Electronically Modulated Defective Cu _1.81 S by FeN ₄ for High‐Performance Nitroarene Hydrogenation

Abstract Copper‐based catalysts are attractive for hydrogenation, exemplified by nitro‑group reduction to industrially important aromatic amines, but are limited by intrinsically weak H 2 activation arising from an inert electronic structure. Herein, a dual‐site catalyst is developed by integrating FeN 4 and defect‐rich Cu 1.81 S nanoparticles anchored on porous carbon (Cu 1.81 S/Fe 1 @PC) via a protein‐metal ion network‐derived route. Cu 1.81 S/Fe 1 @PC features a high specific surface area (1130 m 2 g −1 ) and a unique N, S‐codopant structure. Density functional theory reveals electron transfer from FeN 4 to Cu 1.81 S, and the abundant lattice defects in Cu 1.81 S, which lower the H─H dissociation barrier on Cu sites. At 120 °C and 10 bar H 2 , the as‐prepared Cu 1.81 S/Fe 1 @PC catalyst delivers >99% aniline yield with a turnover frequency of 625 h −1 , ranking among the most active Cu‐ or Fe‐based catalysts for nitroarene hydrogenation. This work provides a new approach for designing and preparing high‐performance dual‐site catalysts, applicable to, but not limited to, hydrogenation reactions.