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Trends in the series of ammine rare-earth-metal borohydrides: Relating structural and thermal properties

DOI: 10.1021/acs.inorgchem.0c03464 DOI Help

Authors: Jakob B. Grinderslev (University of Aarhus) , Torben R. Jensen (Aarhus University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Inorganic Chemistry

State: Published (Approved)
Published: January 2021

Abstract: Ammine metal borohydrides display extreme structural and compositional diversity and show potential applications for solid-state hydrogen and ammonia storage and as solid-state electrolytes. Thirty-two new compounds are reported in this work, and trends in the full series of ammine rare-earth-metal borohydrides are discussed. The majority of the rare-earth metals (RE) form trivalent RE(BH4)3·xNH3 (x = 7–1) compounds, which possess an intriguing crystal chemistry changing with the number of ammonia ligands, varying from structures built from complex ions (x = 5–7), to molecular structures (x = 3, 4), one-dimensional chains (x = 2), and structures built from two-dimensional layers (x = 1). Divalent RE(BH4)2·xNH3 (x = 4, 2, 1) compounds are observed for RE2+ = Sm, Eu, Yb, with structures varying from molecular structures (x = 4) to two-dimensional layered (x = 2, 1) and three-dimensional structures (Yb(BH4)2·NH3). The crystal structure and composition of the compounds depend on the volume of the rare-earth ion. In all structures, NH3 coordinates to the metal, while BH4– has a more flexible coordination and is observed as a bridging and terminal ligand and as a counterion. RE(BH4)3·xNH3 (x = 7–5, 4) releases NH3 stepwise during thermal treatment, while mainly H2 is released for x ≤ 3. In contrast, only NH3 is released from RE(BH4)2·xNH3 due to the lower charge density on the RE2+ ion and higher stability of RE(BH4)2. The thermal stability of RE(BH4)3·xNH3 increase with increasing cation charge density for x = 5, 7, while it decreases for x = 4, 6. For x = 3, the thermal stability decreases with increasing charge density, due to the destabilization of the BH4– group, making it more reactive toward NH3. This research provides a large number of novel compounds and new insight into trends in the crystal chemistry of ammine metal borohydrides and reveals a correlation between the local metal coordination and the thermal stability.

Journal Keywords: Anions; Metals; Ammonia; Crystal structure; Cations

Subject Areas: Chemistry

Instruments: I11-High Resolution Powder Diffraction

Other Facilities: BM01 at ESRF

Added On: 01/02/2021 09:45

Discipline Tags:

Chemistry Inorganic Chemistry

Technical Tags:

Diffraction X-ray Powder Diffraction