钒取代α-Keggin型杂多阴离子簇合物[PVnMo12-nO40](3+n)-(n=1~3)氧化性能的DFT研究

高等学校化学学报 ›› 2009, Vol. 30 ›› Issue (11(1)): 1.

钒取代α-Keggin型杂多阴离子簇合物[PV_nMo_12-nO₄₀]^(3+n)-(n=1~3)氧化性能的DFT研究

王金月¹, 陈洪¹, 王健¹, 傅小红¹, 胡常伟², 熊燕³

1. 宜宾学院应用化学研究所, 化学与化工系, 四川省高校计算物理重点实验室, 宜宾 644007;
2. 绿色化学与技术教育部重点实验室, 四川大学化学学院, 成都 610064;
3. 重庆大学化学化工学院, 重庆 400030

收稿日期:2009-07-28 出版日期:2009-11-30 发布日期:2009-11-30
通讯作者: 王金月, 男, 博士, 副研究员, 主要从事分子团簇及反应过程的分子模拟, 绿色化学等方面研究. E-mial: jywang@163.com
基金资助:
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.

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.

摘要/Abstract

摘要：

综述运用密度泛函理论的O3LYP方法和离散变分法(DFT-DVM), 通过理论计算和模拟, 将不同个数V取代的α-Keggin型磷钼杂多阴离子簇合物以及它们的各个异构体区分开来, 探讨了V的取代效应对所形成物种[PV_nMo_12-nO₄₀]^(3+n)-(n=1~3)氧化活性的影响. 研究结果表明, 当电负性较小的V取代Keggin金属氧笼上的Mo后, 所形成物种的氧化能力得到不同程度的增强. O3LYP的理论模拟结果与实验事实相结合, 首次建立了钒取代的α-Keggin型[PV_nMo_12-nO₄₀]^(n+3)-(n=1~3)的微观结构与其基于单个钒的催化氧化能力之间的线性关系, 该关系不仅适用于苯的氧化羟基化反应, 而且也适用于异丁酸的氧化脱氢, 金刚烷的硝化等反应. DFT-DVM的计算表明, 单钒取代的簇阴离子的氧化活性最高, 其次是二钒取代的物种, 三钒取代的物种活性最低. 将计算得到的结果与实验测得的还原电势进行关联后发现, 这些杂多阴离子簇合物的费米能级(E_f)与其第一还原电势(ERP)之间呈现反比变化, 随着V取代个数n的增加, 簇阴离子所带的负电荷数逐渐增大, E_f值也随之增大, 而相应物种的ERP却逐渐减小.

关键词: 杂多阴离子; α-Keggin型; 钒取代效应; 氧化性能; 密度泛函理论

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:

王金月, 陈洪, 王健, 傅小红, 胡常伟, 熊燕. 钒取代α-Keggin型杂多阴离子簇合物[PV_nMo_12-nO₄₀]^(3+n)-(n=1~3)氧化性能的DFT研究. 高等学校化学学报, 2009, 30(11(1)): 1.

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

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钒取代α-Keggin型杂多阴离子簇合物[PV_nMo_12-nO₄₀]^(3+n)-(n=1~3)氧化性能的DFT研究

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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