Hydrogen–fluorine exchange in NaBH4–NaBF4.

Hydrogen–fluorine exchange in the NaBH₄–NaBF₄ system is investigated using a range of experimental methods combined with DFT calculations and a possible mechanism for the reactions is proposed. Fluorine substitution is observed using in situ synchrotron radiation powder X-ray diffraction (SR-PXD) as a new Rock salt type compound with idealized composition NaBF₂H₂ in the temperature range T = 200 to 215 °C. Combined use of solid-state ¹⁹F MAS NMR, FT-IR and DFT calculations supports the formation of a BF₂H₂⁻ complex ion, reproducing the observation of a ¹⁹F chemical shift at −144.2 ppm, which is different from that of NaBF₄ at −159.2 ppm, along with the new absorption bands observed in the IR spectra. After further heating, the fluorine substituted compound becomes X-ray amorphous and decomposes to NaF at ∼310 °C. This work shows that fluorine-substituted borohydrides tend to decompose to more stable compounds, e.g. NaF and BF₃ or amorphous products such as closo-boranes, e.g. Na₂B₁₂H₁₂. The NaBH₄–NaBF₄ composite decomposes at lower temperatures (300 °C) compared to NaBH₄ (476 °C), as observed by thermogravimetric analysis. NaBH₄–NaBF₄ (1 : 0.5) preserves 30% of the hydrogen storage capacity after three hydrogen release and uptake cycles compared to 8% for NaBH₄ as measured using Sievert’s method under identical conditions, but more than 50% using prolonged hydrogen absorption time. The reversible hydrogen storage capacity tends to decrease possibly due to the formation of NaF and Na₂B₁₂H₁₂. On the other hand, the additive sodium fluoride appears to facilitate hydrogen uptake, prevent foaming, phase segregation and loss of material from the sample container for samples of NaBH₄–NaF. [ABSTRACT FROM AUTHOR]