第一性原理研究O和S掺杂的石墨相氮化碳(g-C_3N_4)_6量子点电子结构和光吸收性质

First principle study of electronic structures and optical absorption properties of O and S doped graphite phase carbon nitride (g-C_3N_4)_6 quantum dots

利用密度泛函和含时密度泛函理论研究了氧(O)和硫(S)原子掺杂的石墨相氮化碳(g-C_3N_4)_6量子点的几何、电子结构和紫外-可见光吸收性质.结果表明:掺杂后(g-C_3N_4)_6量子点杂质原子周围的C-N键长发生了一定的改变,最高电子占据分子轨道-最低电子未占据分子轨道(HOMO-LUMO)能隙显著减小.形成能的计算表明O原子取代掺杂的(g-C_3N_4)_6量子点体系更稳定,且O原子更易取代N3位点,而S原子更易取代N8位点.模拟的紫外-可见电子吸收光谱表明,O和S原子的掺杂改善了(g-C_3N_4)_6量子点的光吸收,使其吸收范围覆盖了整个可见光区域,甚至扩展到了红外区.而且适当的杂质浓度使(g-C_3N_4)_6量子点光吸收在强度和范围上都得到明显改善.通过O和S掺杂的比较,发现二者在可见光区对(g-C_3N_4)_6量子点的光吸收有相似的影响,然而在长波长区域二者的影响有明显差异.总体而言,O掺杂要优于S掺杂对(g-C_3N_4)_6量子点光吸收的影响.

Graphite phase carbon nitride（g-C_3N_4） quantum dots have received much attention due to its good stability, water solubility, biological compatibility, non-toxicity as well as strong fluorescence characteristics. In order to enhance the light absorption and improve photocatalytic activities of the g-C_3N_4 quantum dots, theoretical studies are carried out on the O and S atoms doped（g-C_3N_4）_6 quantum dots. First-principles calculations based on the density functional theory and time dependent density functional theory are performed to investigate the geometries, electronic structures and ultraviolet visible absorption spectra of O and S atoms doped（g-C_3N_4）_6 quantum dots. The results show that the highest electron occupied molecular orbital-the lowest electron unoccupied molecular orbital（HOMO-LUMO） energy gap of doped（g-C_3N_4）_6 quantum dots is significantly reduced though the C-N bond lengths closely related to the impurities only change slightly. The calculated formation energies indicate that the O-doped（g-C_3N_4）_6 quantum dots are more stable, and the O atom tends to substitute for N atom at the N3-site, while the S atoms prefer to substitute for N atom at the N8-site. The simulated spectra indicate that the doping of O and S in（g-C_3N_4）_6 could improve the light absorption. Not only the absorption peaks are extended from the UV to the infrared region（e.g. 200–1600 nm）, but also the corresponding absorption intensities are enhanced significantly by doping the O or S atoms with the appropriate concentration. The increase of proper impurity concentration will lead to a pronounced red shift in light absorption. The effect of doping site on the optical absorption property of（g-C_3N_4）_6 quantum dots shows that the absorption intensity is mainly affected in the visible range, however, besides the influence on the absorption intensity, the light absorptions of some structures are also affected beyond 800 nm. Overall, the O atoms and S atoms have a substantially similar effect on the light absorption of the（g-C_3N_4）_6 quantum dots, while the effects of these impurity atoms are different in the long wavelength region. Oxygen doping is better than sulfur doping in the absorption of（g-C_3N_4）_6 quantum dots by comparing the doping of O and S. These first-principles studies give us a method to effectively improve the light absorption of g-C_3N_4 quantum dots, and could provide a theoretical reference for tuning its electronic optical properties and applications.