铝烷配合物储氢热化学的理论与实验比较
Thermochemistry of Alane Complexes for Hydrogen Storage: A Theoretical and Experimental Comparison
摘要：
铝烷（AlH 3）配合物与电子供体的相对稳定性的知识是必不可少的识别贮氢材料的车辆应用，可以再生的非车载方法，但是，几乎没有热力学数据，使这一评估。为了填补这一空白，我们采用G4（MP2）方法，以确定38铝烷配合物的形成热，熵，和吉布斯自由能与NH 3-nRn（R = Me，Et; n = 0-3），吡啶，吡嗪，三亚乙基二胺（TEDA），奎宁环，OH 2-nRn（R = Me，Et; n = 0-2），二氧六环，和四氢呋喃（THF）。被认为是magnesium，双，和选定的二聚体复杂的几何形状。使用这些数据，我们计算的热力学的关键形成和脱氢反应，将发生在氢气输送和铝烷再生，从复杂的稳定性的趋势被确定。这些预测进行了测试，通过合成六个胺-铝烷络合物，涉及三甲基胺，三乙胺，二甲基乙胺，TEDA，奎宁环，和六胺，并获得上限的δ G为它们形成的金属铝。结合这些计算和实验结果，我们建立了一个标准的复杂的稳定性相关的储氢，可用于评估潜在的配体之前，试图合成的铝烷络合物。基于此，我们得出结论，只有一个子集的叔胺络合物考虑和醚络合物可以成功地通过与铝的直接反应形成和再生的铝烷为基础的储氢系统。
英文摘要：
Knowledge of the relative stabilities of alane (AlH3) complexes with electron donors is essential for identifying hydrogen storage materials for vehicular applications that can be regenerated by off-board methods; however, almost no thermodynamic data are available to make this assessment. To fill this gap, we employed the G4(MP2) method to determine heats of formation, entropies, and Gibbs free energies of formation for thirty-eight alane complexes with NH3-nRn (R = Me, Et; n = 0-3), pyridine, pyrazine, triethylenediamine (TEDA), quinuclidine, OH2-nRn (R = Me, Et; n = 0-2), dioxane, and tetrahydrofuran (THF). Monomer, bis, and selected dimer complex geometries were considered. Using these data, we computed the thermodynamics of the key formation and dehydrogenation reactions that would occur during hydrogen delivery and alane regeneration, from which trends in complex stability were identified. These predictions were tested by synthesizing six amine-alane complexes involving trimethylamine, triethylamine, dimethylethylamine, TEDA, quinuclidine, and hexamine, and obtaining upper limits of delta G for their formation from metallic aluminum. Combining these computational and experimental results, we establish a criterion for complex stability relevant to hydrogen storage that can be used to assess potential ligands prior to attempting synthesis of the alane complex. Based on this, we conclude that only a subset of the tertiary amine complexes considered and none of the ether complexes can be successfully formed by direct reaction with aluminum and regenerated in an alane-based hydrogen storage system.
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