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Bio-Inspired Preparation of Clay–Hexacyanoferrate Composite Hydrogels as Super Adsorbents for Cs+

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journal contribution
posted on 07.07.2020, 22:04 by Huagui Zhang, Chris S. Hodges, Prashant Kumar Mishra, Ji Young Yoon, Timothy N. Hunter, Jae W. Lee, David Harbottle
A facile and low-cost fabrication route, inspired by the adhesive proteins secreted by mussels, has been developed to prepare a clay-based composite hydrogel (DHG­(Cu)) containing hexacyanoferrate (HCF) nanoparticles for the selective removal of Cs+ from contaminated water. Initially, montmorillonite was exfoliated prior to coating with a thin layer of polydopamine (PDOPA) via the self-polymerization of dopamine. Mixing the composite (D-clay) with the HCF precursor, followed by the addition of copper ions, led to the self-assembly of the polymer-coated exfoliated clay nanosheets into a three-dimensional network and in situ growth of KCuHCF nanoparticles embedded within the gel structure. Analytical characterization verified the fabrication route and KCuHCF immobilization by a copper–ligand complexation. Rheology testing revealed the composite hydrogel to be elastic under low strain and exhibited reversible, self-healing behavior following high strain deformation, providing a good retention of KCuHCF nanoparticles in the membrane. The adsorbent DHG­(Cu) showed a superior Cs+ adsorption capacity (∼173 mg/g), with the performance maintained over a wide pH range, and an excellent selectivity for Cs+ when dispersed in seawater at low concentrations of 0.2 ppm. On the basis of its excellent mechanico-chemical properties, the fabricated hydrogel was tested as a membrane in column filtration, showing excellent removal of Cs+ from Milli-Q water and seawater, with the performance only limited by the fluid residence time. For comparison, the study also considered other composite hydrogels, which were fabricated as intermediates of DHG­(Cu) or fabricated with Fe3+ as the cross-linker and reactant for HCF nanoparticle synthesis.