Nanoscale-controlled organic inorganic hybrid spheres for comprehensive enrichment of ultratrace chlorobenzenes in marine and fresh water

The size of the adsorbent has the potential to influence extraction performance, but the size effect at the nanoscale is still poorly understood. In this study, organic-inorganic hybrid nanospheres (OIHNs) with controllable nanoscale sizes of 30, 50, and 100 nm were successfully prepared. These materials were further fabricated as solid phase microextraction (SPME) coatings with similar thicknesses, and coupled with gas chromatography-mass spectrometry (GC-MS) to investigate their extraction performance. The results showed that the extraction capacities of OIHNs for chlorobenzenes (CBs) and polycyclic aromatic hydrocarbons (PAHs) were much better than those of their corresponding derived carbon materials, despite the smaller specific surface areas and lower porosities of them. In addition, the enrichment performance increased significantly with decreasing particle size, and the OIHN-30 coating demonstrated the best performance, with enrichment factors ranging from 1098 to 6853 for CBs. Finally, a highly sensitive and practical analytical method was established with a wide linear range of 0.5–5000 ng·L−1, and the limits of quantification (LOQs) were 0.43–1.7 ng·L−1. The determinations of ultratrace CBs in five marine water samples and five fresh water samples were realized successfully. This study is expected to contribute to a deep understanding of the environmental effects of nanoparticles and the design of high-performance adsorbents.