Abstract
The emergence of Mo-based hybrid zeolitic imidazolate frameworks (HZIFs) with MoO(4)units brings substantial advantages to design and synthesize complex Mo-based electrocatalyst that are not expected in their conventional synthesis path. Herein, as a newly proposed concept, a facile temperature-induced on-site conversion approach (TOCA) is developed to realize the transformation of MoO(4)units to C-Mo-S triatomic coordination in hierarchical hollow architecture. The optimized hybrid (denoted as MoCS(x)1000) shows accelerating oxygen reduction reaction (ORR) kinetics and excellent stability, which are superior to the most reported Mo-based catalysts. Extended X-ray adsorption fine structure (EXAFS) analysis and computational studies reveal that the near-range electronic steering at C-Mo-S triatomic-coordinated nanointerface guarantees moderate ORR intermediates adsorption and thus is responsible for the boosted ORR activity. This work sheds light on exploring the intrinsic activity of catalysts by interfacial electronic steering.