Highly dispersed Ru anchored on nanosheet N-doped carbon for efficient and chemoselective hydrogenation of nitroaromatics to aromatic amines under mild conditions

Abstract An efficient catalyst for chemoselective hydrogenation of nitroaromatics to produce aromatic amines under mild conditions is highly desirable. In this work, a series of N-doped carbon (NC-x) with high nitrogen contents were firstly synthesized by pyrolysis of 1-butyl-3-vinylimidazolium bromide-co-acrylonitrile with a template of g-C3N4. Furthermore, Ru/NC-x catalysts were successfully prepared by ultrasonic-assisted impregnation method. The catalysts were characterized by various methods in details, e.g.X-ray diffraction, N2 physical adsorption-desorption, Transmission electron microscopy, Raman spectra, Scanning electron microscopy, H2 temperature programmed reduction. Characterization results revealed that N-doping on carbon was contributed to the high dispersion of Ru nanoparticles and resulted in the forming of the electron-deficient of Ru species. Nanosheet Ru/NC-2 with high N-doping content of 28 wt.% exhibited superior performance under room temperature, i.e., nitrobenzene conversion >99.0% and aniline selectivity 98.4%. Kinetic study indicated that the hydrogenation of nitrobenzene over Ru/NC-2 was the first-order kinetics with an intrinsic activation energy of 43.7 kJ/mol. Density functional theory calculation results suggested that Ru-Nx species, especially, Ru-pyrrolic-N facilitated nitrobenzene adsorption and H2 dissociation, resulting in enhanced catalytic performance. In addition, the excellent stability of Ru/NC-2 could be essentially reserved for 410 h in fixed-bed reactor. Moreover, Ru/NC-2 exhibited superior performance for the hydrogenation of various nitroaromatics to produce corresponding aromatic amines. This work could provide meaningful guidance on designing effective and stable catalyst for chemoselective hydrogenation of nitroaromatics to synthesize aromatic amines under mild conditions.