Co-Ag alloy protected by nitrogen doped carbon as highly efficient and chemoselective catalysts for the hydrogenation of halogenated nitrobenzenes.

The design of lower-cost alternative heterogeneous catalysts for the hydrogenation of halogenated nitrobenzenes using green method to synthesize the corresponding anilines is highly desirable. In this study, Ag was incorporated into the Co-MOFs during the growing process (Co-Ag(n)-MOFs), and then followed the carbothermal reduction process without any additional procedures, we synthesized a series of Co-Ag(n)@NCs. The self-supported catalysts exhibited excellent and stable catalytic performances for the chemoselective hydrogenation of halogenated nitrobenzenes without obvious dehalogenation. The Co-Ag bimetallic alloy nanoparticles were well-dispersed and protected from aggregation and leaching by the porous nitrogen doped carbon. Besides, either hydrazine hydrate (N2H4·H2O, generating byproducts N2 and H2O) or H2 could be used as green reducing agent with excellent selectivity towards synthesizing the corresponding anilines. And when the Co/Ag content ratio was approximate 1:1, the Co-Ag(1:1)@NC showed the best catalytic performance. Moreover, the Co-Ag(1:1)@NC could be efficiently recovered by using an external magnetic force and reused without obvious decrease of catalytic activity. Thus, such highly efficient, inexpensive, stable and magnetically recyclable catalysts could show great potentials in practical applications for many important reactions.