4.6 Article

Cs sorption of Mn-Fe based Prussian blue analogs with periodic precipitation banding in agarose gel

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PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 24, 期 16, 页码 9374-9383

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ROYAL SOC CHEMISTRY
DOI: 10.1039/d2cp00654e

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  1. JSPS KAKENHI [JP19K05409]

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We investigated the sorption/desorption properties of Cs in agarose gel using Mn-Fe based Prussian blue analogs and Prussian blue. Mn-Fe PBA gel showed better Cs sorption capacity and formed periodic precipitation bands compared to PB gel. Mn-Fe PBA gel effectively suppressed the release of Cs during desorption.
We report the understanding of Cs sorption/desorption properties of Mn-Fe based Prussian blue analogs (Mn-Fe PBA) and Prussian blue (PB) in agarose gel via X-ray fluorescence spectroscopy and scanning electron microscopy. After contacting a 2 mass% agarose gel containing 100 mmol dm(-3) [Fe(CN)(6)](3-) ions (inner electrolyte gel) with a 1 mass% agarose gel containing 550 mmol dm(-3) Mn2+ or Fe2+ ions (outer electrolyte gel) in a plastic straw for 11 days, the clipped 10 mm-long gel columns of uniformly formed precipitates (named Mn-Fe PBA gel and PB gel) were used to investigate their Cs sorption/desorption properties. The Mn-Fe PBA gel showed several interesting features that were not observed in the PB gel. The Cs sorption capacity of the Mn-Fe PBA gel increased over time, and after similar to 1200 h reached a value comparable to the most optimal values previously reported. During Cs sorption, Mn2+ ions were constantly released from the Mn-Fe PBA gel, and several periodic precipitation bands were generated. The positions of the periodic bands agreed with those of the peak distributions of Cs, Mn, and Fe, suggesting that the concentration fluctuation of Mn-II-Fe-III PBA in the gel resulted in the periodic band formation. In these bands, large crystallites (>10 mu m) were dominant, suggesting the contribution of Ostwald ripening. During Cs desorption, while Mn2+ ions were released from the Mn-Fe PBA gel, the release of Cs+ ions was considerably suppressed (similar to 1/3 for the PB gel). Based on these results, a model for Cs sorption by the Mn-Fe PBA gel was proposed, and its potential applications were discussed.

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