Amino modified multi-walled carbon nanotubes/polydimethylsiloxane coated stir bar sorptive extraction coupled to high performance liquid chromatography-ultraviolet detection for the determination of phenols in environmental samples

•4,4′-Diaminodiphenylmethane modified CNTs were employed as a coating for SBSE of phenols.•CNTs-DDM/PDMS coating exhibited excellent extraction efficiency for medium polar phenols.•The developed method is suitable for phenols analysis in various environmental samples.

In this work, amino modified multi-walled carbon nanotubes/polydimethylsiloxane (multi-walled carbon nanotubes-4,4′-diaminodiphenylmethane/polydimethylsiloxane, MWCNTs-DDM/PDMS) was synthesized, and utilized as a novel coating for stir bar sorptive extraction (SBSE) of seven phenols (phenol, 2-chlorophenol, 2-nitrophenol, 4-nitrophenol, 2,4-dimethylphenol, p-choro-m-cresol and 2,4,6-trichlorphenol) in environmental water and soil samples, followed by high performance liquid chromatography-ultraviolet detection (HPLC-UV). The prepared MWCNTs-DDM/PDMS coated stir bar was characterized and good preparation reproducibility was obtained with the relative standard deviations (RSDs) ranging from 4.7% to 11.3% (n = 9) in one batch, and from 4.8% to 13.9% (n = 8) among different batches. Several parameters affecting the extraction of seven target phenols by MWCNTs-DDM/PDMS-SBSE including extraction time, stirring rate, pH, ionic strength, desorption solvent and desorption time were investigated. Under the optimal experimental conditions, the limits of detection (LODs, S/N = 3) were found to be in the range of 0.14 μg/L (2-nitrophenol) to 1.76 μg/L (phenol) and the limits of quantification (LOQs, S/N = 10) were found to be in the range of 0.46 μg/L (2-nitrophenol) to 5.8 μg/L (phenol). The linear range was 5–1000 μg/L for phenol and 4-nitrophenol, 1–1000 μg/L for 2-nitrophenol and 2–1000 μg/L for other phenols, respectively. The RSDs of the developed method were in the range of 6.2–11.6% (n = 8, c = 10 μg/L) and the enrichment factors were from 6.5 to 62.8-fold (theoretical enrichment factor was 100-fold). The proposed method was successfully applied to the analysis of phenols in environmental water and soil samples, and good recoveries were obtained for the spiked samples. The proposed method is simple, highly sensitive and suitable for the analysis of trace phenols in environmental samples with complex matrix.