Thiol-functionalized Fe3O4-modified Membrane for Selective Preconcentration and Sensitive Detection of Metallic Copper Nanoparticles in Environmental Waters

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Membrane filtration is an efficient technique for rapid and precise separation, yet challenges persist in distinguishing and selectively separating nanoparticles with identical elemental compositions, especially copper-based nanoparticles.Here, we report for the first time the immobilization of thiol-functionalized Fe3O4 nanoparticles (Fe3O4 -RSH NPs) onto mixed cellulose ester membranes for the selective separation and preconcentration of copper nanoparticles (Cu NPs).The Fe3O4-RSH NPsmodified membrane demonstrated significantly greater retention of Cu NPs than CuS and CuO NPs of comparable size.The functionalized membrane exhibits exceptional separation performance, achieving over 90% retention of Cu NPs and an enrichment factor of ~23, as verified by inductively coupled plasma mass spectrometry (ICP-MS).Notably, the retention rate of Cu NPs remained unaffected by other copper species, demonstrating the excellent selectivity of the modified membrane toward Cu NPs.Under optimized conditions, the method reached a limit of detection (LOD) of 2.2 pg mL⁻¹ for Cu NPs.Furthermore, the approach enabled successful detection of Cu NPs in river water samples from Chengdu.This strategy provides a rapid, reliable, and cost-effective pretreatment method for trace nanoparticle analysis in environmental samples and offers a promising platform for the development of low-cost, on-site nanoparticle monitoring technologies.

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