Tuning the p‐Orbital Electron Structure of s‐Block Metal Ca Enables a High‐Performance Electrocatalyst for Oxygen Reduction

Abstract

Most previous efforts are devoted to developing transition metals as electrocatalysts guided by the d-band center model. The metals of the s-block of the periodic table have so far received little attention in the application of oxygen reduction reactions (ORR). Herein, a carbon catalyst with calcium (Ca) single atom coordinated with N and O is reported, which displays exceptional ORR activities in both acidic condition (E_1/2 = 0.77 V, 0.1 m HClO₄ ) and alkaline condition (E_1/2 = 0.90 V, 0.1 m KOH). The CaN, O/C exhibits remarkable performance in zinc-air battery with a maximum power density of 218 mW cm^-2 , superior to a series of catalysts reported so far. X-ray absorption near-edge structure (XANES) characterization confirms the formation of N- and O-atom-coordinated Ca in the carbon matrix. Density functional theory (DFT) calculations reveal that the high catalytic activity of main-group Ca is ascribed to the fact that its p-orbital electron structure is regulated by N and O coordination so that the highest peak (E_P ) of the projected density of states (PDOS) for the Ca atom is moved close to the Fermi level, thereby facilitating the adsorption of ORR intermediates and electron transfer.