An XAFS study of Cs adsorption by the precipitation bands of Mn-Fe-based Prussian blue analogues spontaneously formed in agarose gel

The adsorption of Cs+ ions by the precipitation bands of a Mn-Fe based Prussian blue analogue (Mn-Fe PBA) that form spontaneously in agarose gel was investigated by X-ray absorption fine structure spectroscopy coupled with scanning electron microscopy (SEM) and X-ray fluorescence (XRF) distribution analysis. Two gel samples were prepared by contacting a gel containing 0.05 M [Fe(CN)(6)](3-) and 2.3 mass% agarose with a 0.50 M MnSO4 solution, into one of which a 0.10 M CsCl solution was introduced. The SEM images and the XRF intensity distributions reveal that Mn-Fe PBA forms cubic crystallites (approx. 3 x 3 x 3 mu m in size) in the gels that trap Cs+ ions with considerably high affinity. Cs L-3-edge and Mn K-edge X-ray absorption near-edge structure (XANES) spectra, which were analyzed with the aid of FEFF simulations, strongly suggest that Cs adsorption occurs at relatively large defect sites close to the sub-cube faces in the PBA. This suggestion is supported by Cs L-3-edge extended X-ray absorption fine structure spectroscopy, which suggested that the first and second coordination shells around the Cs+ ions are at a Cs-O distance of 0.35 +/- 0.02 nm and a Cs-N distance of 0.43 +/- 0.01 nm, respectively, with coordination numbers of 1.5 +/- 0.5 and 3.0 +/- 0.5. The Mn K-edge XANES data also suggest that H2O molecules, which initially occupy many cubic centers in the Mn-Fe PBAs, are mostly displaced during Cs adsorption. These findings provide valuable insight toward fully understanding Cs adsorption by Mn-Fe PBA.