Green Crop Yam-Derived Carbons: Off-Plane Active Sites for Oxygen Electroreduction Identified by First-Principles

Plant-derived nonprecious metal catalysts are considered one of the promising candidates of platinum for oxygen reduction reaction (ORR). In this work, the typical microscopic morphology of fresh green crop yam is first detected by cryoscanning electronic microscopy. Using the green and widely sourced yam with spherical starch in nature as a precursor, well-defined spherical carbons are prepared via hypersaline-assisted hydrothermal carbonization and NH3activation, featuring a high heteroatom doping level and a hierarchical porous structure. Experimental results and density functional theory (DFT) calculations reveal that diverse off-plane Fe–Nx–Cy ensembles on the spherical carbons trigger the high performance that exceeds state-of-art Pt/C and most reported carbon catalysts toward ORR in a KOH solution. The increased charge density and the bond length of Fe coordinated in the sites should be responsible for the significantly improved property. The easily editing of off-plane active sites from the simple carbon morphology may shed light on optimizing nonprecious carbons as next-generation catalysts for ORR.