Engineering Triple Phase Interface and Axial Coordination Design of Single‐Atom Electrocatalysts for Rechargeable Zn─air Batteries

Abstract Bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are highly desirable for rechargeable Zn─air batteries (rZABs). Herein, a space optimized 3D heterostructure Co‐N‐C@MoS ₂ catalyst with Co single atom and Co cluster sites is developed by pyrolysis of ZIF‐67 and in situ grown ultrathin MoS ₂ nanosheets. The introduced MoS ₂ not only has abundant defective structures, but also regulates the Co electronic distribution, thus introducing additional active sites and enhancing Co‐N _x activity. In addition, the MoS ₂ modification leads to an appropriate increase in hydrophilicity which can make a stable liquid/gas/solid triple phase interface, facilitating the approachability of electrolytes into the porous channels and promotes the mass transfer through ensuring a favorite contact among the catalyst, electrolyte and reactants and enhancing utility of active reaction sites. Comprehensive analysis and theoretical simulation indicate that the enhancement of activity stems from the axial coordination of Co cluster over Co single‐atom active sites to regulate local electronic structure, thereby optimizing the adsorption of ORR intermediates and enhancing the catalytic activity. Compared with the commercial Pt/C and IrO ₂ , the structurally optimized Co‐N‐C@MoS ₂ catalyst displays exceptional bifunctional electrocatalytic activity and long‐time stability toward both OER and ORR. Moreover, the Co‐N‐C@MoS ₂ catalyst exhibits higher peak power density and superior stability in liquid and flexible ZABs compared to the commercial Pt/C + IrO ₂ catalyst.