论文标题
实验合成的基于己嗪的和三嗪的二维石墨氮化碳的新结构候选
New structure canditates for the experimentally synthesized heptazine-based and triazine-based two dimensional graphitic carbon nitride
论文作者
论文摘要
基于己嗪的二维(2D)石墨氮化碳(G-C $ _3 $ n $ _4 $)的广泛使用的晶体结构是平坦的P-6M2配置。但是,实验合成的2D G-C $ _3 $ n $ _4 $具有0.2-0.5 nm的厚度,表明理论上使用的Flat P-6M2配置不是正确的接地状态。在这项工作中,我们提出了三个新的波纹结构P321,P3M1和PCA21,其能量为66(86),77(87)和78(89)MEV/ATOM,低于基于甲基嗪的(基于甲基苯)的G-C $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4 $ _4。这些波纹结构与扁平P-6M2的结构具有非常相似的周期性模式,并且很难根据其顶级视图将它们彼此区分。在1.347-3.142Å中的三个波纹结构的优化厚度与实验结果非常吻合。第一原理结果表明,这些波纹结构候选者也是半导体,带隙略大于相应平坦的P-6M2。此外,它们还具有合适的带边缘位置,用于在$ ph = 0 $和$ pH = 7 $环境下以日光照射驱动的水分。我们的结果表明,对于实验合成的G-C $ _3 $ n $ _4 $,这三个新结构是更有希望的候选人。
The widely used crystal structures for both heptazine-based and triazine-based two-dimensional (2D) graphitic carbon nitride (g-C$_3$N$_4$) are the flat P-6m2 configurations. However, the experimentally synthesized 2D g-C$_3$N$_4$ possess thickness ranging in 0.2-0.5 nm, indicating that the theoretically used flat P-6m2 configurations are not the correct ground states. In this work, we propose three new corrugated structures P321, P3m1 and Pca21 with energies of 66 (86), 77 (87) and 78 (89) meV/atom lower than that of the corresponding heptazine-based (triazine-based) g-C$_3$N$_4$ in flat P-6m2 configuration, respectively. These corrugated structures have very similar periodic patterns to the flat P-6m2 ones and they are difficult to be distinguished from each other according to their top-views. The optimized thicknesses of the three corrugated structures ranging in 1.347-3.142 Å are in good agreement with the experimental results. The first-principles results show that these corrugated structural candidates are also semiconductors with band gaps slightly larger than those of the correspondingly flat P-6m2 ones. Furthermore, they possess also suitable band edge positions for sun-light-driven water-splitting at both $pH=0$ and $pH=7$ environments. Our results show that these three new structures are more promising candidates for the experimentally synthesized g-C$_3$N$_4$.