Electrocatalytic, Kinetic, and Mechanism Insights into the Oxygen‐Reduction Catalyzed Based on the Biomass‐Derived FeO<i>_x</i>@N‐Doped Porous Carbon Composites

Abstract

A valid strategy for amplifying the oxygen reduction reaction (ORR) efficiency of non-noble electrocatalyst in both alkaline and acid electrolytes by decorated with a layer of biomass derivative nitrogen-doped carbon (NPC) is proposed. Herein, a top-down strategy for the generally fabricating NPC matrix decorated with trace of metal oxides nanoparticles (FeO_x NPs) by a dual-template assisted high-temperature pyrolysis process is reported. A high-activity FeO_x /FeNC (namely Hemin/NPC-900) ORR electrocatalyst is prepared via simply carbonizing the admixture of Mg₅ (OH)₂ (CO₃ )₄ and NaCl as dual-templates, melamine and acorn shells as nitrogen and carbon source, hemin as a natural iron and nitrogen source, respectively. Owing to its unique 3D porous construction, large BET areas (819.1 m² ∙g^-1 ), and evenly dispersed active sites (FeN_x , CN, and FeO parts), the optimized Hemin/NPC-900 catalyst displays comparable ORR catalytic activities, remarkable survivability to methanol, and preferable long-term stability in both alkali and acid electrolyte compared with benchmark Pt/C. More importantly, density function theory computations certify that the interaction between Fe₃ O₄ nanoparticles and arm-GN (graphitic N at armchair edge) active sites can effectually promote ORR electrocatalytic performance by a lower overpotential of 0.81 eV. Accordingly, the research provides some insight into design of low-cost non-precious metal ORR catalysts in theory and practice.