A Pre‐Coordinated Strategy Precisely Tailors the Coordination Structure of Single‐Atom Sites Toward Efficient Catalysis
Fengliang Cao, Qingshan Zhao, Xiaojie Tan, Qian Xu, Libo Wang, Biao Zhu, Yue Yan, Debin Kong, Linjie Zhi, Mingbo Wu
Abstract
Abstract Coordination structure engineering represents a promising approach for optimizing the catalytic properties of single‐atom catalysts (SACs). However, the precise tailoring of single‐atom sites remains challenging. Herein, a pre‐coordination strategy is proposed to design SACs with tunable local coordination environments on 2D honeycomb‐like carbon nanofoams. By pre‐coordinating the metal precursor with customized functional groups on a layered Mg(OH) 2 template through strong d‐p orbital hybridization, SACs featuring Co─N 4 (Co 1 /NC), Co─C 4 (Co 1 /CC), and Co─C 2 S 2 (Co 1 /CSC) configurations are fabricated. The lamellar honeycomb‐like architecture facilitates active site exposure, reactant enrichment, and mass transfer during the reaction process. Consequently, the Co 1 /NC catalyst, despite its extremely low Co loading of 0.12 wt.%, demonstrates exceptional catalytic activity and stability for nitroaromatics reduction, achieving an impressive overall turnover frequency (TOF) of 73668 h −1 for the conversion of 4‐nitrophenol to 4‐nitroaniline, surpassing most reported catalysts. Theoretical calculations indicate the Co─N 4 configuration possesses moderate Fermi electronic states compared to Co─C 4 and Co─C 2 S 2 , significantly promoting the formation and utilization of reactive H * species and accelerating the reaction kinetics for aromatic nitroreduction. This work establishes a novel avenue for the meticulous manipulation of coordination structures in SACs, paving the way for the advancement of sophisticated catalytic materials for chemical transformations.