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锐钛矿型TiO₂(101)表面负载Au₈团簇的从头算研究。

Ab Initio Studies of Anatase TiO2 (101) Surface-supported Au8 Clusters.

作者信息

Mikolajczyk A, Pinto H P, Gajewicz A, Puzyn T, Leszczynski J

机构信息

Interdisciplinary Center for Nanotoxicity, Department of Chemistry, Jackson State University, 1400 JR. Lynch St, 39217 Jackson, USA.

出版信息

Curr Top Med Chem. 2015;15(18):1859-67. doi: 10.2174/1568026615666150506151826.

Abstract

Supported transition metals on TiO2 surfaces have shown exceptional catalytic properties in many important process such as CO oxidation, selective propane oxidation, hydrogenation, water adsorption and other catalytic and photocatalytic oxidation reaction at low-temperature. Among the three polymorphs of TiO2, the anatase crystal is the more photoactive. The anatase (101) surface attracts more attention since it has lower surface energy relative to (001) and (100) surfaces and it is observed to adsorb small molecules on its surface. Using density-functional theory (DFT) with on-site Coulomb interactions corrections, we have computed the structural and electronic properties of selected Au8 clusters interacting with clean and reduced anatase TiO2(101) surfaces. The computed adsorption energies are suggesting that the considered Au8 clusters are only physisorbed onto pristine TiO2(101) surface. Oxygen vacancies are found to enhance the absorption of Au8 on the Ti2(101) surface. Accurate simulations required spin polarized DFT since the ground state of Au8 interacting with defective TiO2(101) shows magnetic solutions. The results show that Au8 clusters are chemically bonded to the surface around the locality of the oxygen vacancy. The surface oxygen vacancy is found to be energetically more favourable than sub-surface oxygen vacancy configuration. These vacancy sites may act as nucleation sites for small Au clusters or Au atoms. Finally, the computed electronic structure of all the Au8/TiO2(101) configurations considered in this work are analysed in the light of available experimental data.

摘要

负载在TiO₂表面的过渡金属在许多重要过程中表现出卓越的催化性能,如CO氧化、丙烷选择性氧化、氢化、水吸附以及其他低温催化和光催化氧化反应。在TiO₂的三种多晶型中,锐钛矿晶体的光活性更强。锐钛矿(101)表面更受关注,因为相对于(001)和(100)表面,它具有更低的表面能,并且观察到其表面能吸附小分子。使用带有在位库仑相互作用校正的密度泛函理论(DFT),我们计算了选定的Au₈团簇与清洁和还原的锐钛矿TiO₂(101)表面相互作用的结构和电子性质。计算得到的吸附能表明,所考虑的Au₈团簇仅物理吸附在原始的TiO₂(101)表面上。发现氧空位会增强Au₈在Ti₂(101)表面的吸附。由于与有缺陷的TiO₂(101)相互作用的Au₈的基态显示出磁解,因此精确的模拟需要自旋极化DFT。结果表明,Au₈团簇与氧空位附近的表面发生化学键合。发现表面氧空位在能量上比次表面氧空位构型更有利。这些空位位点可能充当小Au团簇或Au原子的成核位点。最后,根据现有的实验数据对本工作中考虑的所有Au₈/TiO₂(101)构型的计算电子结构进行了分析。

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