Fluorine Dopant-Mediated Electron Buffering Effect to Stabilize Nickel Sites for Reinforced Electrochemiluminescence Durability

Abstract Efficient O2 activation by co-reaction accelerators is instrumental in boosting luminol–O2 electrochemiluminescence (ECL) performance, delivering enhanced emission intensity. However, the operational durability remains fundamentally limited by alkaline-mediated support corrosion and progressive destabilization of active sites during O2 activation, resulting in metal dissolution and structural degradation, which compromises the durability of the ECL system. Herein, fluorine (F)-doped Ni single-atom catalysts (SACs) (NiNFC SACs) were developed as co-reaction accelerators for O2 activation, which significantly enhanced ECL stability. Experimental studies and theoretical calculations reveal that F serves as an electron-buffering site through efficient and concerted electron transfer with Ni during O2 activation to adjust Ni electron density, alleviating the burden on Ni and preserving Ni–N bond stability. Finally, based on the inhibition effect of organic pollutants toward proposed ECL platform, a dual-channel sensor array is constructed to distinguish and simultaneously detect five different ionization potential value organic pollutants with high selectivity. This innovative strategy offers new insights for achieving the stable ECL emission required for practical applications.