DFT Theoretical Studies on the Effects of Vanadium(V)-substitution on the Oxidative Property of α-Keggin\|type Heteropolyanion Clusters\|progress

Chem. J. Chinese Universities ›› 2009, Vol. 30 ›› Issue (11(1)): 1.

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DFT Theoretical Studies on the Effects of Vanadium(V)-substitution on the Oxidative Property of α-Keggin\|type Heteropolyanion Clusters\|progress

WANG Jin-Yue^1*, FU Xiao-Hong¹, WANG Jian¹, HU Chang-Wei², XIONG Yan³

1. Institute of Applied Chemistry, Department of Chemistry and Chemical Engineering, Key Laboratory of Computational Physics in Universities of Sichuan, Yibin University, Yibin 644007, China;
2. Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China;
3. Department of Chemistry and Chemical Engineering Chongqing 400030, China

Received:2009-07-28 Online:2009-11-30 Published:2009-11-30
Contact: WANG Jin-Yue. E-mial: jywang@163.com
Supported by:
四川省教育厅重点实验室专项(批准号: 2006ZD051)、国家自然科学基金(批准号: 20072024)和宜宾学院博士科研项目(批准号: 2006B03)的资助.

Abstract

Abstract:

The redox properties of α-Keggin\|type heteropolyanion clusters [XM₁₂O₄₀]^n-(X=Si, P; M=Mo, W) mainly depend on their constituent outer metal\|oxygen cages {M₁₂O₃₆}. They are just as “reservoirs”, through which the transfer and transition of electrons and protons may occur. At the atomic and molecular level, the redox properties of these clusters can be controlled and also tuned by modifying the metal M on the cages and the central heteroatom X of the clusters. Combined with the experimental results, this review summarized our recent theoretical investigation of the vanadium-substitution on the redox properties of the Keggin anion clusters. Theoretical modeling and calculation results showed that the oxidative ability of the modified species was increased by partially substitution of the cage M atoms of the Keggin clusters by lower electronegativity of vanadium atoms. A linear correlation between the catalytic efficiency based on the vanadium atom and the micro\|structures of the vanadium(V)-substituted heteropolyanions [PV_nMo_12-nO₄₀]^(3+n)-(n=1-3) was established for the first time. This relationship may be suitable to interpret the catalytic behaviors of the title compounds in the benzene hydroxylation to phenol, and it's also preferable used in the reactions of the oxidative dehydrogenation of isobutyric acid, the nitration of the adamantine, etc. The establishment of this nearly linear structure\|property may lay the foundation of understanding and illustrating the behavior of the title compound in the homogeneous catalytic oxidation reactions, and may direct the catalysis design and the chosen of the catalytic reactions. The results showed that the oxidative activity of the mono-vanadium\|substituted cluster was the highest among the titled species, while the oxidative activities of the di- and tri-vanadium-substituted clusters lied behind, with the former more active than the latter. Combined the calculated results with the available experimental electron reduction potentials(ERP) data, it was found that the Fermi energy levels(E_f) of these species change inversely with their ERPs, that is the E_f gets higher with increasing substituted vanadium number(n) of vanadium atom, the corresponding ERP gets smaller. Further calculations on the tungsten heteropolyanion clusters as the α-Keggin-type [XW₁₂O₄₀]^n-(X=Co^Ⅱ, Fe^Ⅲ, Si^Ⅳ, P^Ⅴ) also showed that the same relationship of E_f and ERP.

Key words: Polyoxometalate; Heteropolyanion; α-Keggin\, type; Vanadium-substitution; Oxidative property; Density functional theory

TrendMD:

WANG Jin-Yue*, FU Xiao-Hong, WANG Jian, HU Chang-Wei, XIONG Yan. DFT Theoretical Studies on the Effects of Vanadium(V)-substitution on the Oxidative Property of α-Keggin\|type Heteropolyanion Clusters\|progress[J]. Chem. J. Chinese Universities, 2009, 30(11(1)): 1.

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DFT Theoretical Studies on the Effects of Vanadium(V)-substitution on the Oxidative Property of α-Keggin\|type Heteropolyanion Clusters\|progress

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