Asymmetric Coordination of Single‐Atom Co Sites Achieves Efficient Dehydrogenation Catalysis
Hu Liu, Qian Lei, Ruoyan Miao, Mingzi Sun, Chuanjian Qin, Liang Zhang, Gan Ye, Yao Yao, Bolong Huang, Zhenhui Ma
Abstract
Abstract Tuning asymmetric coordination of metal single‐atom (SA) sites can provide a new opportunity for optimizing the electronic structure of catalysts to achieve efficient catalysis, however, achieving such controllable design remains a grand challenge. Herein, an asymmetrically coordinated Co‐N 4 P SA site as a new catalyst system for achieving superior dehydrogenation catalysis of formic acid (HCOOH) is reported. The experimental results show that the Co atom is coordinated by four N atoms and one asymmetric P atom, forming the unique Co‐N 4 P SA sites. The Co‐N 4 P SA sites exhibit an impressive mass activity of 4285.6 mmol g –1 h –1 with 100% selectivity and outstanding stability for HCOOH dehydrogenation catalysis at 80 °C, which is 5.0, 25.5, and 23.1 times that of symmetrically coordinated Co‐N 4 SA sites, commercial Pd/C and Pt/C, respectively. The in situ ATR‐IR analysis demonstrates the mono‐molecular H 2 produced mechanism over Co‐N 4 P SA sites, and theoretical calculations further reveal that the asymmetric P sites not only can boost the CH bond cleavage of HCOO* by largely reducing the energy barrier but also facilitate the proton adsorption to achieve the fast generation of H 2 in Co‐N 4 P SA sites. This study opens a new way for rationally designing novel SA sites to achieve efficient catalysis.