Near-range modulation of single-atomic Fe sites by simultaneously integrating heteroatom and nanocluster for efficient oxygen reduction

Modulation strategies are widely developed to regulate electronic state of single-atom catalysts (SACs) to reinforce the catalytic activity of oxygen reduction reaction (ORR). However, the modulation effect using only single coordination regulation is often insufficient to optimize the electronic and geometric structure of metal active centers. Herein, a general strategy to modify the activity of single-atomic Fe site is achieved by dual decoration of Fe centers with contiguous sulfur atoms and metal nanoclusters via an aggregation-redispersion route. Under near-range engagement, the adjacent S atoms and Fe nanoclusters can break the symmetric electronic interface of Fe-N moiety, and act as the modulators to synergistically tune the electronic configurations of Fe centers, leading to less electron transfer to *OH, and subsequent favorable desorption. In situ spectroscopic characterization and theoretical results reinforces the significant roles of S atoms and metal clusters in tandem by correlating their induced electron redistribution with ORR activity, which ultimately accelerates the adsorption/desorption of oxygenated intermediates for robust catalytic performance. Due to the improvement of graphitization degree, carbon supports possess efficient active sites and exhibit superior anti-corrosion. The resultant FeNC-2 M demonstrates outstanding ORR activity with high power density, maintaining remarkable durability in Zn-air batteries and microbial fuel cells. This work provides effective and universal way to modulate microenvironment of single metal sites, facilitating the open up of potential application spaces for various SACs. [Display omitted] •Optimization of electronic and geometric structure of single-atomic Fe sites.•Dual decoration of Fe centers with contiguous sulfur atoms and metal nanoclusters.•Effect of decoration on breaking the symmetric electronic interface of Fe-N moiety.•Correlation of electron redistribution with ORR activity by spectroscopic study.•Outstanding ORR activity with high power density in ZAB and MFCs.