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Computational Screening and Stabilization of Boron-Substituted Type-I and Type-II Carbon Clathrates
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-12-05 , DOI: 10.1021/jacs.3c08362 Tiange Bi 1 , Bryce T Eggers 2 , R E Cohen 1 , Branton J Campbell 2 , Timothy Strobel 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-12-05 , DOI: 10.1021/jacs.3c08362 Tiange Bi 1 , Bryce T Eggers 2 , R E Cohen 1 , Branton J Campbell 2 , Timothy Strobel 1
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Boron substitution represents a promising approach to stabilize carbon clathrate structures, but no thermodynamically stable substitution schemes have been identified for frameworks other than the type-VII (sodalite) structure type. To investigate the possibility for additional tetrahedral carbon-based clathrate networks, more than 5000 unique boron decoration schemes were investigated computationally for type-I and type-II carbon clathrates with a range of guest elements including Li, Na, K, Rb, Cs, Mg, Ca, Sr, and Ba. Density functional theory calculations were performed at 10 and 50 GPa, and the stability and impact of boron substitution were evaluated. The results indicate that the boron-substituted carbon clathrates are stabilized under high-pressure conditions. Full cage occupancies of intermediate-sized guest atoms (e.g., Na, Ca, and Sr) are the most favorable energetically. Clathrate stability is maximized when the boron atoms are substituted within the hexagonal rings of the large [51262]/[51264] cages. Several structures with favorable formation enthalpies <−200 meV/atom were predicted, and type-I Ca8B16C30 is on the convex hull at 50 GPa. This structure represents the first thermodynamically stable type-I clathrate identified and suggests that boron-substituted carbon clathrates may represent a large family of diamond-like framework materials with a range of structure types and guest/framework substitutions.
中文翻译：
硼取代的 I 型和 II 型碳包合物的计算筛选和稳定化
硼取代是一种稳定碳笼形结构的有前景的方法，但除了VII型（方钠石）结构类型之外，尚未确定用于骨架的热力学稳定取代方案。为了研究额外四面体碳基包合物网络的可能性，通过计算研究了 5000 多种独特的硼装饰方案，用于具有一系列客体元素（包括 Li、Na、K、Rb、Cs、镁、钙、锶和钡。在 10 和 50 GPa 下进行密度泛函理论计算，并评估硼替代的稳定性和影响。结果表明，硼取代的碳笼形物在高压条件下是稳定的。中等大小的客体原子（例如，Na、Ca 和 Sr）的全笼占据在能量上是最有利的。当硼原子在大的[5 12 6 2 ]/[5 12 6 4 ]笼的六角环内被取代时，包合物稳定性最大化。预测了几种具有有利形成焓<−200 meV/原子的结构，并且I型Ca 8 B 16 C 30位于50 GPa的凸包上。该结构代表了第一个确定的热力学稳定的 I 型包合物，并表明硼取代的碳包合物可能代表了一大类具有一系列结构类型和客体/骨架替代的类金刚石骨架材料。
更新日期：2023-12-05
中文翻译：
硼取代的 I 型和 II 型碳包合物的计算筛选和稳定化
硼取代是一种稳定碳笼形结构的有前景的方法，但除了VII型（方钠石）结构类型之外，尚未确定用于骨架的热力学稳定取代方案。为了研究额外四面体碳基包合物网络的可能性，通过计算研究了 5000 多种独特的硼装饰方案，用于具有一系列客体元素（包括 Li、Na、K、Rb、Cs、镁、钙、锶和钡。在 10 和 50 GPa 下进行密度泛函理论计算，并评估硼替代的稳定性和影响。结果表明，硼取代的碳笼形物在高压条件下是稳定的。中等大小的客体原子（例如，Na、Ca 和 Sr）的全笼占据在能量上是最有利的。当硼原子在大的[5 12 6 2 ]/[5 12 6 4 ]笼的六角环内被取代时，包合物稳定性最大化。预测了几种具有有利形成焓<−200 meV/原子的结构，并且I型Ca 8 B 16 C 30位于50 GPa的凸包上。该结构代表了第一个确定的热力学稳定的 I 型包合物，并表明硼取代的碳包合物可能代表了一大类具有一系列结构类型和客体/骨架替代的类金刚石骨架材料。
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