The facile production of p-chloroaniline facilitated by an efficient and chemoselective metal-free N/S co-doped carbon catalyst

The catalytic hydrogenation of the toxic and harmful p-chloronitrobenzene to produce the value-added p-chloroaniline is an essential reaction for the sustainable chemical industry. Nevertheless, ensuring satisfactory control of its chemoselectivity is a great challenge. In this work, a N/S co-doped metal-free carbon catalyst has been fabricated by using cysteine as a source of C, N, and S. The presence of calcium citrate (porogen agent) in the mixture subjected to pyrolysis provided the carbon with porosity, which permitted us to overcome the issues associated with the loss of heteroatoms during an otherwise necessary activation thermal treatment. Full characterization was carried out and the catalytic performance of the metal-free carbon material was tested in the hydrogenation reaction of p-chloronitrobenzene to selectively produce p-chloroaniline. Full selectivity was obtained but conversion was highly dependent on the introduction of S due to the synergetic effect of S and N heteroatoms. The N/S co-doped carbon (CYSCIT) exhibits a mesoporous architecture which favors mass transfer and a higher doping level, with more exposed N and S doping atoms which act as catalytic sites for the hydrogenation of p-chloronitrobenzene, resulting in enhanced catalytic performance when compared to the N-doped carbon obtained from melamine and calcium citrate (MELCIT) used as a reference.