Graphene oxide lamellar membrane with enlarged inter-layer spacing for fast preconcentration and determination of trace metal ions

Abstract

We report a graphene oxide (GO) lamellar membrane with increased inter-layer spacing for efficient permeation of water molecules and heavy metal ions through nanoporous graphene oxide. The inter-layer spacing of the GO sheets in the lamellar structure was increased by introducing poly-aminophosphonic acid (APA) in between the GO sheets. We demonstrate experimentally, the use of a prepared membrane (GO–APA) by a SPE technique for the preconcentration and extraction of heavy metal ions by chelate formation and their determination by ICP-OES. We found that this sub-micrometer-thick membrane allows unimpeded permeation of water molecules through two-dimensional capillaries formed across the pores and by closely spaced graphene sheets. Compared to the bulk GO sorbent, GO–APA membrane offers enhanced sensitivity and permeability for heavy metal ions due to relatively large inter-layer spacing and high surface area (extraction phase) with a high number of active functional groups. The potential of this technique for the preconcentration and extraction of Pb(II), Cd(II) and Cu(II) is illustrated with the contaminated ground water and industrial waste water analysis. The detection limit achieved for studied ions was 1.1 ng L⁻¹, under optimized experimental conditions. The co-existing ions did not hinders the extraction of trace heavy metal ions. Accuracy of the developed method was assessed by analyzing Standard Reference Materials. The Student's t test values were found to less than the critical Student's t value of 4.303 at the 95% confidence level. The method shows good precision as coefficients of variation for five replicate measurements were found to be 4–5%.