Single-atom Fe nanozymes with excellent oxidase-like and laccase-like activity for colorimetric detection of ascorbic acid and hydroquinone.

ABSTRACT

Although traditional Fe-based nanozymes have shown great potential, generally only a small proportion of the Fe atoms on the catalyst's surface are used. Herein, we synthesized single-atom Fe on N-doped graphene nanosheets (Fe-CNG) with high atom utilization efficiency and a unique coordination structure. Active oxygen species including superoxide radicals (O2•-) and singlet oxygen (1O2) were efficiently generated from the interaction of the Fe-CNG with dissolved oxygen in acidic conditions. The Fe-CNG nanozymes were found to display enhanced oxidase-like and laccase-like activity, with Vmax of 2.07 × 10-7 M∙S-1 and 4.54 × 10-8 M∙S-1 and Km of 0.324 mM and 0.082 mM, respectively, which is mainly due to Fe active centers coordinating with O and N atoms simultaneously. The oxidase-like performance of the Fe-CNG can be effectively inhibited by ascorbic acid (AA) or hydroquinone (HQ), which can directly obstruct the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB). Therefore, a direct and sensitive colorimetric method for the detection of AA and HQ activity was established, which exhibited good linear detection and limit of detection (LOD) of 0.048 µM and 0.025 µM, respectively. Moreover, a colorimetric method based on the Fe-CNG catalyst was fabricated for detecting the concentration of AA in vitamin C. Therefore, this work offers a new method for preparing a single-atom catalyst (SAC) nanozyme and a promising strategy for detecting AA and HQ.