Planar Chlorination Engineering: A Strategy of Completely Breaking the Geometric Symmetry of Fe-N₄ Site for Boosting...

Introducing asymmetric elements and breaking the geometric symmetry of traditional metal-N₄ site for boosting oxygen reduction reaction (ORR) are meaningful and challenging. Herein, the planar chlorination engineering of Fe-N₄ site is first proposed for remarkably improving the ORR activity. The Fe-N₄/CNCl catalyst with broken symmetry exhibits a half-wave potential (E_1/2) of 0.917 V versus RHE, 49 and 72 mV higher than those of traditional Fe-N₄/CN and commercial 20 wt% Pt/C catalysts. The Fe-N₄/CNCl catalyst also has excellent stability for 25 000 cycles and good methanol tolerance ability. For Zn-air battery test, the Fe-N₄/CNCl catalyst has the maximum power density of 228 mW cm^-2 and outstanding stability during 150 h charge-discharge test, as the promising substitute of Pt-based catalysts in energy storage and conversion devices. The density functional theory calculation demonstrates that the adjacent C─Cl bond effectively breaks the symmetry of Fe-N₄ site, downward shifts the d-band center of Fe, facilitates the reduction and release of OH^*, and remarkably lowers the energy barrier of rate-determining step. This work reveals the enormous potential of planar chlorination engineering for boosting the ORR activity of traditional metal-N₄ site by thoroughly breaking their geometric symmetry.