Electronic Asymmetry Engineering of Fe–N–C Electrocatalyst via Adjacent Carbon Vacancy for Boosting Oxygen Reduction Reaction

• Published in: Advanced science 2023-11, Vol.10 (32), p.e2305194-e2305194
• Main Authors: Tu, Huanlu, Zhang, Haixia, Song, Yanhui, Liu, Peizhi, Hou, Ying, Xu, Bingshe, Liao, Ting, Guo, Junjie, Sun, Ziqi
• Format: Article
• Language: English
• Subjects: Adsorption; Asymmetry; Carbon; Catalysis; electronic asymmetry engineering; Energy; Etching; Fe–N–C catalysts; Morphology; Nanoparticles; oxygen reduction reaction; Spectrum analysis; Symmetry; universal pH range
• ISSN: 2198-3844; 2198-3844
• DOI: 10.1002/advs.202305194

Single‐atomic transition metal–nitrogen–carbon (M–N–C) structures are promising alternatives toward noble‐metal‐based catalysts for oxygen reduction reaction (ORR) catalysis involved in sustainable energy devices. The symmetrical electronic density distribution of the M─N 4 moieties, however, leads to unfavorable intermediate adsorption and sluggish kinetics. Herein, a Fe–N–C catalyst with electronic asymmetry induced by one nearest carbon vacancy adjacent to Fe─N 4 is conceptually produced, which induces an optimized d‐band center, lowered free energy barrier, and thus superior ORR activity with a half‐wave potential ( E 1/2 ) of 0.934 V in a challenging acidic solution and 0.901 V in an alkaline solution. When assembled as the cathode of a Zinc–air battery (ZAB), a peak power density of 218 mW cm −2 and long‐term durability up to 200 h are recorded, 1.5 times higher than the noble metal‐based Pt/C+RuO 2 catalyst. This work provides a new strategy on developing efficient M–N–C catalysts and offers an opportunity for the real‐world application of fuel cells and metal–air batteries.