Pupysheva Olga V, Farajian Amir A, Yakobson Boris I
Department of Mechanical Engineering & Materials Science, Rice University, Houston, TX 77005, USA.
Nano Lett. 2008 Mar;8(3):767-74. doi: 10.1021/nl071436g. Epub 2007 Oct 9.
We model fullerene nanocages filled with hydrogen, of the general formula Hn@Ck, and study the capacity of such endohedral fullerenes to store hydrogen. It is shown using density functional theory that for large numbers of encapsulated hydrogen atoms, some of them become chemisorbed on the inner surface of the cage. A maximum of 58 hydrogen atoms inside a C60 cage is found to still remain a metastable structure, and the mechanism of its breaking is studied by ab initio molecular dynamics simulations. Hydrogen pressure inside the fullerene nanocage is estimated for the first time and is shown to reach the values only a few times smaller than the pressure of hydrogen metallization. We provide a general relation between the hydrogen pressure and resulting C-C bond elongation for fullerene nanocages of arbitrary radii. This opens a way to assess possible hydrogen content inside larger carbon nanocages, such as giant fullerenes, where significant capacity can be reached at reasonable conditions.
我们对通式为Hn@Ck的充满氢的富勒烯纳米笼进行建模,并研究此类内嵌富勒烯储存氢的能力。利用密度泛函理论表明,对于大量被封装的氢原子,其中一些会化学吸附在笼的内表面。发现C60笼内最多58个氢原子仍为亚稳结构,并通过从头算分子动力学模拟研究了其分解机制。首次估算了富勒烯纳米笼内的氢压力,结果表明其达到的值仅比氢金属化压力小几倍。我们给出了任意半径富勒烯纳米笼的氢压力与由此导致的C-C键伸长之间的一般关系。这为评估更大碳纳米笼(如巨型富勒烯)内可能的氢含量开辟了一条途径,在合理条件下,巨型富勒烯可达到显著的储氢容量。