Sinthika S, Kumar E Mathan, Surya V J, Kawazoe Y, Park Noejung, Iyakutti K, Thapa Ranjit
SRM Research Institute, SRM University, Kattankulathur, Tamil Nadu, 603203, India.
New Industry Creation Hatchery Center (NICHe), Tohoku University, Sendai, Japan.
Sci Rep. 2015 Dec 2;5:17460. doi: 10.1038/srep17460.
Using density functional theory we investigate the electronic and atomic structure of fullerene-like boron nitride cage structures. The pentagonal ring leads to the formation of homonuclear bonds. The homonuclear bonds are also found in other BN structures having pentagon line defect. The calculated thermodynamics and vibrational spectra indicated that, among various stable configurations of BN-60 cages, the higher number of homonuclear N-N bonds and lower B:N ratio can result in the more stable structure. The homonuclear bonds bestow the system with salient catalytic properties that can be tuned by modifying the B atom bonding environment. We show that homonuclear B-B (B2) bonds can anchor both oxygen and CO molecules making the cage to be potential candidates as catalyst for CO oxidation via Langmuir-Hinshelwood (LH) mechanism. Moreover, the B-B-B (B3) bonds are reactive enough to capture, activate and hydrogenate CO2 molecules to formic acid. The observed trend in reactivity, viz B3 > B2 > B1 is explained in terms of the position of the boron defect state relative to the Fermi level.
利用密度泛函理论，我们研究了类富勒烯氮化硼笼状结构的电子结构和原子结构。五边形环导致了同核键的形成。在具有五边形线缺陷的其他氮化硼结构中也发现了同核键。计算得到的热力学和振动光谱表明，在氮化硼 - 60笼的各种稳定构型中，同核氮 - 氮键数量越多且硼与氮的比例越低，结构越稳定。同核键赋予该体系显著的催化性能，可通过改变硼原子的键合环境进行调节。我们表明，同核硼 - 硼（B2）键能够锚定氧分子和一氧化碳分子，使得该笼状结构有可能成为通过朗缪尔 - 欣谢尔伍德（LH）机制催化一氧化碳氧化的候选催化剂。此外，硼 - 硼 - 硼（B3）键具有足够的反应活性，能够捕获、活化二氧化碳分子并将其氢化为甲酸。观察到的反应活性趋势，即B3 ＞ B2 ＞ B1，是根据硼缺陷态相对于费米能级的位置来解释的。
