Asymmetrical anchor way of manganese atoms on carbon domain edge for enhanced oxygen reduction reaction

Abstract

Single atomic catalysts (SACs), especially the catalysts featured by well-developed M-N4 moieties, show excellent catalytic activity and spark enormous attention. However, the highly symmetric active sites may result in some degenerate electronic states for the d orbitals of the center metal atom, which suffer from the unsatisfactory adsorption-desorption behaviors during reaction. Herein, we develop an asymmetric anchor site by two types of nitrogen (sp-N and pyridinic N) created in the inherent edge-rich carbon domain of hydrogen-substituted graphdiyne (HsGDY), where atomic catalyst like manganese atoms can be asymmetrically anchored on the one side of hexagon carbon rings. The abundant elegant hexagon carbon rings on HsGDY not only facilitate the creation of edge sites, but also provide available space for the coordination of terminal ligands (OH) with Mn atoms. The as-synthesized Mn-N-HsGDY exhibits excellent ORR activity and an impressive long-term cyclability for over 3800 cycles in a rechargeable Zn-air battery.