Understanding the Intra‐Molecular Proton Transfer of Octahydrotriborate and Exploring the Dehydrogenation Pathways of NH4B3H8 by DFT Calculations,Advanced Theory and Simulations

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Understanding the Intra‐Molecular Proton Transfer of Octahydrotriborate and Exploring the Dehydrogenation Pathways of NH4B3H8 by DFT Calculations
Advanced Theory and Simulations ( IF 2.9 ) Pub Date : 2021-02-11 , DOI: 10.1002/adts.202000287
Peng Gao ₁ , Jie Zhang _{2,

3}

Affiliation

The intra‐molecular proton transfer of octahydrotriborate, [B₃H₈]⁻, is discovered by density functional theory (DFT) computational studies; such a transfer can largely impact its dehydrogenation pathways. The DFT calculation results further disclose the generation of another triborane intermediate product, B₃H₉, which is formed via inter‐molecular proton transfer from [NH₄]⁺ to [B₃H₈]⁻. Additionally, this intermediate product is unstable and can release hydrogen easily, as the corresponding energy barrier via this pathway is only 12.0 kcal mol⁻¹. Such a relative energy is much lower than that of the routinely raised pathway, which mainly depends on the dihydrogen interaction between the

B - H^{δ -}

and

N - H^{δ +}

. This new mechanism is able to explain several experimental observations involving the dehydrogenation of NH₄B₃H₈. Moreover, the detailed dehydrogenations of NH₄B₃H₈ in different states are also studied, and the role of chemical environment during dehydrogenation is demonstrated.

中文翻译：

通过DFT计算了解八氢三硼酸盐的分子内质子转移并探索NH4B3H8的脱氢途径

八氢_三硼酸盐[B ₃ H ₈ ] ^-的分子内质子转移是通过密度泛函理论（DFT）的计算研究发现的。这种转移可大大影响其脱氢途径。DFT计算结果进一步揭示了另一种三硼烷中间产物B ₃ H _9的生成，该产物是通过分子间质子从[NH ₄ ] ⁺转移至[B ₃ H ₈ ] ^-形成的。另外，该中间产物不稳定并且容易释放氢，因为通过该途径的相应能量屏障仅为12.0 kcal mol ^-1。这样的相对能量比常规升高的途径的能量要低得多，后者主要取决于氢原子之间的二氢相互作用。