First-Principles Prediction of Intermediate Products in the Decomposition of Metal Amidoboranes

Journal Article · Thu Dec 27 04:00:00 EST 2012 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/jp3106293· OSTI ID:1064595

Zhang, Yongsheng; Autrey, Tom; Wolverton, C.

The non-volatile products remaining after the thermal decomposition of metal amidoboranes ([M]n+[NH2BH3]^- , M = alkali or alkaline metal atom) are amorphous and incompletely characterized increasing the complexity of devising regeneration strategies for these potential hydrogen storage materials. Utilizing the combined prototype electrostatic ground state search (PEGS) and density-functional theory (DFT) methodology (PEGS+DFT), we have searched for crystal structures of possible intermediate phases with [NHBH2]^-, [NBH]^-, [N3H2B3H3]^-, and polymer-M[NHBH2] anion groups in the decomposition of lithium amidoborane (LiAB) and calcium amidoborane (CaAB). All these potential reaction products are calculated to be significantly endothermic, in contrast to the experimentally measured nearly thermo neutral values [3 to 5 kJ/(mol H2) in LiAB and 3.5 kJ/(mol H2) in CaAB] suggesting that there are alternative products formed. The dianion group [NHBHNHBH3]^2- has recently been suggested to form in the decomposition of a calcium amidoborane complex in solution. In LiAB and CaAB, we use PEGS+DFT calculations to predict intermediate metal-dianion compounds, and the static H2 release enthalpy is 27.4 kJ/(mol H2) in LiAB and 27.3 kJ/(mol H2) in CaAB, respectively. Introducing vibrational effects by phonon calculations, the enthalpies are shifted down by a roughly constant amount, _25 kJ/(mol H2) at 0 K and _22 kJ/(mol H2) at 300 K. Thus, our theoretical H2 release enthalpies agree with the experimentally measured nearly thermo-neutral data in the decomposition of LiAB and CaAB. This agreement supports the existence of the dianion phases as products in the decomposition of metal amidoboranes. Then, using the dianion compound as an intermediate in the decomposition of MAB, we further study the stability trends of a series of MAB (M=Li, Na, K, Ca), and find that the reaction enthalpies generally obey the following trend: The amidoborane becomes more stable, i.e., MAB stability increases as the metal cation moves down in the periodic table along a given column (LiAB>NaAB>KAB), or as metal cation moves to the left along a given row (KAB>CaAB). T.A. acknowledges the Fuel Cell Technology Program at USDOE, Office of Energy Efficiency and Renewable Energy. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1064595
• Report Number(s): PNNL-SA-89945; HT0202000
• Journal Information: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 51 Vol. 116; ISSN 1932-7447
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

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36 MATERIALS SCIENCE