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Reactive Hydrogen-Mediated Peroxydisulfate Activation for Boosting Carbon Nitride Electrochemiluminescence
Chunjing Li1, Juan He1, Ying Qin1
1State Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensing Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, P. R. China.
Abstract:
Peroxydisulfate (PDS) is widely used as a coreactant in nanomaterial-based electrochemiluminescence (ECL) systems because its activation produces highly oxidative sulfate radical intermediates (SO4•-). However, the symmetrical structure of PDS results in a high activation energy for the cleavage of its O-O bond. This necessitates highly negative cathodic potentials, triggering competing hydrogen evolution reactions (HER) and reducing ECL efficiency. In this study, we exploit the dual functionality of carbon nitride-supported palladium single atoms (PdSA) and nanoparticles (PdNP) for hydrogen-mediated PDS activation. PdNP supply reactive hydrogen species (H*) through electrocatalytic water reduction, while neighboring PdSA sites simultaneously adsorb and activate PDS. The breaking of O-O bonds in PDS is achieved through the interaction of these migrating H* intermediates. The experimental results and theoretical calculations demonstrate that this H*-involved synergistic effect facilitates the activation of PDS, leading to an approximately 2.58-fold enhancement in the ECL intensity of CN-PdSA+NP compared to pristine CN. Furthermore, the constructed ECL sensing platform exhibits remarkable sensitivity for glutathione S-transferase detection. This work provides valuable insights into the H*-mediated coreactant activation mechanism and bridges the gap between HER and ECL.
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