Na₃SO₄H—The First Representative of the Material Class of Sulfate Hydrides

Abstract

The first representative of a novel class of mixed‐anionic compounds, the sulfate hydride Na3SO4H, and the corresponding deuteride Na3SO4D were obtained from the solid‐state reaction of NaH or NaD with dry Na2SO4. Precise reaction control is required, because too harsh conditions lead to the reduction of sulfate to sulfide. A combined X‐ray and neutron diffraction study revealed that the compound crystallizes in the tetragonal space group P4/nmm with the lattice parameters a=7.0034(2) Å and c=4.8569(2) Å. The sole presence of hydride and absence of hydroxide ions is proven by vibrational spectroscopy and comparison with spectra predicted from quantum chemical calculations. 1H and 23Na MAS NMR spectra are consistent with the structure of Na3SO4H: a single 1H peak at 2.9 ppm is observed, while two peaks at 15.0 and 6.2 ppm for the inequivalent 23Na sites are observed. Elemental analysis and quantum chemical calculations further support these results.

Expanding the hydride chemistry: antiperovskites A3MO4H (A = Rb, Cs; M = Mo, W) introducing the transition oxometalate hydrides

“…The tolerance factor deviates even more from 1 in Na 3 SO 4 H which represents a further antiperovskite-like hydride ( P 4/ nmm , Ag 3 CrO 4 Cl-type). 20 Compared to the structure types presented in this work, the assembly is different in Na 3 SO 4 H as the alkaline (Na + ) ions are now considerably smaller than the hydride ions. In turn, the sulfate anions demand less space within the cuboctrahedral voids in relation to the larger oxometalate anions.…”

“…The transition oxometalate hydrides are synthetically accessible by a solid-state reaction under hydrogen pressure with controlled conditions. As inspired by a recent study about a novel sulfate hydride, 20 a thermal synthesis route is applied to synthesize the herein presented compounds. In a typical synthesis, the alkaline metal A (A = Rb, Cs) is reacted with the quasi-binary oxometalate salts (A 2 MoO 4 , A 2 WO 4 ) at 528 K for the molybdate hydrides and 600 K for the tungstate hydrides under an applied hydrogen pressure of 10 bar.…”

“…As inspired by a recent study about a Chair of Inorganic Chemistry with Focus on Novel Materials, Technical University of Munich, Lichtenbergstrasse 4, 85748 Garching, Germany. E-mail: Alex.Mutschke@ tum.de; ga74lud@mytum.de b Felix Bloch Institute for Solid State Physics Leipzig University, Linnéstrasse 5, 04103 Leipzig, Germany 20 a thermal synthesis route is applied to synthesize the herein presented compounds. In a typical synthesis, the alkaline metal A (A ¼ Rb, Cs) is reacted with the quasi-binary oxometalate salts (A 2 MoO 4 , A 2 WO 4 ) at 528 K for the molybdate hydrides and 600 K for the tungstate hydrides under an applied hydrogen pressure of 10 bar.…”

Trendbericht Festkörperchemie 2022

“…Kunkel und Coautor:innen haben ebenfalls ein neues Hydrid präsen-tiert, genauer gesagt ein Sulfathydrid. 3) Na 3 SO 4 H entsteht in einer Festkörperreaktion aus NaH und Na 2 SO 4 . Dass ausschließlich Hydrid und keine Hydroxidionen vorliegen, belegen Vergleiche schwingungsspektroskopischer Messungen mit Resultaten von DFT-Rechnungen.…”

Anti‐perovskite materials for energy storage batteries

“…However, these hydride-based antiperovskite SSEs were experimentally measured to possess relatively low ionic conductivity, for example, Na 2.9 HSe 0.9 I 0.1 delivered an ionic conductivity of 1 Â 10 À4 S cm À1 at 100 C with the activation barrier of 0.42 eV. Simultaneously, Mutschke et al 51 developed another hydride-based antiperovskite Na 3 HSO 4 with SO 4 2À divalent anion cluster at the dodecahedral center. But the ionic conductivity of Na 3 HSO 4 needs to be experimentally investigated.…”