Atomically Dispersed Zn‐Nx Sites in N‐Doped Carbon for Reductive N‐formylation of Nitroarenes with Formic Acid

Abstract Replacement of noble metal catalysts with low‐cost, non‐noble heterogeneous catalysts is highly desirable. Herein, we prepared a reactive, inexpensive and stable isolated single‐atom Zn/N‐doped porous carbon (ZnNC) catalyst derived from a versatile zeolitic imidazolate framework precursor. The optimized ZnNC‐1000 with Zn‐N x species possesses high zinc loading (5.2 wt%) and nitrogen content (6.73 wt%), exhibits efficient catalytic performance in the one‐pot N‐formylation of nitroarene to the corresponding formamides by using formic acid as the hydrogen donor and formylation agent. H 2 ‐D 2 exchange reaction and HCOOH‐chemisorption experiments demonstrated that atomically dispersed Zn‐N x species are essential for the activation of hydrogen and HCOOH molecules, which finally contributed to the highest catalytic activity of ZnNC‐1000 for the reductive N‐formylation reaction.