Base-Metal Nanoparticle-Catalyzed Hydrogen Release from Ammine Yttrium and Lanthanum Borohydrides

Mostajeran, Mehdi; Ye, Eric; Desgreniers, Serge; Baker, R. Tom

doi:10.1021/acs.chemmater.6b04585

Cited by 4 publications

(12 citation statements)

References 63 publications

(128 reference statements)

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“… a Structural model could not be verified by DFT. b This structural model provides a very convincing fit to diffraction data measured for compounds previously reported to have the compositions A (BH 4 ) 3 ·4NH 3 ( A = Y, La, Gd, Dy). , c This structural model provides a very convincing fit to diffraction data measured of A (BH 4 ) 3 ·5NH 3 ( A = Y, Gd, Dy) and is considered as a more convincing structural model also for these compounds. d Diffraction data collection temperature. …”

Section: Results and Discussionmentioning

confidence: 66%

“…This structural model provides a very convincing fit to diffraction data measured for compounds previously reported to have the compositions A (BH 4 ) 3 ·4NH 3 ( A = Y, La, Gd, Dy). , …”

Section: Results and Discussionmentioning

confidence: 99%

“…Ammine metal borohydrides often release a mixture of both hydrogen and ammonia upon thermolysis. The systems may be tuned toward release of hydrogen by changing the BH 4 /NH 3 ratio by mixing with the corresponding metal borohydride, , by forming ammines of bimetallic borohydrides, i.e., introducing additional BH 4 groups, ,, or by introducing other compounds that can react with the NH 3 , e.g., NH 3 BH 3 or other M(BH 4 ) x compounds. − Other strategies involve nanoconfinement, , fluorine substitution, , or metal nanoparticle catalysis . In this work, we present trends in synthesis and structures of seven new halide-free ammine metal borohydrides based on lanthanum and cerium, investigated by in situ synchrotron powder X-ray diffraction (SR-PXD), Fourier-transformed infrared spectroscopy (FTIR), density functional theory (DFT) calculations, thermal analysis, and nuclear magnetic resonance (NMR) spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

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Ammine Lanthanum and Cerium Borohydrides, M(BH₄)₃·nNH₃; Trends in Synthesis, Structures, and Thermal Properties

et al. 2020

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Ammine metal borohydrides show potential for solid-state hydrogen storage and can be tailored toward hydrogen release at low temperatures. Here, we report the synthesis and structural characterization of seven new ammine metal borohydrides, M(BH4)3·nNH3, M = La (n = 6, 4, or 3) or Ce (n = 6, 5, 4, or 3). The two compounds with n = 6 are isostructural and have new orthorhombic structure types (space group P21212) built from cationic complexes, [M(NH3)6(BH4)2]+, and are charge balanced by BH4 –. The structure of Ce(BH4)3·5NH3 is orthorhombic (space group C2221) and is built from cationic complexes, [Ce(NH3)5(BH4)2]+, and charge balanced by BH4 –. These are rare examples of borohydride complexes acting both as a ligand and as a counterion in the same compound. The structures of M(BH4)3·4NH3 are monoclinic (space group C2), built from neutral molecular complexes of [M(NH3)4(BH4)3]. The new compositions, M(BH4)3·3NH3 (M = La, Ce), among ammine metal borohydrides, are orthorhombic (space group Pna21), containing molecular complexes of [M(NH3)3(BH4)3]. A revised structural model for A(BH4)3·5NH3 (A = Y, Gd, Dy) is presented, and the previously reported composition A(BH4)3·4NH3 (A = Y, La, Gd, Dy) is proposed in fact to be M(BH4)3·3NH3 along with a new structural model. The temperature-dependent structural properties and decomposition are investigated by in situ synchrotron radiation powder X-ray diffraction in vacuum and argon atmosphere and by thermal analysis combined with mass spectrometry. The compounds with n = 6, 5, and 4 mainly release ammonia at low temperatures, while hydrogen evolution occurs for M(BH4)3·3NH3 (M = La, Ce). Gas-release temperatures and gas composition from these compounds depend on the physical conditions and on the relative stability of M(BH4)3·nNH3 and M(BH4)3.

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Section: Results and Discussionmentioning

confidence: 66%

“…This structural model provides a very convincing fit to diffraction data measured for compounds previously reported to have the compositions A (BH 4 ) 3 ·4NH 3 ( A = Y, La, Gd, Dy). , …”

Section: Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ammine Lanthanum and Cerium Borohydrides, M(BH₄)₃·nNH₃; Trends in Synthesis, Structures, and Thermal Properties

et al. 2020

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“…The compounds RE(BH 4 ) 3 ·3NH 3 (RE 3+ = Pr, Nd, Tb, Ho, Er, Tm) crystallize in the orthorhombic space group Pna 2 1 (Figure ), isostructural with RE(BH 4 ) 3 ·3NH 3 (RE 3+ = La, Ce) . This is a revised structural model and composition of the previously reported RE(BH 4 ) 3 ·4NH 3 (RE 3+ = Y, La, Gd, Dy). ,, In the structure of RE(BH 4 ) 3 ·3NH 3 , one unique RE 3+ position is coordinated by three terminal BH 4 – groups and three NH 3 molecules, forming neutral [RE(NH 3 ) 3 (BH 4 ) 3 ] octahedral complexes in the fac isomer. The molecular complexes are arranged in hexagonal patterns in the ab plane and are stacked in the sequence ABAB along the c axis.…”

Section: Resultsmentioning

confidence: 76%

“…62 This is a revised structural model and composition of the previously reported RE(BH 4 ) 3 •4NH 3 (RE 3+ = Y, La, Gd, Dy). 61,73,76 In the structure of RE(BH 4 ) 3 •3NH 3 , one unique RE 3+ position is coordinated by three terminal BH 4…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Trends in the Series of Ammine Rare-Earth-Metal Borohydrides: Relating Structural and Thermal Properties

Grinderslev

2021

Inorg. Chem.

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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(BH 4 ) 3 •xNH 3 (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), onedimensional chains (x = 2), and structures built from two-dimensional layers (x = 1). Divalent RE(BH 4 ) 2 •xNH 3 (x = 4, 2, 1) compounds are observed for RE 2+ = Sm, Eu, Yb, with structures varying from molecular structures (x = 4) to two-dimensional layered (x = 2, 1) and threedimensional structures (Yb(BH 4 ) 2 •NH 3 ). The crystal structure and composition of the compounds depend on the volume of the rare-earth ion. In all structures, NH 3 coordinates to the metal, while BH 4 − has a more flexible coordination and is observed as a bridging and terminal ligand and as a counterion. RE(BH 4 ) 3 •xNH 3 (x = 7−5, 4) releases NH 3 stepwise during thermal treatment, while mainly H 2 is released for x ≤ 3. In contrast, only NH 3 is released from RE(BH 4 ) 2 •xNH 3 due to the lower charge density on the RE 2+ ion and higher stability of RE(BH 4 ) 2 . The thermal stability of RE(BH 4 ) 3 •xNH 3 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 BH 4 − group, making it more reactive toward NH 3 . 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.

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Hydrogen storage in complex hydrides: past activities and new trends

et al. 2022

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Intense literature and research efforts have focussed on the exploration of complex hydrides for energy storage applications over the past decades. A focus was dedicated to the determination of their thermodynamic and hydrogen storage properties, due to their high gravimetric and volumetric hydrogen storage capacities, but their application has been limited because of harsh working conditions for reversible hydrogen release and uptake. The present review aims at appraising the recent advances on different complex hydride systems, coming from the proficient collaborative activities in the past years from the research groups led by the experts of the Task 40 “Energy Storage and Conversion Based on Hydrogen” of the Hydrogen Technology Collaboration Programme of the International Energy Agency. An overview of materials design, synthesis, tailoring and modelling approaches, hydrogen release and uptake mechanisms and thermodynamic aspects are reviewed to define new trends and suggest new possible applications for these highly tuneable materials.

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Base-Metal Nanoparticle-Catalyzed Hydrogen Release from Ammine Yttrium and Lanthanum Borohydrides

Cited by 4 publications

References 63 publications

Ammine Lanthanum and Cerium Borohydrides, M(BH₄)₃·nNH₃; Trends in Synthesis, Structures, and Thermal Properties

Ammine Lanthanum and Cerium Borohydrides, M(BH₄)₃·nNH₃; Trends in Synthesis, Structures, and Thermal Properties

Trends in the Series of Ammine Rare-Earth-Metal Borohydrides: Relating Structural and Thermal Properties

Hydrogen storage in complex hydrides: past activities and new trends

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Base-Metal Nanoparticle-Catalyzed Hydrogen Release from Ammine Yttrium and Lanthanum Borohydrides

Cited by 4 publications

References 63 publications

Ammine Lanthanum and Cerium Borohydrides, M(BH4)3·nNH3; Trends in Synthesis, Structures, and Thermal Properties

Ammine Lanthanum and Cerium Borohydrides, M(BH4)3·nNH3; Trends in Synthesis, Structures, and Thermal Properties

Trends in the Series of Ammine Rare-Earth-Metal Borohydrides: Relating Structural and Thermal Properties

Hydrogen storage in complex hydrides: past activities and new trends

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Product

Resources

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Ammine Lanthanum and Cerium Borohydrides, M(BH₄)₃·nNH₃; Trends in Synthesis, Structures, and Thermal Properties

Ammine Lanthanum and Cerium Borohydrides, M(BH₄)₃·nNH₃; Trends in Synthesis, Structures, and Thermal Properties