A graphene oxide-based polymer composite coating for highly-efficient solid phase microextraction of phenols

Sensitivity and selectivity of the solid phase microextraction (SPME) in analysis are mostly determined by the coating material of the fiber used. Graphene oxide (GO) has attracted great attention because of its large specific surface area, rich oxygen functional groups, good dispersibility in aqueous solution and high reactivity. However, the low thermal stability of the functional groups limits the wide application of GO in SPME coating design. Highly cross-linked polyoxyethylene (POE) is a substrate widely used for composite material construction, which could significantly improve the thermal stability, water resistance as well as biocompatibility of the functional materials. In this study, we incorporated GO with highly cross-linked POE as a novel fiber coating material for SPME through the gluing approach. The obtained fiber possessed a wrinkled shape surface, which could increase the accessible surface area. In addition, the thermal and chemical stability of the fiber coating were also improved, rendering the fiber rigid enough for more than 100 repetitive extraction cycles. The performance of this developed SPME method for phenols was evaluated by headspace extraction of phenols in aqueous samples. Compared with three commercial fibers, the home-made fiber showed excellent extraction efficiencies towards phenols. Under the optimized conditions, it showed low detection limits (0.12-1.36 ng· L^-1), good precision (<8.4%), good fiber-to-fiber repeatability (3.1%-8.1%), wide linear range (almost 5-1000 ng·L^-1and correlation coefficients (R²) >99%), as well as good enrichment efficiencies (enrichment factors (EFs), 172-1752). Furthermore, the method was successfully applied in simultaneous analyses of five phenols for real water samples with satisfactory recoveries (81-113% for the Pearl River samples).