Zn-Induced Synthesis of Porous Fe-N,S-C Electrocatalyst with Iron-Based Active Sites Containing Sulfides, Oxides and Nitrides for Efficient Oxygen Reduction and Zinc-Air Batteries.

There is an urgent need to design and synthesize non-noble metal electrocatalysts (NNMEs) for the replacement of platinum-based electrocatalysts to enhance the sluggish oxygen reduction reaction (ORR) for Zn-air batteries and fuel cells. Herein, Fe-N,S-C materials were fabricated through two steps: first, reprecipitating hemin by adjusting the pH and, then, decorating it with melamine and cysteine in the presence of Zn. The resulting Fe-N,S-C-950 (Zn) was prepared after pyrolysis at 950 °C. Using this method, abundant iron-based active species with good dispersion were obtained. The fabrication of more micropores in Fe-N,S-C-950 (Zn) plays a positive role in the improvement of ORR activity. On comparison, Fe-N,S-C-950 (Zn) outperforms Fe-N,S-C-950 and Fe-N-C-950 (Zn) with respect to the ORR due to its larger specific surface area, porous structure, multiple iron-based active sites and N- and S-doped C. Fe-N,S-C-950 (Zn) achieves outstanding ORR performances, including a half-wave potential (E) of 0.844 V and 0.715 V versus a reversible hydrogen electrode (RHE) in 0.1 M KOH and 0.1 M HClO solution, respectively. In addition, Fe-N,S-C-950 (Zn) shows an outstanding Zn-air battery performance with an open-circuit voltage (OCV) of 1.450 V and a peak power density of 121.9 mW cm, which is higher than that of 20 wt% Pt/C. As a result, the as-prepared electrocatalyst in this work shows the development of the Zn-assisted strategy combined with the assembly of porphyrins as NNMEs for the enhancement of the ORR in both alkaline and acidic solutions.