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Effects of vanadium(V)-substitution on the oxidative properties of α-Keggin-type heteropolyanion clusters—progress in DFT theoretical studies

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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 act 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 in the cages and the central heteroatom X of the clusters. Combined with relevant experimental results, this review summarizes our recent theoretical investigations of the effect of vanadium substitution on the redox properties of Keggin anion clusters. Theoretical modeling and calculation results showed that the oxidative ability of the modified species was increased by partial substitution of the cage M atoms of the Keggin clusters by vanadium atoms which have lower electronegativity. A linear correlation between the catalytic efficiency per vanadium atom and the microstructures of the vanadium(V)-substituted heteropolyanions [PV n Mo12−n O40](3+n)− (n = 1−3) was established for the first time. This relationship may be suitable to interpret the catalytic behavior of the title compounds in the hydroxylation of benzene to phenol, and may also be used in understanding other reactions such as the oxidative dehydrogenation of isobutyric acid and the nitration of adamantine. The establishment of this nearly linear structure-property relationship may lay the foundations of understanding the behavior of the title compounds in homogeneous catalytic oxidation reactions, and may direct the design of future catalysts and the choice of other catalytic reactions.

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Authors and Affiliations

  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

    JinYue Wang, XiaoHong Fu & Jian Wang

  2. Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, China

    ChangWei Hu

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  1. JinYue Wang
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  2. XiaoHong Fu
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Correspondence to JinYue Wang.

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Supported by the Special Project of Key Laboratory of the Sichuan Provincial Department of Education (Grant No. 2006ZD051), the National Natural Science Foundation of China (Grant No. 20072024), and the Doctoral Fund Project of Yibin University (Grant No. 2006B03)

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Wang, J., Fu, X., Wang, J. et al. Effects of vanadium(V)-substitution on the oxidative properties of α-Keggin-type heteropolyanion clusters—progress in DFT theoretical studies. Sci. China Ser. B-Chem. 52, 2096–2105 (2009). https://doi.org/10.1007/s11426-009-0191-z

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  • DOI: https://doi.org/10.1007/s11426-009-0191-z

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