Atomically Dispersed Co–S–N Active Sites Anchored on Hierarchically Porous Carbon for Efficient Catalytic Hydrogenation of Nitro Compounds

It is highly desired but challenging to develop non-noble metal-based hydrogenation catalysts that can replace noble metal-based ones for selective reduction of nitro compounds into amino compounds. Herein, we reported a hierarchically porous carbon-supported N,S dual-coordinated cobalt single-atom catalyst (Co 1 /NSC-AT) for hydrogenation of nitro compounds. The unique coordination environment of Co centers, combined with the hierarchically porous structure of carbon supports, endows Co 1 /NSC-AT with an excellent catalytic performance; the hydrogenation reaction can be efficiently performed under mild conditions (35 °C, ∼1bar H 2 ) with high conversion and selectivity. The theoretical calculation reveals that the N,S dual-coordinated cobalt single-atom center (Co 1 S 1 N 3 ) in Co 1 /NSC-AT acts as an active site for the hydrogenation reaction. Co 1 S 1 N 3 possesses a lower reaction barrier for the rate-determining step than Co 1 N 4 and Co nanoparticles. Moreover, N,S dual-coordinated environments can tailor the electronic structures of Co single atoms, which facilitate the desorption of H from the active sites, thus promoting the hydrogenation process.