Advanced and Stable Metal-Free Electrocatalyst for Energy Storage and Conversion: The Structure–Effect Relationship of Heteroatoms in Carbon

[Image: see text] Ever-developing energy device technologies require the exploration of advanced materials with multiple functions. Heteroatom-doped carbon has been attracting attention as an advanced electrocatalyst for zinc–air fuel cell applications. However, the efficient use of heteroatoms and the identification of active sites are still worth investigating. Herein, a tridoped carbon is designed in this work with multiple porosities and high specific surface area (980 m(–2) g(–1)). The synergistic effects of nitrogen (N), phosphorus (P), and oxygen (O) in micromesoporous carbon on oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) catalysis are first investigated comprehensively. Metal-free N-, P-, and O-codoped micromesoporous carbon (NPO-MC) exhibits attractive catalytic activity in zinc–air batteries and outperforms a number of other catalysts. Combined with a detailed study of N, P, and O dopants, four optimized doped carbon structures are employed. Meanwhile, density functional theory (DFT) calculations are made for the codoped species. The lowest free energy barrier for the ORR can be attributed to the pyridine nitrogen and N–P doping structures, which is an important reason for the remarkable performance of NPO-MC catalyst in electrocatalysis.