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Non-precious metal catalysts play a significant role in the field of hydrogenation. This study synthesized Co-BTC from cobalt nitrate hexahydrate and 1,3,5-tricarboxylic acid benzene. By changing the calcination temperature of Co-BTC in an inert atmosphere, a series of novel non-precious metal Co/C microsphere catalysts were successfully prepared. The composition and structure of the Co/C-n catalysts were characterised by FESEM, TEM, XRD, IR, XPS and BET. These results confirm that 1,3,5-benzenetricarboxylic acid provides a rich carbon matrix and metallic Co nanoparticles are generated by self-reduction on the carbon matrix. The graphite matrix formed during the calcination process has a rich pore structure and good dispersion of active components on the catalyst surface, which is very favourable for the catalytic reaction. In the hydrogenation of o-chloronitrobenzene (o-CNB) to o-chloroaniline (o-CAN), the Co/C-500 catalyst showed the best catalytic performance. At 80 °C and 2 MPa H2 for 60 minutes, the conversion rate of o-CNB reached 99% and the selectivity reached 99%. When the reaction takes 5 minutes, the conversion rate reaches 10.5%, and the TOF value reaches 36.3 h−1. The Co/C-500 catalyst can be easily recycled and reused after reaction with the help of a magnetic field. Moreover, this catalyst is also effective in the selective hydrogenation of other nitroaromatic hydrocarbons containing halogen or unsaturated groups to corresponding aniline. This simple and direct synthesis method may lead to the economic production of large-scale Co/C catalysts, which is an attractive prospect for the industrial trial production of corresponding aniline. [ABSTRACT FROM AUTHOR]