ZnS anchored on porous N, S-codoped carbon as superior oxygen reduction reaction electrocatalysts for Al-air batteries.

The development of non-precious based oxygen reduction reaction (ORR) catalysts with outstanding catalytic performance is desirable but still a grand challenge for practical Al-air battery. Herein, we report a vulcanization-assisted pyrolysis strategy for creating zeolitic imidazolate framework-derived catalysts with a N, S co-doped carbon support and highly exposed ZnS and Zn-N sites. The trithiocyanuric acid (TCA) is found not only to introduce S into the carbon derived from ZIF-8 and ZnS to adjust the electronic structure of carbon matrix during the pyrolysis, but also result in a shrinkage of carbon framework with a hierarchical porous structure. Such an architecture boosts abundant active sites exposed and accelerates remote mass transportation. As a result, the optimized 3.5ZnS/NSC-NaCl-900 delivers an impressive enhanced performance toward ORR in alkaline medium with a high half-wave potential of 0.905 V (vs. reversible hydrogen electrode), which is superior to most of non-precious metal-based catalysts. Density functional theory calculations unveil that the ZnS in 3.5ZnS/NSC-NaCl-900 can effectively lower the Gibbs energy barrier of crucial steps and therefore promotes the reaction kinetics. Furthermore, 3.5ZnS/NSC-NaCl-900 also displays greater power density and specific capacity than Pt/C in Al-air batteries.