Prussian blue analogues (PBAs) are commonly believed to reversibly insert divalent ions, such as calcium and magnesium, rendering them as perspective cathode materials for aqueous magnesium‐ion batteries. In this study, the occurrence of Mg2+ insertion into nanosized PBA materials is shown to be a misconception and conclusive evidence is provided for the unfeasibility of this process for both cation‐rich and cation‐poor nickel, iron, and copper hexacyanoferrates. Based on structural, electrochemical, IR spectroscopy, and quartz crystal microbalance data, the charge compensation of PBA redox can be attributed to protons rather than to divalent ions in aqueous Mg2+ solution. The reversible insertion of protons involves complex lattice water rearrangements, whereas the presence of Mg2+ ion and Mg salt anion stabilizes the proton (de)insertion reaction through local pH effects and anion adsorption at the PBA surface. The obtained results draw attention to the design of proton‐based batteries operating in environmentally benign aqueous solutions with low acidity.

Hydrophilic colloids (PSS-[Ln2(TCAi)2] and PSS-[LnCAi], where i = 1, 2, or 3 and Ln = Gd or Tb) were prepared by precipitation of Gd­(III) or Tb­(III) complexes with tetrathiacalix[4]­arenes (TCAi) and calix[4]­arenes bearing two 1,3-diketone groups (CAi) from dimethylformamide to an aqueous solution of poly­(sodium 4-styrenesulfonate) (PSS). Dynamic light scattering and transmission electron microscopy demonstrated the formation of nanoparticles coated by the polymer. Luminescence decay measurements on Tb­(III)-based colloids allowed hydration numbers of 2 and 4 per metal ion to be determined for PSS-[Ln2(TCAi)2] and PSS-[LnCAi] samples, respectively. Longitudinal and transverse water proton relaxivity values measured at 20.8 MHz were remarkably high for the PSS-[GdCAi] colloids but unexpectedly low for the PSS-[Gd2(TCAi)2] ones. 1H fast field cycling nuclear magnetic resonance relaxometry was applied to shed light on the origin of the different relaxation enhancement in the investigated systems. Extremely slow exchange with the bulk of water molecules coordinated to Gd­(III) and the scarce accessibility of Gd­(III) sites to water were highlighted as the main causes of limited relaxivity.

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The superior rate capabilities of metal ion battery materials based on Prussian blue analogues (PBAs) are almost exclusively ascribed to the extremely fast solid-state ionic diffusion, which is possible due to structural voids and spacious three-dimensional channels in PBA structures. We performed a detailed electroanalytical study of alkali ion diffusivities in nanosized cation-rich and cation-poor PBAs obtained as particles or electrodeposited films in both aqueous and non-aqueous media, which resulted in a solid conclusion about the exceptionally slow ionic transport. We show that the impressive rate capability of PBA materials is determined solely by the small size of the primary particles of PBAs, while the apparent diffusion coefficients are 3−5 orders of magnitude lower than those reported in earlier studies. Our finding calls for a reconsideration of the apparent facility of ionic transport in PBA materials and deeper analysis of the charge carrier−host interactions in PBAs.

A series of novel polysaccharide-based biocomposites was obtained by impregnation of bacterial cellulose produced by Komagataeibacter rhaeticus (BC) with the solutions of negatively charged polysaccharides—hyaluronan (HA), sodium alginate (ALG), or κ-carrageenan (CAR)—and subsequently with positively charged chitosan (CS). The penetration of the polysaccharide solutions into the BC network and their interaction to form a polyelectrolyte complex changed the architecture of the BC network. The structure, morphology, and properties of the biocomposites depended on the type of impregnated anionic polysaccharides, and those polysaccharides in turn determined the nature of the interaction with CS. The porosity and swelling of the composites increased in the order: BC–ALG–CS > BC–HA–CS > BC–CAR–CS. The composites show higher biocompatibility with mesenchymal stem cells than the original BC sample, with the BC–ALG–CS composite showing the best characteristics.