From single Cu atoms to sub-nanometric copper clusters deposited on TiO2: a DFT study

IF 2.1 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY Structural Chemistry Pub Date : 2024-02-16 DOI:10.1007/s11224-024-02288-3
Dorota Rutkowska-Zbik, Agnieszka Drzewiecka-Matuszek, Renata Tokarz-Sobieraj
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Abstract

The growing interest in a material composed of Cu single atoms and/or their sub-nanometric clusters deposited on titania prompted us to perform systematic theoretical studies on the system comprising the anatase phase of titania, modelled by a (TiO2)34 cluster with copper particles of 1–7 atoms on top of it. The ground-state geometric structures were proposed and compared with the available literature data derived from EXAFS experiments done for Cu-TiO2 materials. Copper atoms prefer to aggregate and form larger clusters on TiO2, as seen from the computed nucleation energies. The models were characterised by the following electronic properties: electronic band structure, natural population charges, and frontier orbitals (HOMO, LUMO, and SOMO). The copper phase becomes oxidised once it is deposited on titania. The charge distribution in the resulting structures indicates that the atoms that are the closest to the Cu-TiO2 interface would become the active sites for catalytic processes; copper atoms would act as electrophilic, while oxygen atoms would act as nucleophilic. The calculated binding energies between the two phases show that the formation of the composite system is favourable from the thermodynamic point of view, and the interaction between the small copper clusters and the titania surface is mostly of electrostatic nature.

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从沉积在二氧化钛上的单个铜原子到亚纳米铜簇:DFT 研究
人们对沉积在二氧化钛上的由铜单个原子和/或其亚纳米团簇组成的材料的兴趣与日俱增,这促使我们对由二氧化钛锐钛矿相组成的系统进行了系统的理论研究,该系统由(TiO2)34 团簇和位于其顶部的 1-7 个原子的铜颗粒组成。我们提出了基态几何结构,并将其与针对 Cu-TiO2 材料进行的 EXAFS 实验所获得的现有文献数据进行了比较。从计算得出的成核能量可以看出,铜原子更倾向于在 TiO2 上聚集并形成较大的团块。这些模型具有以下电子特性:电子带结构、自然群体电荷和前沿轨道(HOMO、LUMO 和 SOMO)。铜相沉积在二氧化钛上后会被氧化。所得结构中的电荷分布表明,最靠近铜-二氧化钛界面的原子将成为催化过程的活性位点;铜原子起亲电作用,而氧原子起亲核作用。计算得出的两相之间的结合能表明,从热力学角度来看,复合体系的形成是有利的,小铜簇与二氧化钛表面之间的相互作用主要是静电性质的。
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来源期刊
Structural Chemistry
Structural Chemistry 化学-化学综合
CiteScore
3.80
自引率
11.80%
发文量
227
审稿时长
3.7 months
期刊介绍: Structural Chemistry is an international forum for the publication of peer-reviewed original research papers that cover the condensed and gaseous states of matter and involve numerous techniques for the determination of structure and energetics, their results, and the conclusions derived from these studies. The journal overcomes the unnatural separation in the current literature among the areas of structure determination, energetics, and applications, as well as builds a bridge to other chemical disciplines. Ist comprehensive coverage encompasses broad discussion of results, observation of relationships among various properties, and the description and application of structure and energy information in all domains of chemistry. We welcome the broadest range of accounts of research in structural chemistry involving the discussion of methodologies and structures,experimental, theoretical, and computational, and their combinations. We encourage discussions of structural information collected for their chemicaland biological significance.
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