Density functional theory calculations were applied to investigate LiF decoration of B₁₂N₁₂ cage in terms of the structures and stabilities. Then, the resulted LiF-decorated B₁₂N₁₂ cages were explored to find their capability as hydrogen storage. The DFT results showed that decoration of BN cages is independent of the previously decorated BN bonds. LiF decoration of BN bonds leads to charge redistribution so that charges of the atoms nearest to the decorated bonds change and charges of the other ones remain rather unchanged. Hydrogen prefers to bind to the B atoms that are nearest to the decorated Li. It was revealed that H atoms bind more strongly to B atoms of LiF-decorated B₁₂N₁₂ cages in comparison to pristine B₁₂N₁₂ cage. Two types of hydrogen bonding were formed in B₁₂N₁₂Li₄F₄ and B₁₂N₁₂Li₆F₆, binding of hydrogens in a quasi-molecular form to the decorated Li atoms, and also binding of hydrogen in atomic to B atoms. Calculated binding energies showed that binding of hydrogen to the models is an intermediate between physical and chemical adsorption, indicating that the LiF-decorated B₁₂N₁₂ cages are suitable as hydrogen storage materials.

Graphic abstract

中文翻译：

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LiF修饰的BN笼作为储氢材料的理论探索

应用密度泛函理论计算来研究 B ₁₂ N ₁₂笼的LiF 装饰的结构和稳定性。然后，探索所得的 LiF 装饰的 B ₁₂ N ₁₂笼子，以发现它们作为储氢的能力。DFT 结果表明，BN 笼的装饰与先前装饰的 BN 键无关。BN 键的 LiF 装饰导致电荷重新分布，因此最接近装饰键的原子的电荷发生变化，而其他原子的电荷保持不变。氢更喜欢与最靠近装饰锂的 B 原子结合。结果表明，H 原子与 LiF 装饰的 B ₁₂ N _{12 的}B 原子结合更强笼与原始 B ₁₂ N ₁₂笼相比。在B ₁₂ N ₁₂ Li ₄ F ₄和B ₁₂ N ₁₂ Li ₆ F ₆中形成了两种类型的氢键，准分子形式的氢与装饰的Li原子结合，以及氢原子与B的结合原子。计算的结合能表明，氢与模型的结合是物理和化学吸附之间的中间体，表明 LiF 装饰的 B ₁₂ N ₁₂笼适合作为储氢材料。

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