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VOxH2O (x= 15)团簇的结构及稳定性研究

金蓉 谌晓洪

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VOxH2O (x= 15)团簇的结构及稳定性研究

金蓉, 谌晓洪

Structures and stabilities of VOxH2O (x= 15) clusters

Jin Rong, Chen Xiao-Hong
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  • 用密度泛函理论(DFT),在B3LYP/DZP水平上对H2O分子与VOx形成的团簇VOxH2O (x= 15)进行结构优化、能量和频率的计算,研究了团簇的稳定结构、稳定性和频率特性.结果表明VOxH2O (x= 15) 团簇的基态构型的电子态均为2A, 对称性均属C1对称点群,其中x= 1, 4, 5时基态构型中水分子已被解离.水分子倾向于吸附在团簇VOx上, 形成VOxH2O (x= 15)团簇. VOxH2O (x= 15)团簇中, VOxH2O (x= 1,4,5) 的化学活性小于VOxH2O (x= 2, 3)的化学活性.此外, H2O体系与VOx之间的结合强弱顺序为 VO4H2O VO5H2O VOH2O VO3H2O VO2H2O. VOH2O中离解出H原子的能量为2.88 eV和从VO5H2O中离解出OH基团的能量为2.38 eV, 均在可见光能量范围内,这两个化学过程有可能在可见光催化条件下进行.可以通过团簇的红外和拉曼谱特征, 初步判断水分子在VOxH2O团簇中是否离解.
    The equilibrium geometries, vibrational frequencies of VOxH2O (x= 15) and interactions between H2O with VOx(x= 15) are studied by using the density functional theory B3LYP/DZP method. The results show that ground states for VOxH2O (x= 15) belong to C1 point group symmetry,their electronic state is 2A, and in ground state of VOxH2O (x= 1, 4, 5) water molecule H2O is dissociated; H2O molecule is absorbed easily in VOx(x= 15) and VOxH2O(x= 15) are formed; In VOxH2O(x=15), chemical activations of VOxH2O (x= 1, 4, 5) are lower than those of VOxH2O (x= 2, 3); the sequence of interaction strength between H2O and VOx(x= 15) is VO4H2O VO5H2O VOH2O VO3H2O VO2H2O; there is possibility that OH segment and H atom are dissociated easily from VOH2O and VO5H2O, respectively by visible light exposure. Criterion that H2O molecule is dissociated in VOxH2O(x= 15) is obtained by analyzing frequency spectrum.
    • 基金项目: 四川省教育厅重点项目(批准号: 10ZA105, 10ZX012)和 四川省科技厅科技支撑计划(批准号: 2009PZ0055)资助的课题.
    • Funds: Project supported by the Education Bureau of Sichuan Provincial Government (Grant Nos. 10ZA105, 10ZX012), and the Science and Technology Bureau of Sichuan Provincial Government (Grant No. 2009PZ0059).
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    Sun K Q, Zhong Q 2008 Environmental Chemistry 27 33 (in Chinese) [孙克勤, 钟秦, 黄丽娜 2008 环境化学 27 33]

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  • [1]

    Cox P A 1992 Transition Metal Oxides An Introduction to Their Electronic Structure and Properties (Oxford:Clarendon Press)

    [2]

    Rao C N R, Raveau B 1995 Transition metal oxides (New York: VCH Publishers)

    [3]

    Busca G, Lietti L, Ramis G, Berti F 1998 Appl. Catal. B: Environmental 18 1

    [4]

    Pasel J, Käßner P, Montanari B, Gazzano M, Vaccari A, Makowski W, Lojewski T, Dziembaj R, Papp H 1998 Appl. Catal. B: Environmental 18 199

    [5]

    Yamanaka I, Morimoto K, Soma M, Otsuka K 1998 J. Mol. Catal. A 133 251

    [6]

    Viparelli P, Ciambelli P, Lisi L, Ruoppolo G, Russo G, Volta J C 1999 Appl. Catal. A 184 291

    [7]

    Gao X T, Wachs I E 2000 J. Phys. Chem. B 104 1261

    [8]

    Calatayud M, Silvi B, Andrés J, Beltrán A 2001 Chemical Physics Letters 333 493

    [9]

    Calatayud M, Andrés J, Beltrán A 2001 J. Phys. Chem. A 105 9760

    [10]

    Vyboishchikov S F, Sauer J 2000 J. Phys. Chem. A 104 10913

    [11]

    Chertihin G V, Bare W D, Andrews L 1997 J. Phys. Chem. A 101 5090

    [12]

    Engeser M, Weiske T, Schröder D, Schwarz H 2003 J. Phys. Chem. A 107 2855

    [13]

    Weckhuysen B M, Keller D E 2003 Catal. Today 78 25

    [14]

    Cortez G G, Banares M A 2002 J. Catal. 209 197

    [15]

    Balducci G, Gigli G, Guido M 1983 J. Chem. Phys. 79 5616

    [16]

    Pykavy M, Wüllen van C 2003 J. Phys. Chem. A 107 5566

    [17]

    Du Q, Wang L, Sheng X H, Gao T 2006 Acta Phys. Sin. 55 6308 (in Chinese) [杜泉, 王玲, 谌晓洪, 高涛 2006 物理学报 55 6308]

    [18]

    Du Q, Wang L, Sheng X H 2008 Acta Chim. Sin. 66 23 (in Chinese) [杜泉, 王玲, 谌晓洪, 王红艳, 高涛, 朱正和 2008 化学学报 66 23]

    [19]

    Bjarnason A, Ridge D 1998 Organometallics 17 1889

    [20]

    Jakubikova E, Bernstein E R, 2007 J. Phys. Chem. A 111 13339

    [21]

    Avdeev V I, Tapilin V M 2010 J. Phys. Chem. C 114 3609

    [22]

    Sun K Q, Zhong Q 2008 Environmental Chemistry 27 33 (in Chinese) [孙克勤, 钟秦, 黄丽娜 2008 环境化学 27 33]

    [23]

    Becke A D 1993 J. Chem. Phys. 98 5648

    [24]

    Lee C, Yang W, Parr R G 1988 Phys. Rev. B 37 785

    [25]

    Hunzinaga S 1965 J. Chem. Phys. 42 1293

    [26]

    Dunning T H 1970 J. Chem. Phys. 53 2823

    [27]

    Zhou G D, Duan L Y 2002 Fundamentals of Structural Chemistry (Beijing: Peking university press)pp242, 178, 179 (in Chinese) [周公度, 段连云 2002 结构化学基础 (北京: 北京大学出版社)第242, 178, 179页]

    [28]

    Chen H S, Meng F S, Li X F, Zhang S L 2009 Acta Phys. Sin. 58 0887 (in Chinese) [陈宏善, 孟凡顺, 李向富, 张素玲 2009 物理学报 58 0887]

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  • PDF下载量:  686
  • 被引次数: 0
出版历程
  • 收稿日期:  2011-06-20
  • 修回日期:  2012-05-10
  • 刊出日期:  2012-05-05

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