Shape stable poly(vinyl alcohol) hydrogels with immobilized metal hexacyanoferrates for cesium removal from waters.

The metal hexacyanoferrates with transition metal ions to replace ferric ions in the face center cubic structure of Prussian blue (PB) crystals are candidate adsorbents for radioactive cesium ions in waters. This study for the first time synthesized the shape stable poly(vinyl alcohol) (PVA) hydrogels with immobilized metal hexacynoferrate (PB analogue) that can be stored at dry and can efficiently adsorb cesium ions from waters after rewetting. A total of eight PB analogue particles in two families M3[Fe(III)(CN)6]2 (MFe(III)) or M4[Fe(II)(CN)6]2 (MFe(II)) with M=Zn, Ni, Cu, or Co were synthesized and were immobilized in the PVA hydrogels following boric acid and sulfate crosslinking. The produced PVA-PB analogue hydrogels are all stable in shape after dry and rewet, and the rewet hydrogels can adsorb cesium ions from waters at much higher rates. As predicted by the diffusion-reaction model, the apparent reaction constants for cesium ion adsorption are 4.2×10-4 1/s, 3.4×10-4 1/s, 3.9×10-4 1/s, 4.1×10-4 1/s, 4.1×10-4 1/s, 3.8×10-4 1/s, 1.1×10-3 1/s, and 9.6×10-4 1/s, for ZnFe(III), ZnFe(II), NiFe(III), NiFe(II), CuFe(III), CuFe(II), CoFe(III), and CoFe(II), respectively. The corresponding maximum adsorption capacities based on Langmuir isotherm model at 25 °C are 232.6 mg/g, 389.0 mg/g, 193.9 mg/g, 256.8 mg/g, 388.2 mg/g, 395.1 mg/g, 297.3 mg/g, and 391.2 mg/g, respectively. The use of PVA-CoFe(III) is the candidate for enhanced Cs removal from waters comparing the use of other PB analogues as adsorbent.

Poly(vinyl alcohol) and alginate cross-linked matrix with immobilized Prussian blue and ion exchange resin for cesium removal from waters.

Cesium (Cs) removal from contaminated water bodies is an emerging issue after the disaster at the Fukushima Daiichi Nuclear Power Plant. The Prussian blue (PB) is an effective Cs adsorbent but will release hexacyanoferrate fragments from the adsorbent matrix during adsorption. Alginate is an affordable biopolymer for PB particles immobilization. This study synthesized poly(vinyl alcohol) (PVA) and alginate cross-linked matrix for immobilization of PB nano-sized particles and a surface-modified styrene-ethyl styrene divinyl benzene resin and tested their swelling stability and Cs adsorption performance in fresh water and in seawater. The PVA-alginate granules have high structural stability in both fresh water and seawater, with the Cs adsorption capability higher for the former than the latter. The adopted resin effectively remove released PB fragments from the tested granules. The transport and reaction parameters for the granules and for the sand filter bed were estimated.