Adjusting the electronic structure of the active center is a highly effective strategy for improving the performance of catalysts. Herein, we report an atomically dispersed catalyst (FeCl1N4/CNS), which realized for the first time a great improvement of the ORR by controlling the electronic structure of the central metal with a coordinated chlorine. The half-wave potential of FeCl1N4/CNS is E_1/2 = 0.921 V, which is the highest among the reported values for non-precious metal electrocatalysts and far exceeds that of FeN4/CN and commercial Pt/C in alkaline solution. Besides an exceptionally high kinetic current density (J_k) of 41.11 mA cm⁻² at 0.85 V, it also has a good methanol tolerance and outstanding stability. Experiments and DFT demonstrated that the near-range interaction with chlorine and the long-range interaction with sulfur of Fe modulated the electronic structure of the active site, thus resulting in a great improvement of the ORR in alkaline media. The present findings could open new avenues for the design of superior electrocatalysts.

中文翻译：

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电子结构工程通过控制中心金属的配位来提高氧还原活性†

调整活性中心的电子结构是提高催化剂性能的高效策略。本文中，我们报道了一种原子分散的催化剂（FeCl1N4 / CNS），该催化剂通过用配位氯控制中心金属的电子结构，首次实现了ORR的极大改进。FeCl1N4 / CNS的半波电势为E _1/2 = 0.921 V，在非贵金属电催化剂的报告值中最高，并且远远超过FeN4 / CN和市售Pt / C的碱性溶液。除了具有41.11 mA cm ^-2的极高动电流密度（J _k）在0.85 V时，它还具有良好的甲醇耐受性和出色的稳定性。实验和DFT表明，Fe与氯的近距离相互作用和与硫的远距离相互作用调节了活性位点的电子结构，从而导致ORR在碱性介质中的显着改善。本研究结果可为高级电催化剂的设计开辟新途径。