Manipulating the Coordination Structure of Biomass‐Derived Zinc Single‐Atom Sites to Boost Selective Catalytic Hydrogenation of Nitroarenes

Constructing highly efficient and stable non‐noble metal catalysts for selective hydrogenation of nitroarenes is a very appealing yet challenging task in the fields of materials science and catalysis. Herein, a series of N‐doped carbon‐anchored Zn single‐atom catalysts were prepared by pyrolyzing the biomass‐based composite precursors composed of chitosan, tannic acid, and ZnCl 2 . The optimal sample of Zn‐Cl/NC‐3_900 displays superior catalytic activity with a turnover frequency of 4817 h −1 at 80°C, selectivity (∼99%), and recyclability (without any post‐treatment) for hydrogenation of p ‐chloronitrobenzene to p ‐chloroaniline with N 2 H 4 ·H 2 O. Its catalytic performance is well kept even after HCl or KSCN treatments, revealing excellent chemical stability and anti‐poisoning capability. Additionally, a very high p ‐chloroaniline selectivity (∼98%) could be obtained under mild conditions (1.0 MPa, 100°C) when H 2 is used as reductant. Characterization results and theory calculations demonstrate that introducing an appropriate amount of N/Cl species may finely modulate the local coordination environments of Zn single‐atoms. The resultant axially Cl‐coordinated ZnN 2 sites (Zn‐N 2 Cl) possess moderated adsorption/desorption capability and lower activation barriers, in line with the Sabatier principle, thereby significantly boosting the catalytic hydrogenation performance. This work provides a simple and effective approach for developing efficient hydrogenation catalysts through manipulating the coordination structure of metal single‐atom sites.