Asymmetric Coordination of Single‐Atom Co Sites Achieves Efficient Dehydrogenation Catalysis

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 CH 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.