrobenzene (reaction conditions: 53 mg p-chloronitrobenzene, 2.8 wt % equiv. Ni@NCNs-600 catalyst, 2 mL solvent (ethanol/H₂O = 8/2), 90 °C, 20 min). (d) Effect of hydrogen pressure on the room-temperature hydrogenation of p-chloronitrobenzene (reaction conditions: 53 mg p-chloronitrobenzene, 2.8 wt % equiv. Ni@NCNs-600 catalyst, 1.5 mL solvent (ethanol/H₂O = 8/2), room temperature, 20 h).

Fig.7 (a) Recycling test of Ni@NCNs-600 in the hydrogenation of p-chloronitrobenzene (reaction conditions: 53 mg p-chloronitrobenzene, 2.8 wt % equiv. Ni@NCNs-600 catalyst, 2 mL solvent (ethanol/H₂O = 8/2), 90 °C, 1.5 MPa H₂, 20 min). (b) PXRD patterns of fresh and spent Ni@NCNs-600 catalysts. (c) The filtration experiment of Ni@NCNs-600 (reaction conditions: 53 mg p-chloronitrobenzene, 2.8 wt % equiv. Ni@NCNs-600 catalyst, 2 mL solvent (ethanol/H₂O = 8/2), 80 °C, 2 MPa H₂).

Tab.1 Selective hydrogenation of various sensitive-group-substituted nitroarenes ^a)

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