Robust and selective electrochemical sensing of hazardous photographic developing agents using a MOF-derived 3D porous flower-like Co3O4@C/graphene nanoplate composite

Abstract

Here we present a facile, rapid and reliable electrochemical sensor for quantitative analysis of hazardous photographic developing agents, including metol (MT), hydroquinone (HQ) and catechol (CC). They have been identified as usual contaminants in environment and water samples. This sensor is based on a nanocomposite of three-dimensional (3D) porous flower-like Co3O4@C hybrid and graphene nanoplates (Co3O4@C/GNP). The Co3O4@C/GNP compoiste is prepared by a two-steps procedure, consisting of the composite synthesis of a Co-MOF precursor and GNPs in the first step and subsequently direct calcination process in the N2 atmosphere. The morphology, composition, and electrochemical behavior of the Co3O4@C/GNP composite is characterized by using microscopic methods and electrochemical techniques, revealing its 3D porous structure, abundant pores, a large electrode active area, a high conductivity, outstanding electrocatalytic and sensing performance toward MT, HQ, and CC. Taking advantages of a huge electroactive surface area and a fast electron transfer rate of GNPs and strong electrical catalytic ability of the Co3O4@C hybrid, the fabricated Co3O4@C/GNP sensor displays high sensitivity for quantitative analysis of MT, HQ and CC. Their detection limits are as low as 5.1, 14.7 and 169 nM (S/N = 3), respectively. Beyond that, the proposed Co3O4@C/GNP electrochemical sensor shows strong reproducibility, good stability and selectivity in the voltammetric quantitation of these analytes. It has been also successfully applied in measuring these photographic developing agents in water environment. Consequently, the fabricated Co3O4@C/GNP composite is expected to be an excellent electrode material in the applications of electrochemical sensing.