Highly Active Ni Nanoparticles on N‐doped Mesoporous Carbon with Tunable Selectivity for the One‐Pot Transfer Hydroalkylation of Nitroarenes with EtOH in the Absence of H2

Abstract Cost‐effective and environmentally friendly conversion of nitroarenes into value‐added products is desirable but still challenging. In this work, highly dispersed Ni nanoparticles (NPs) supported on N‐doped mesoporous carbon (Ni/NC‐x) were synthesized via novel ion exchange‐pyrolysis strategy. Their catalytic performance was investigated for one‐pot transfer hydroalkylation of nitrobenzene (NB) with EtOH in absence of H 2 . Interestingly, the catalytic performance could be easily manipulated by tuning the morphology and electronic state of Ni NPs via varying the pyrolysis temperature. It was found that the Ni/NC‐650 achieved 100 % nitrobenzene conversion and approx. 90 % selectivity of N,N‐diethyl aniline at 240 °C for 5 h, more active than those of homogeneous catalysts or supported Ni catalysts prepared by impregnation (Ni/NC‐650‐IM, Ni/SiO 2 ). This can be ascribed to the higher dispersion and better reducibility as well as richer surface basicity of the catalyst. More interestingly, the Ni/NC‐650 catalyst achieved complete conversion of various nitroarenes, yielding imines, secondary amines, or tertiary amines selectively by simply controlling the reaction temperature at 180, 200 and 240 °C, respectively. The one‐pot hydrogen‐free process with non‐noble metal catalysts, as demonstrated in this work, shows great promise for selective conversion of nitroarenes with ethanol to various anilines at industrial scale, from an economic, environmental, and safety viewpoint.