Cu₂O nanocubes-grafted highly dense Au nanoparticles with modulated electronic structures for improving peroxidase...

Based on the intermediate states of metal ions in metal oxide nanomaterials (NMs) that acted as the primary active species, the design of high-performance nanozymes has greatly stimulated current research in diverse biomedical applications. Herein, Cu₂O nanocubes-grafted highly dense Au nanoparticles (NPs) was developed as an appealing nanozyme for H₂O₂ colorimetric sensor and antioxidant detections. The obtained Au/Cu₂O heterostructures show efficient electron-transfer from metallic NPs to Cu₂O nanocubes owing to the difference of Fermi energy between two components. The modulated electronic structure of Au/Cu₂O hybrids enables them to possess enhanced peroxidase catalytic activity for the oxidation of 3, 3', 5, 5'-tetramethylbenzidine (TMB) in the presence of H₂O₂, which is about 32% higher than that of pristine Cu₂O nanocubes. Then, an excellent H₂O₂ colorimetric sensor was established by using Au/Cu₂O heterostructures with a low limit of detection (LOD) of 0.054 μM, which is much lower than the H₂O₂ allowance level of US FDA regulations (ca.15 μM, 0.05 wt%). The obtained Au/Cu₂O nanoproducts exhibit pronounced long-time stability with 95% peroxidase activity maintained after keeping them for 30 days, while residual 64.5% via Cu₂O nanocubes. Furthermore, we assessed the anti-oxidative behavior of three natural antioxidants (tannic acid, gallic acid, tartaric acid) with the LODs as low as 0.039, 0.16 and 1.55 μM, respectively, and the antioxidant capacity in the following order: tannic acid > gallic acid > tartaric acid. Therefore, it is believed that the as-prepared Au/Cu₂O nanozymes have promising potential applications in fields of biomedicine and food safety.