Two-Electron or\nFour-Electron Nanocatalysis for Aerobic\nGlucose Oxidation: A Mechanism-Driven Prediction Model

The nanomaterial-catalyzed oxidation of glucose can produce\nH<sub>2</sub>O<sub>2</sub> or H<sub>2</sub>O as the oxygen reduction\nproducts.\nHowever, the theoretical model predicting the selection between H<sub>2</sub>O<sub>2</sub> and H<sub>2</sub>O products is still lacking,\nwhich limits the rational design of aerobic glucose oxidation nanocatalysts\nfor H<sub>2</sub>O<sub>2</sub>-targeted applications in disease diagnoses\nand therapies. In this work, a mechanism-driven prediction model that\ncan predict whether a nanocatalyst preferably undergoes the 2e-catalysis\nto produce H<sub>2</sub>O<sub>2</sub> or the 4e-catalysis to produce\nH<sub>2</sub>O is developed. The development of the model is first\nbased on the reaction thermodynamics, and then a correction constant\nis introduced in conjunction with experimental reports to compensate\nto some extent for the lack of consideration of other influencing\nfactors such as the reaction kinetics. The predictive power of the\nmodel is verified by density functional theory investigations on the\nmechanisms and kinetics of the experimentally reported noble metal\nnanocatalysts. Using the model, binary alloy nanomaterials, which\npreferably undergo 2e-catalysis to produce H<sub>2</sub>O<sub>2</sub>, have been predicted. This work provides theoretical guidelines\nfor the rational design of aerobic glucose oxidation nanocatalysts\ncapable of producing H<sub>2</sub>O<sub>2</sub> and facilitates their\napplication in H<sub>2</sub>O<sub>2</sub>-targeted biomedicine.