MIL-53 (Al) derived single-atom Rh catalyst for the selective hydrogenation of m-chloronitrobenzene into m-chloroaniline

Abstract The catalytic hydrogenation of halonitroarenes to haloanilines is a green and sustainable process for the production of key nitrogen-containing intermediates in fine chemical industry. Chemoselective hydrogenation poses a significant challenge, which requires the rational design of the catalysts with proper hydrogenation ability for nitro group and simultaneously preventing dehalogenation of halogen group. Herein, a highly effective Rh@Al2O3@C single-atom catalyst (SAC) was developed for the hydrogenation of m-chloronitrobenzene (m-CNB) to m-chloroaniline (m-CAN), through an in-situ grafting of metal during the assembly of MIL-53 (Al), followed by confined pyrolysis. Extensive characterizations reveal an exquisite structure of the Rh@Al2O3@C, containing atomically dispersed Rh sites onto Al2O3 confined by the amorphous carbon. The five-coordinated aluminum (AlV) species are essential for achieving the atomic dispersion of Rh atoms, providing the unsaturated coordinative sites for metal. Compared to the benchmark Rh/γ-Al2O3 and Rh/C nanocatalysts, the Rh@Al2O3@C SAC affords an excellent turnover frequency of 2317 molm-CNB·molRh–1·h–1, the highest value to date in heterogeneous catalyst systems for the hydrogenation of m-CNB at 313 K and 20 bar H2, together with a sustained selectivity to m-CAN (~98%) during five consecutive runs. The superior catalytic performance of the Rh@Al2O3@C is attributed to a proper modulation of electronic structure of hydrogenation metal by forming SAC, together with an enhanced accessibility of acid function sites.