CuO nanorod-decorated hemin-graphene with enhanced peroxidase-mimicking performance for the colorimetric and electrochemical determination of 4-aminophenol with a smartphone

Abstract

The detection of 4-aminophenol (4-AP) is of critical importance due to its high toxicity, and the development of accurate, sensitive, and portable methods for this purpose is essential. Here, a facile colorimetric and electrochemical dual-mode sensor based on a CuO nanorod-decorated hemin-functionalized graphene nanocomposite (CuO/H-Gr) is successfully constructed for the detection of 4-AP. CuO/H-Gr exhibited superior peroxidase-mimicking activity, catalyzing the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) by H₂O₂ and generating a colorimetric signal. The catalytic system was found to contain hydroxyl radicals, as revealed by reactive oxygen species trials. Meanwhile, TMB was found to be an electroactive indicator that could be oxidized on a glassy carbon electrode. In the presence of CuO/H-Gr and H₂O₂, an enhanced electrochemical signal of TMB was generated. Upon the addition of 4-AP, the catalytic performance of CuO/H-Gr in the oxidation of TMB was significantly reduced, leading to a decrease in colorimetric and electrochemical signals. Based on this, a dual-mode sensor for the detection of 4-AP was developed. The linear response ranges for colorimetric and electrochemical sensors are 1.00–200 μM and 0.0100–300 μM, with detection limits of 0.687 μM and 0.00756 μM, respectively. Real water samples were tested to estimate the feasibility of the dual-mode sensor, and the recoveries were found to be consistent with those obtained by high-performance liquid chromatography. In addition, a smartphone-based assay was used to evaluate the levels of 4-AP, which opened a new path for on-site detection.