Two-Electron or Four-Electron Nanocatalysis for Aerobic Glucose Oxidation: A Mechanism-Driven Prediction Model

The nanomaterial-catalyzed oxidation of glucose can produce
H2O2 or H2O as the oxygen reduction
products.
However, the theoretical model predicting the selection between H2O2 and H2O products is still lacking,
which limits the rational design of aerobic glucose oxidation nanocatalysts
for H2O2-targeted applications in disease diagnoses
and therapies. In this work, a mechanism-driven prediction model that
can predict whether a nanocatalyst preferably undergoes the 2e-catalysis
to produce H2O2 or the 4e-catalysis to produce
H2O is developed. The development of the model is first
based on the reaction thermodynamics, and then a correction constant
is introduced in conjunction with experimental reports to compensate
to some extent for the lack of consideration of other influencing
factors such as the reaction kinetics. The predictive power of the
model is verified by density functional theory investigations on the
mechanisms and kinetics of the experimentally reported noble metal
nanocatalysts. Using the model, binary alloy nanomaterials, which
preferably undergo 2e-catalysis to produce H2O2, have been predicted. This work provides theoretical guidelines
for the rational design of aerobic glucose oxidation nanocatalysts
capable of producing H2O2 and facilitates their
application in H2O2-targeted biomedicine.