TiO2表面上小分子吸附的吸附能和HOMO能级之间的线性关系,The Journal of Physical Chemistry C

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TiO2表面上小分子吸附的吸附能和HOMO能级之间的线性关系
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2019-08-19 , DOI: 10.1021/acs.jpcc.9b05707
Takashi Kamachi _{1,

2} , Toshinobu Tatsumi ₁ , Takashi Toyao _{2,

3} , Yoyo Hinuma _{4,

5} , Zen Maeno ₃ , Satoru Takakusagi ₃ , Shinya Furukawa _{2,

3} , Ichigaku Takigawa _{6,

7} , Ken-ichi Shimizu _{2,

3}

Affiliation

吸附是在固体表面催化的基本步骤，因此，对其理解对于解释其行为很重要。这项工作研究了各种小分子的吸附，包括H ₂，N ₂，CO，CO ₂，CH ₄，NH ₃，H ₂ O，H ₂ S，二甲基亚砜，烷烃，烯烃，炔烃，芳族化合物，醇， TiO ₂的锐钛矿（101）和金红石（110）表面上的醛，酮，腈，羧酸，酰胺和胺，使用周期密度泛函理论计算和统计方法。在相同的理论水平上计算吸附能以获得干净一致的数据集。观察到这些分子的吸附能与其最高占据分子轨道（HOMO）水平之间存在线性关系，而对于最低未占据分子轨道水平，则没有明显的相关性。通过将这些分子分为两个子类：碳氢化合物和含杂原子的化合物，可以提高吸附能与HOMO含量之间的相关性。考虑了前沿分子轨道与表面之间的相互作用，以更好地了解已确定的重要相关性。₂面。使用机器学习进行的统计分析表明，就合理化和预测吸附能而言，HOMO和偶极矩分别是第一和第二最重要的属性。

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Linear Correlations between Adsorption Energies and HOMO Levels for the Adsorption of Small Molecules on TiO2 Surfaces

Adsorption is a fundamental step in catalysis on a solid surface, and therefore, its understanding is important for explaining its behavior. This work investigated the adsorption of various small molecules, including H₂, N₂, CO, CO₂, CH₄, NH₃, H₂O, H₂S, dimethyl sulfoxide, alkanes, alkenes, alkynes, aromatic compounds, alcohols, aldehydes, ketones, nitriles, carboxylic acids, amides, and amines, on the anatase (101) and rutile (110) surfaces of TiO₂, using periodic density functional theory calculations and statistical methods. Adsorption energies were computed at the same level of theory to obtain a clean and consistent data set. A linear relationship was observed between the adsorption energies of these molecules and their highest occupied molecular orbital (HOMO) levels, whereas no obvious correlation was evident for the lowest unoccupied molecular orbital levels. Improved correlations between the adsorption energies and HOMO levels were generated by dividing these molecules into two subgroups: hydrocarbons and heteroatom-containing compounds. Interactions between frontier molecular orbitals and the surfaces were considered, to gain a better understanding of the significant correlations that were identified. The data show that these relationships can be primarily ascribed to the interactions between the HOMO of the small molecule and conduction state of the TiO₂ surface. The statistical analysis using machine learning demonstrated that the HOMO and dipole moment are the first and second most important properties, respectively, in terms of rationalizing and predicting the adsorption energies.

更新日期：2019-08-20

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