Nanomaterials-based biomimetic catalysts with multiple functions are necessary to address challenges in artificial enzymes mimicking physiological processes. Here we report a metal-free nanozyme of modified graphitic carbon nitride and demonstrate its bifunctional enzyme-mimicking roles. With oxidase mimicking, hydrogen peroxide is generated from the coupled photocatalysis of glucose oxidation and dioxygen reduction under visible-light irradiation with a near 100% apparent quantum efficiency. Then, the in situ generated hydrogen peroxide serves for the subsequent peroxidase-mimicking reaction that oxidises a chromogenic substrate on the same catalysts in dark to complete the bifunctional oxidase-peroxidase for biomimetic detection of glucose. The bifunctional cascade catalysis is successfully demonstrated in microfluidics for the real-time colorimetric detection of glucose with a low detection limit of 0.8 μM within 30 s. The artificial nanozymes with physiological functions provide the feasible strategies for mimicking the natural enzymes and realizing the biomedical diagnostics with a smart and miniature device.

Significance: Photocatalysts frequently require simultaneous loading of oxidative and reductive cocatalysts to achieve both efficient half-reactions within a single material. Nevertheless, unregulated loading and distribution of two cocatalysts will result in direct contact between oxidation and reduction centers, leading to detrimental charge recombination. This research presents a center/edge approach to load two redox cocatalysts with controlled physical separation in atomistic scale using single-atom architecture. This spatial separation is critical for enhancing surface charge separation and achieving efficient H ₂ O ₂ production. We report that redox cocatalysts are spatially separated on a two-dimensional (2D) photocatalyst, which opens an approach for achieving both efficient oxidation and reduction reactions on 2D photocatalysts.