Single-atom catalyst (SAC), one of the most attractive catalysts in the field of energy conversion and storage, was proven as efficient accelerator for luminol-dissolved oxygen electrochemiluminescence (ECL) via the catalysis of oxygen reduction reaction (ORR). In this work, we synthesized heteroatom doping SACs of Fe–N/P–C for the catalysis of cathodic luminol ECL. The doping of P could lower the reaction energy barrier of the OH* reduction, and promote catalytic efficiency toward ORR. The formation of reactive oxygen species (ROS) during ORR triggered cathodic luminol ECL. Greatly enhanced ECL emission catalyzed by SACs proved that Fe–N/P–C exhibited higher catalytic activity to ORR compared with Fe–N–C. Since the system was highly dependent on oxygen, an ultra-sensitive detection of a typical antioxidant, ascorbic acid, was achieved with detection limit of 0.03 nM. This study provides possibility to greatly enhance the performance of ECL platform through rational tailoring of SACs via heteroatom doping.

单原子催化剂 (SAC) 是能量转换和存储领域最具吸引力的催化剂之一，通过氧还原反应（ORR）的催化作用。在这项工作中，我们合成了用于催化阴极鲁米诺 ECL 的 Fe-N/P-C 杂原子掺杂 SAC。P的掺杂可以降低OH*还原的反应能垒，提高ORR的催化效率。ORR 过程中活性氧 (ROS) 的形成触发了阴极鲁米诺 ECL。由 SAC 催化的 ECL 发射大大增强，证明与 Fe-N-C 相比，Fe-N/P-C 对 ORR 表现出更高的催化活性。由于该系统高度依赖氧气，因此实现了典型抗氧化剂抗坏血酸的超灵敏检测，检测限为 0.03 nM。本研究通过杂原子掺杂对 SAC 进行合理剪裁，为大大提高 ECL 平台的性能提供了可能性。