Nanozyme Catalytic Turnover and Self-Limited Reactions

Enzymes have catalytic turnovers. The field of nanozyme endeavors to engineer nanomaterials as enzyme mimics. However, a discrepancy in the definition of "nanozyme concentration" has led to an unrealistic calculation of nanozyme catalytic turnovers. To date, most of the reported works have considered either the atomic concentration or nanoparticle (NP) concentration as nanozyme concentration. These assumptions can lead to a significant under- or overestimation of the catalytic activity of nanozymes. In this article, we review some classic nanozymes including Fe3O4, CeO2, and gold nanoparticles (AuNPs) with a focus on the reported catalytic activities. We argue that only the surface atoms should be considered as nanozyme active sites, and then the turnover numbers and rates were recalculated based on the surface atoms. According to the calculations, the catalytic turnover of peroxidase Fe3O4 NPs is validated. AuNPs are self-limited when performing glucose-oxidase like activity, but they are also true catalysts. For CeO2 NPs, a self-limited behavior is observed for both oxidase- and phosphatase-like activities due to the adsorption of reaction products. Moreover, the catalytic activity of single-atom nanozymes is discussed. Finally, a few suggestions for future research are proposed.