Rh Catalyzed Selective Hydrogenation of Nitroarenes under Mild Conditions: Understanding the Functional Groups Attached to the Nanoparticles

Abstract

AbstractModifying the surface of metal catalyst is a crucial subject for improving the heterogeneous metal catalysts. It is still a great challenge to understand the structure‐activity relationship (SAR) between the surface supporting groups and the metal particles. Herein, Rh NPs supported on the magnetic silica sphere with various functional groups (−NH2, −SH, −SO3H, −N=CH2, −Cl, −NHCOCH3 and −NHCH2Ph) have been prepared for catalytic hydrogenation of nitroarenes under atmospheric pressure at room temperature. We discover that the chemical state of Rh NPs depends on the supporting groups significantly. The electron‐donating functionalities can effectively elevate the Rh0/Rh3+ ratio, which increase the catalytic performance both in conversion and selectivity. The amino group decorated catalyst has such a good selectivity that no dechlorination reaction is observable in the hydrogenation of 2‐chloro‐3‐nitropyridine. What's more, by introducing magnetic Fe3O4 nuclei and mesoporous silica encapsulating layer, the catalyst can be recovered conveniently by an external magnet, and can be reused 10 cycles without any loss of activity.