Functionalized calcium silicate nanofibers with hierarchical structure derived from oyster shells and their application in heavy metal ions removal

Abstract

Inorganic hierarchical nanostructures have remarkable potential applications in environmental metal remediation; however, their applications usually suffer from low capacity, high cost, and difficulties in the recycling of adsorbents. We previously reported a facile strategy to synthesize acid-insoluble calcium silicate hydrates (CSH) from oyster shells, a representative kind of biowaste. However, little is known of the structure, size, and morphology of the as-prepared CSH, which hampers the improvement of their adsorption capacities. In this work, systematic investigation of the structures of as-generated CSH demonstrate that they have a hierarchically porous structure composed of thin nano-sheets, where each nano-sheet is assembled by nano-fibers with width of around ten nanometers. The hierarchical nanostructures with pore size of ∼12 nm provide a significant amount of active sites to graft polyethyleneimine (PEI), which enables the efficient extraction of both Cu(II) cations and Cr(VI) anions from the aqueous solution. Batch experiments further indicate that the PEI-modified PCSH exhibit a maximum adsorption capacity of 203 and 256 mg g⁻¹ for Cu(II) and Cr(VI), respectively, much higher than that of CSH, OS and many other adsorbents in literature. The adsorption of Cu(II) and Cr(VI) proved to be spontaneous and exothermic. Combining the pH-dependent experiments with X-ray photoelectron spectroscopy analysis, the underlying mechanism is discussed. PCSH derived from OS biowaste maintains an efficient extraction ability toward Cu(II) and Cr(VI) after five adsorption–desorption cycles. It is also applicable for treating various kinds of heavy metal ions and organic pollutants, showing potentially wide applications in water treatment.