Magnetic hierarchical titanium ferrocyanide for the highly efficient and selective removal of radioactive cesium from water.

Selective adsorption is the most suitable technique for eliminating trace amounts of 137Cs from various volumes of 137Cs-contaminated water, including seawater. Although various metal ferrocyanide (MFC)-functionalized magnetic adsorbents have been developed for the selective removal of 137Cs and magnetic recovery of adsorbents, their adsorption capacity for Cs remains low. Here, magnetic hierarchical titanium ferrocyanide (mh-TiFC) was synthesized for the first time for enhanced Cs adsorption. Hierarchical TiFC, comprising 2-dimensional TiFC flakes, was synthesized on SiO2-coated magnetic Fe3O4 particles using a sacrificial TiO2 shell as a source of Ti4+ via a reaction with ferrocyanide under acidic conditions. The resultant mh-TiFC exhibited the highest maximum adsorption capacity (434.8 mg g-1) and enhanced Cs selectivity with an excellent Kd value (6,850,000 mL g-1) compared to those of previously reported magnetic Cs adsorbents. This enhancement was attributed to the hierarchical structure, which reduced intracrystalline diffusion and increased the surface area available for direct Cs adsorption. Additionally, mh-TiFC (0.1 g L-1) demonstrated an excellent removal efficiency of 137Cs exceeding 99.85% for groundwater and seawater containing approximately 22 ppt 137Cs. Therefore, mh-TiFC offers promising applications for the treatment of 137Cs-contaminated water.

Helical magnetic micromotors decorated with nickel ferrocyanide for the active and rapid adsorption of radiocesium in water.

Separating radioactive cesium from nuclear waste and contaminated environments is critical to mitigate radiological hazards. In response to this need, remote-controllable and Cs-selective micromotor adsorbents have been considered as a promising technology for rapid in-situ cleanup while minimizing secondary waste and radiation exposure to workers. In this study, we demonstrate the active and rapid removal of a radioactive contaminant from water by leveraging the magnetic manipulation capabilities of a helical and magnetic Ni micromotor coated with Cs-selective nickel ferrocyanide (NiFC). The use of polyvinyl alcohol fibers as a template enables the straightforward preparation of the helical wire structure, allowing for precise control over the diameter and pitch of the helix through simple twisting with Ni wires. By harnessing Ni2+ ions eluted from the Ni micromotor in an acid solution, we successfully fabricate NiFC-coated Ni (NiFC/Ni) micromotors that exhibit a selective removal efficiency greater than 98% for 137Cs, even in the presence of high concentrations of competing Na+ ions. Under the influence of an external magnetic field, the NiFC/Ni micromotor demonstrates rapid motion, achieving a pulling motion (100 body lengths per second) through a magnetic gradient and a tumbling motion (46 body lengths per second) induced by a rotating magnetic field. The tumbling motion of the NiFC/Ni micromotor substantially improves the Cs adsorption rate, resulting in a rate that surpasses that achieved under nonmoving conditions by a factor of 21. This improved adsorption rate highlights the considerable potential of magnetically manipulated micromotor self-propulsion for efficient water-pollution treatment.