Proton-exchange mechanism of specific Cs+ adsorption via lattice defect sites of Prussian blue filled with coordination and crystallization water molecules.

We have revealed the fundamental mechanism of specific Cs(+) adsorption into Prussian blue (PB) in order to develop high-performance PB-based Cs(+) adsorbents in the wake of the Fukushima nuclear accident. We compared two types of PB nanoparticles with formulae of Fe(III)4[Fe(II)(CN)6]3·xH2O (x = 10-15) (PB-1) and (NH4)0.70Fe(III)1.10[Fe(II)(CN)6]·1.7H2O (PB-2) with respect to the Cs(+) adsorption ability. The synthesised PB-1, by a common stoichiometric aqueous reaction between 4Fe(3+) and 3[Fe(II)(CN)6](4-), showed much more efficient Cs(+) adsorption ability than did the commercially available PB-2. A high value of the number of waters of crystallization, x, of PB-1 was caused by a lot of defect sites (vacant sites) of [Fe(II)(CN)6](4-) moieties that were filled with coordination and crystallization water molecules. Hydrated Cs(+) ions were preferably adsorbed via the hydrophilic defect sites and accompanied by proton-elimination from the coordination water. The low number of hydrophilic sites of PB-2 was responsible for its insufficient Cs(+) adsorption ability.

Synthesis, Structure, and Redox Properties of [{(η(5) -C5 H5 )Co(S2 C6 H4 )}2 Mo(CO)2 ], a Novel Metalladithiolene Cluster.

Metal-metal bond formation by a cobaltadithiolene complex was observed for the first time in the reaction of [Co(η(5) -C5 H5 )(S2 C6 H4 )] with [Mo(CO)3 (py)3 ] and BF3 to give the Co-Mo-Co cluster 1. Cyclic voltammetry reveals that 1 undergoes two one-electron reduction steps at the Co centers, which is indicative of transmission of the Co-Co electronic interaction through the Mo center.