Ultrasound and defect engineering-enhanced nanozyme with high laccase-like activity for oxidation and detection of phenolic compounds and adrenaline

Abstract

Perusing metal-based redox nanozyme offers new opportunity for pollutant removal and biosensor, but ultrasound (US)-driven laccase-like nanozyme remains a significant challenge, especially in combination with defect engineering strategy. Herein, the Cu2Ov@Ce-TCPP was synthesized by doping Ce3+ on the surface of Cu2O nanocube and then coating with the porphyrin sonosensitizer. The Ce-doped porphyrin metal-structure in nanozyme was demonstrated to generate oxygen vacancy defects, which could obviously promote the laccase-like activity of Cu2Ov@Ce-TCPP nanozyme under US. XPS characterization and density functional theory (DFT) theoretical calculation revealed that the ultrasonic stimulation is beneficial to accelerate the electron transfer rate and O2 adsorption to improve catalytic activity, and Cu2Ov@Ce-TCPP nanozyme exhibits low adsorption energy and activation energy due to the presence of oxygen defect site, resulting in high laccase-like activity. The interaction between Ce atom and porphyrin structure also improved the sonocatalytic ability of the nanozyme. Meanwhile, Cu2Ov@Ce-TCPP nanozyme has been used for detecting and degrading a series of phenolic compounds. The detection adrenaline method has a linear range of 3.3–1000 μM and a detection limit as low as 0.96 μM with good reproducibility. The developed US-enhancing and recyclable laccase-like nanozyme system provides a promising strategy for the oxidation and detection of phenolic compounds.