A Stable Metal Chalcogenide Cluster-Based Framework Decorated with Transition Metal Complexes for an Efficient Electrocatalytic O2 Reduction Reaction.

Highly efficient and stable non-Pt-based electrocatalysts for oxygen reduction reactions (ORRs) are highly desirable in energy conversion and storage systems. Herein, we report a hydrothermally synthesized metal chalcogenide cluster-based framework (NCF-3-Mn), which is decorated with transition metal complexes ([Mn(TEPA)]2+, TEPA = tetraethylenepentamine), for an electrocatalytic O2 reduction reaction (ORR). Benefitting from the abundant Mn-S bonds and Mn-N-C structures in NCF-3-Mn, it was found that NCF-3-Mn displayed a high onset potential (0.90 V) and an efficient four-electron transfer reaction pathway, which are much better than those of its analogue framework (T2-GaSbS). Moreover, NCF-3-Mn also exhibited a considerable long-term stability and methanol resistance toward ORRs. This work will present new opportunities for exploring the utilization of chalcogenide frameworks as novel non-Pt electrocatalysts for ORRs.