Engineering adjacent N, P and S active sites on hierarchical porous carbon nanoshells for superior oxygen reduction reaction and rechargeable Zn-air batteries

Heteroatom-doped carbon materials have been regarded as sustainable alternatives to the noble-metal catalysts for oxygen reduction reaction (ORR), while the catalytic performances still remain unsatisfactory. Herein, we develop a metal-free adjacent N, P and S-codoped hierarchical porous carbon nanoshells (NPS-HPCNs) through a novel layer-by-layer template coating method. The NPS-HPCNs is rationally fabricated by crosslinking of polyethyenemine (PEI) and phytic acid (PA) on nano-SiO2 template surface and subsequently coating of viscous sulfur-bearing petroleum pitch, followed by pyrolysis and alkaline etching. Soft X-ray absorption near-edge spectroscopy (XANES) analysis and density functional theory (DFT) calculations prove the engineering of adjacent N, P and S atoms to generate synergistic and reinforced active sites for oxygen electrocatalysis. The NPS-HPCNs manifests excellent ORR activity with a half-wave potential (E1/2) of 0.86 V, as well as promoted durability and methanol tolerance in alkaline medium. Remarkably, the NPS-HPCNs-based Zn-air battery delivers an open-circuit voltage of 1.479 V, a considerable peak power density of 206 mW cm-2 and robust cycling stability (over 200 h), even exceeding the commercial Pt/C catalyst. This study offers fundamental insights into the construction and synergistic mechanism of adjacent heteroatoms on carbon substrate, providing advanced metal-free electrocatalysts for Zn-air batteries and other energy conversion and storage devices.