新型光催化材料石墨炔-TiO2的第一性原理研究

doi:10.6023/A12090705

摘要/Abstract

采用基于色散矫正密度泛函理论的第一性原理方法, 研究石墨炔和石墨烯对TiO₂光催化性能提高的机理. 通过研究发现在石墨炔-TiO₂(101)复合物中, 石墨炔和TiO₂(101)间相互作用较强, TiO₂(101)表面上的O原子和其top位的C原子形成离域性强的C—O共价键. 电子密度, 电子差分密度和 Mulliken 电荷的计算结果显示, 石墨炔复合TiO₂(101)晶面更有利于电子在界面间的转移, 并减低电子-空穴的复合率. 通过对电子结构的分析发现, 在石墨炔-TiO₂(101)复合物的带隙中引入了多条杂质能级, 而石墨烯-TiO₂(101)复合物的带隙中没有杂质能级的出现. 杂质能级能够为光激发时电子的跃迁提供辅助平台作用, 有利于光催化性能的提高. 同时石墨炔-TiO₂(101)复合物的价带位置比石墨烯- TiO₂(101)复合物更低, 说明其氧化能力更强, 有利于其光催化性能的提高.

关键词: 石墨炔, 石墨烯, 第一性原理计算, TiO₂

We study mechanism for combinet graphdiyne and graphene on TiO₂ which can improve the photocatalytic performance of TiO₂ by density functional theory with dispersion corrections (DFT-D) methods. Because of the different lattice parameters of graphdiyne, graphene and TiO₂(101), we used (1×1) graphdiyne supercell with (1×4) TiO₂(101) supercell to built the graphdiyne-TiO₂(101) composite, and (2×6) graphdiyne supercell with (1×5) TiO₂(101) supercell to built the graphene-TiO₂(101) composite. In detail, as the strong adsorption between carbon atom and the TiO₂ support, numbers of new high electron delocalization C—O covalent bonds were formed by O atom in TiO₂ surface and atop C atom in graphdiyne. While for the graphene-TiO₂(101) composite, the equilibrium distances between graphene and TiO₂ are so large that even the nearest C atoms were far as 2.869 ? to the TiO₂ planes, indicating the weak interaction between graphene and TiO₂ surface. The electron density, electron density difference were analyzed, the result shown that the graphdiyne combined with TiO₂(101) surface is beneficial to the charge transfer. The Mulliken charge population shows that the graphdiyne or graphene surface has a positive Mulliken charge, forming large opposite interface dipole at the interface, leading to a strong built-in electric field throughout the superlattice, which can resist the possibility of electron-hole recombination. Since the magnitude of charge accumulation in graphdiyne is larger than graphene surface, stronger electrons capture ability of graphdiyne- TiO₂(001) composite could be expected compared to graphene-TiO₂(001) composite. The electronic band structure shown that in the graphdiyne-TiO₂(101) composite, numbers of isolated energy levels were localized in the band gap which can reduce the electronic excitation energy from the isolated energy levels to the conductive band. The graphene-TiO₂(101) composite had no isolated energy level appeared in the band gap. The graphdiyne-TiO₂(101) composite has a lower valence band position than the graphene-TiO₂(101) composite ones, means compared with graphene composite, graphdiyne composite always shows higher oxidation ability, which induce a higher photocatalytic performance.

Key words: graphdiyne, graphene, first principles calculation, TiO₂

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刘媛媛. 新型光催化材料石墨炔-TiO₂的第一性原理研究[J]. 化学学报, 2013, 71(02): 260-264.

Liu Yuanyuan. First-Principles Study on New Photocatalytic Materials Graphdiyne-TiO₂[J]. Acta Chimica Sinica, 2013, 71(02): 260-264.

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新型光催化材料石墨炔-TiO₂的第一性原理研究

First-Principles Study on New Photocatalytic Materials Graphdiyne-TiO₂

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