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[en] The crystallization of terbium 5,5"'-azobis[1H-tetrazol-1-ide] (ZT) in the presence of trace amounts (ca. 50 Bq, ca. 1.6 pmol) of americium results in 1) the accumulation of the americium tracer in the crystalline solid and 2) a material that adopts a different crystal structure to that formed in the absence of americium. Americium-doped [Tb(Am)(H_2O)_7ZT]_2 ZT.10 H_2O is isostructural to light lanthanide (Ce-Gd) 5,5"'-azobis[1H-tetrazol-1-ide] compounds, rather than to the heavy lanthanide (Tb-Lu) 5,5"'-azobis[1H-tetrazol-1-ide] (e.g., [Tb(H_2O)_8]_2ZT_3.6 H_2O) derivatives. Traces of Am seem to force the Tb compound into a structure normally preferred by the lighter lanthanides, despite a 10"8-fold Tb excess. The americium-doped material was studied by single-crystal X-ray diffraction, vibrational spectroscopy, radiochemical neutron activation analysis, and scanning electron microscopy. In addition, the inclusion properties of terbium 5,5"'-azobis[1H-tetrazol-1-ide] towards americium were quantified, and a model for the crystallization process is proposed. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)
[en] A series of rare earth element (REE) mixed-anion 5,5'-azobis(1H-tetrazol-1-ide)-carbonate ([REE2(ZT)2CO3(H2O)10].2H2O; REE = lanthanides plus yttrium) coordination compounds were synthesized, characterized, and analyzed. Syntheses by simple metathesis reactions under a CO2 atmosphere were carried out at ambient (La-Gd and Ho) and elevated pressures (55 bar; Tb, Dy, Er, Tm, Yb, and Y). The resulting crystalline materials were characterized principally by single-crystal X-ray diffraction and vibrational spectroscopy (infrared and Raman). All materials are structurally isotypic, crystallizing in the space group C2/c and show nearly identical spectroscopic properties for all the elements investigated. Cell parameters, bond lengths, and bond angles differ marginally, revealing only a slight variation coinciding with the lanthanide (Ln) contraction, that is, the change in the ionic radii of the trivalent rare earth elements. The herein reported series of rare earth element azobis[tetrazolide]-carbonates represents a remarkable exception as they are a series of isotypic REE coordination compounds with tetrazolide-derived ligands unaffected by the ''gadolinium break''. (copyright 2018 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)
[en] Highlights: • An automated search for reaction systems suitable for thermochemical energy storage was performed. • Algorithm to build reaction systems for thermochemical energy storage is presented. • Close to 1000 possible reaction systems for 5 different reactive gases were found. • The VIENNA TCES-database for thermochemical energy storage materials is presented. - Abstract: Thermochemical energy storage (TCES) is considered as an emerging green technology for increased energy utilization efficiency, thereby achieving a reduction of greenhouse gases. Various reaction systems based on different substance classes (e.g. hydrates, hydroxides, oxides) were suggested and investigated so far. Nevertheless, the number of know reactions which are suitable is still limited, as the main focus concentrates on the investigation of a handful known substances, their further improvement or applicability. To find novel promising candidates for thermochemical energy storage and also to allow for a broader view on the topic, this work present a systematic search approach for thermochemical storage reactions based on chemical databases. A mathematical search algorithm identifies potential reactions categorized by the reactant necessary for the reaction cycle and ranked by storage density. These candidates are listed in the online available VIENNA TCES-database, combined with experimental results, assessing the suitability of these reactions regarding of e.g. decomposition/recombination temperature, reversibility, cycle stability, etc.
[en] Highlights: • CaC_2O_4·H_2O dehydration is fully reversible between 25 °C and 200 °C. • Isothermal cycling between hydrate and anhydrate phase can be triggered by the water vapour concentration. • High reaction rates and full reversibility demonstrated over 100 cycles. • Material shows no ageing effects or reactivity decrease. - Abstract: The dehydration and subsequent rehydration of calcium oxalate monohydrate has yet to find application in thermochemical energy storage. Unlike for many other salt hydrates, complete reversibility of the dehydration-rehydration reaction was observed. Additionally, it was found that the rehydration temperature is strongly affected by the water vapour concentration: Full reversibility is not only achieved at room-temperature, but, depending on the water vapour concentration, at up to 200 °C. This allows isothermal switching of the material between charging and discharging by a change of the H_2O-partial pressure. Cycle stability of the material was tested by a long-term stress experiment involving 100 charging and discharging cycles. No signs of material fatigue or reactivity loss were found. In-situ powder X-ray diffraction showed complete rehydration of the material within 300 s. The experimental findings indicate that the CaC_2O_4·H_2O/CaC_2O_4 system is perfectly suited for technical application as a thermochemical energy storage medium.