Dehydrogenation Tuning of Ammine Borohydrides Using Double-Metal Cations

Guo, Yanhui; Wu, Hui; Zhou, Wei; Yu, Xuebin

doi:10.1021/ja1105893

Cited by 106 publications

(124 citation statements)

References 38 publications

(55 reference statements)

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“…[15] Since then, a range of novel ammine metal borohydrides have been examined, [17][18][19][20] and one of the most successful is Zn(BH 4 ) 2 ·2NH 3 , which releases 8.9 wt % of pure H 2 below 115 8C within 15 min. [21] Remarkably, Zn(BH 4 ) 2 is not stable on its own and can be stabilized by less electronegative atoms in bimetallic borohydrides.…”

Section: Soloveichik Et Al Showed In 2009mentioning

confidence: 99%

Tailoring the Properties of Ammine Metal Borohydrides for Solid‐State Hydrogen Storage

et al. 2015

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A series of halide-free ammine manganese borohydrides, Mn(BH4 )2 ⋅nNH3 , n=1, 2, 3, and 6, a new bimetallic compound Li2 Mn(BH4 )4 ⋅6NH3 , and the first ammine metal borohydride solid solution Mg1-x Mnx (BH4 )2 ⋅6NH3 are presented. Four new crystal structures have been determined by synchrotron radiation powder X-ray diffraction and the thermal decomposition is systematically investigated for all the new compounds. The solid-gas reaction between Mn(BH4 )2 and NH3 provides Mn(BH4 )2 ⋅6NH3 . The number of NH3 per Mn has been varied by mechanochemical treatment of Mn(BH4 )2 ⋅6NH3 -Mn(BH4 )2 mixtures giving rise to increased hydrogen purity for n/m≤1 for M(BH4 )m ⋅nNH3 . The structures of Mg(BH4 )2 ⋅3NH3 and Li2 Mg(BH4 )4 ⋅6NH3 have been revisited and new structural models are presented. Finally, we demonstrate that ammonia destabilizes metal borohydrides with low electronegativity of the metal (χp <∼1.6), while metal borohydrides with high electronegativity (χp >∼1.6) are generally stabilized.

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Section: Soloveichik Et Al Showed In 2009mentioning

confidence: 99%

Tailoring the Properties of Ammine Metal Borohydrides for Solid‐State Hydrogen Storage

et al. 2015

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“…[36][37][38][39] Interestingly,d estabilization is observed for most metal borohydrides with low electronegativity (c p <~1.6), whereas metal borohydrides with ah igh electronegativity (c p >~1.6) are stabilized by NH 3 (i.e.,they releaseg as at higher temperatures). [4,15] However, the generalm echanism for decomposition is not fully understood.…”

Section: Mechanism For the Decomposition Of Ammine Metal Borohydridesmentioning

confidence: 99%

Ammine Calcium and Strontium Borohydrides: Syntheses, Structures, and Properties

et al. 2015

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A new series of solvent- and halide-free ammine strontium metal borohydrides Sr(NH3 )n (BH4 )2 (n=1, 2, and 4) and further investigations of Ca(NH3 )n (BH4 )2 (n=1, 2, 4, and 6) are presented. Crystal structures have been determined by powder XRD and optimized by DFT calculations to evaluate the strength of the dihydrogen bonds. Sr(NH3 )(BH4 )2 (Pbcn) and Sr(NH3 )2 (BH4 )2 (Pnc2) are layered structures, whereas M(NH3 )4 (BH4 )2 (M=Ca and Sr; P21 /c) are molecular structures connected by dihydrogen bonds. Both series of compounds release NH3 gas upon thermal treatment if the partial pressure of ammonia is low. Therefore, the strength of the dihydrogen bonds, the structure of the compounds, and the NH3 /BH4 (-) ratio for M(NH3 )n (BH4 )m have little influence on the composition of the released gasses. The composition of the released gas depends mainly on the thermal stability of the ammine metal borohydride and the corresponding metal borohydride.

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“…Metal amidoboranes (MNH2BH3, MAB) and metal borohydride ammoniates (MBH4·nNH3, MBA) are currently among the most promising candidate materials [1][2][3][4][5][6]. Recent demonstration of the regeneration of ammonia borane derivatives using hydrazine in liquid ammonia point to the feasibility of off-board reversibility [7][8][9].…”

Section: Introductionmentioning

confidence: 99%