Citation: ZHENG Ming, ZHANG Hong-Xing, YUAN Fu-Long, PAN Qing-Jiang. Relativistic DFT Calculations of Interaction between Rutile TiO₂ Nanoparticle Clusters and Uranyl Species[J]. Chinese Journal of Inorganic Chemistry, ;2018, 34(5): 874-882. doi: 10.11862/CJIC.2018.120 shu

Relativistic DFT Calculations of Interaction between Rutile TiO₂ Nanoparticle Clusters and Uranyl Species

1.
Key Laboratory of Functional Inorganic Material Chemistry of Education Ministry, School of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, China
2.
Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China

Corresponding author: YUAN Fu-Long, panqjitc@163.com PAN Qing-Jiang, yuanfulong@hlju.edu.cn
Received Date: 28 October 2017
Revised Date: 7 February 2018

Figures(6)

The interaction between rutile TiO₂ nanoparticle clusters (NPCs) and aquouranyl species have been examined using a relativistic functional theory (DFT). Effects of NPCs with various layers (1~4) and different surface areas on structural parameters of uranium adsorption complexes as well as adsorption interaction energies were investigated. It is found that the two-layered (2L) NPC (labeled as 2L-Ti15) with a surface area of 1.1 nm×0.6 nm and containing 63 atoms can reasonably stand for experimentally real TiO₂ nanocrystallite. Moreover, the model is able to save computational resources. Calculations reveal a covalent bonding interaction in the 2L-Ti15-[(UO₂)(H₂O)₃]²⁺ complex. The direct evidences include that the bond lengths of U-O_surf were optimized to be 0.233~0.238 nm, which fall well within the range of U-O distances of reported uranyl complexes. The process that the NPC adsorbs aquouranyl species is exothermic in the gas phase, releasing energy of -3.02 eV; the consideration of environment media of solution results in a slightly uphill process, requiring 0.16 eV energy. The energetic decomposition indicates that U-O_surf bonds are dominated by orbital interactions, accounting for 94%; other factors show a little effect, although electrostatic attraction is a little larger than Pauli repulsion. Electron density-based QTAIM (quantum theory of atoms in molecule) analyses unravel that the U-O_surf interaction is a dative bond per se, whose strength is stronger than that of U-OH₂, but much weaker than that of U=O_yl. Inspection of wavefunction demonstrates that HOMO is contributed by O(2p) of NPC TiO₂ mixed with a small amount of σ(U=O) bonding character, while LUMO is U(5f)-based character modified by Ti(3d). The HOMO-LUMO gap was calculated to be 2.40 eV, which much narrower than the one of NPC semiconductor (3.35 eV). From a point of view of absorption spectra, the complex system would present a visible light-harvesting capability.
- rutile TiO₂ nanoparticle clusters,
- uranium contaminant,
- adsorption interaction nature,
- electronic structures,
- relativistic DFT
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沈阳化工大学材料科学与工程学院沈阳 110142

Relativistic DFT Calculations of Interaction between Rutile TiO2 Nanoparticle Clusters and Uranyl Species

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通讯作者: 陈斌, bchen63@163.com

Relativistic DFT Calculations of Interaction between Rutile TiO₂ Nanoparticle Clusters and Uranyl Species