Destabilization of NaBH4 by Transition Metal Fluorides

With the goal of improving performance of a hydrogen-rich storage medium, the influence of a collection of first and second period transition metal fluorides on the destabilization of NaBH4 is studied on samples produced by ball milling NaBH4 with 2 mol% of a metal fluoride additive. The effects obtained by increasing additive amount and changing oxidation state are also evaluated for NbF5, CeF3, and CeF4. The as-milled products are characterized by in-house power X-ray diffraction, while the hydrogen release and decomposition are monitored by temperature programmed desorption with residual gas analysis, differential scanning calorimetry, and thermogravimetry. The screening of samples containing 2 mol% of additive shows that distinctive groups of transition metal fluorides affect the ball milling process differently depending on their enthalpy of formation, melting point, or their ability to react at the temperatures achieved during ball milling. This leads to the formation of NaBF4 in the case of TiF4, MnF3, VF4, CdF2, NbF5, AgF, and CeF3 and the presence of the metal in CrF3, CuF2, and AgF. There is no linear correlation between the position of the transition metal in the periodic table and the observed behavior. The thermal behavior of the products after milling is given by the remaining NaBH4, fluoride, and the formation of intermediate metastable compounds. A noticeable decrease of the decomposition temperature is seen for the majority of the products, with the exceptions of the samples containing YF3, AgF, and CeF3. The largest decrease of the decomposition temperature is observed for NbF5. When comparing increasing amounts of the same additive, the largest decrease of the decomposition temperature is observed for 10 mol% of NbF5. Higher amounts of additive result in the loss of the NaBH4 thermal signal and ultimately the loss of the crystalline borohydride. When comparing additives with the same transition metal and different oxidation states, the most efficient additive is found to be the one with a higher oxidation state. Furthermore, among all the samples studied, higher oxidation state metal fluorides are found to be the most destabilizing agents for NaBH4. Overall, the present study shows that there is no single parameter affecting the destabilization of NaBH4 by transition metal fluorides. Instead, parameters such as the transition metal electronegativity and oxidation state or the enthalpy of formation of the fluoride and its melting point are competing to influence the destabilization. In particular, it is found that the combination of a high metal oxidation state and a low fluoride melting point will enhance destabilization. This is observed for MnF3, NbF5, NiF2, and CuF2, which lead to high gas releases from the decomposition of NaBH4 at the lowest decomposition temperatures.

Benchmarking Density Functionals on First Row Transition Metal Fluorides (ScF−MnF)

In this work, we have assessed the performances of ten density functionals for the bond length, vibrational frequency and bond dissociation energy values of first row transition metal fluorides (TMFs). The selected density functionals are, TPSSh, B3LYP, B97, PBE0, ɷB97X, ɷB97X-D, M05, M05-2X, M06 and M06-2X respectively. The obtained results are in agreement with the previous experimental or theoretical results. From this study, it is found that the mean deviation in the metal-fluoride bond length is in the range of 0.01−0.06 Å and the mean deviation in the metal-fluoride bond energy is in the range of 0.16−0.74 eV. Based on this study, we suggest that the B3LYP, TPSSh, B97 and PBE0 functionals can produce good results for selected metal fluoride systems and will be recommended for the above systems.

Densification of Magnesium Aluminate Spinel Using Manganese and Cobalt Fluoride as Sintering Aids

Highly dense magnesium aluminate spinel bodies are usually fabricated using pressure-assisted methods, such as spark plasma sintering (SPS), in the presence of lithium fluoride as a sintering aid. The present work investigates whether the addition of transition metal fluorides promotes the sintering of MgAl2O4 bodies during SPS. At the same time, such fluorides can act as a source of optically active dopants. A commercial MgAl2O4 was mixed with 0.5 wt% of LiF, MnF2, and CoF2 and, afterwards, consolidated using SPS at 1400 °C. Although MnF2 and CoF2 promote the densification as effectively as LiF, they cause significant grain growth.

Deoxyfluorination Using CuF2

<div>Deoxyfluorination is a primary method for the formation of C–F bonds. Bespoke reagents are commonly used due to issues associated with the low reactivity of metal fluorides. Here, we report the development of a simple strategy for deoxyfluorination using first-row transition metal fluorides that overcomes these limitations. Using CuF2 as an exemplar, activation of an O-alkylisourea adduct formed in situ allows effective nucleophilic fluoride transfer to a range of primary and secondary alcohols. Spectroscopic investigations have been used to probe the origin of the enhanced reactivity of CuF2. The utility of the process towards enabling 18F-radiolabeling is also presented.</div>