平面型十三聚合铝形态水交换反应的密度泛函研究

金晓艳, 严喻, 杨文静, 唐杰, 毕树平. 平面型十三聚合铝形态水交换反应的密度泛函研究[J]. 环境化学, 2013, 32(7): 1123-1128. doi: 10.7524/j.issn.0254-6108.2013.07.002
引用本文: 金晓艳, 严喻, 杨文静, 唐杰, 毕树平. 平面型十三聚合铝形态水交换反应的密度泛函研究[J]. 环境化学, 2013, 32(7): 1123-1128. doi: 10.7524/j.issn.0254-6108.2013.07.002
JIN Xiaoyan, YAN Yu, YANG Wenjing, TANG Jie, BI Shuping. Density functional theory study for exploring the water-exchange reactions of Flat aluminum tridecamers[J]. Environmental Chemistry, 2013, 32(7): 1123-1128. doi: 10.7524/j.issn.0254-6108.2013.07.002
Citation: JIN Xiaoyan, YAN Yu, YANG Wenjing, TANG Jie, BI Shuping. Density functional theory study for exploring the water-exchange reactions of Flat aluminum tridecamers[J]. Environmental Chemistry, 2013, 32(7): 1123-1128. doi: 10.7524/j.issn.0254-6108.2013.07.002

平面型十三聚合铝形态水交换反应的密度泛函研究

  • 基金项目:

    国家自然科学基金(21177054)资助和安徽省高校省级优秀青年人才基金(2012SQRL117)资助.

Density functional theory study for exploring the water-exchange reactions of Flat aluminum tridecamers

  • Fund Project:
  • 摘要: 采用密度泛函DFT量子化学计算,初步探讨了平面型十三聚合铝(F-Al13)的水交换反应. 在B3LYP/6-31G水平下模拟了气相体系中全水合F-Al1315+与脱质子形态(F-Al139+和F-Al133+)中-OH2(1)键合水位点的水交换反应; 比较了F-Al13和K-Al13两种不同十三聚合铝形态的水交换反应特点; 讨论了不同铝形态(二聚铝Al2、三聚铝Al3、Al6六元环以及Al7 Anderson内核等)水交换反应研究对于阐明F-Al13形成机制的重要意义.
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  • [1] Casey W H. Large aqueous aluminum hydroxide molecules [J]. Chem Rev, 2006, 106(1): 1-16
    [2] [2] Pascual-Cosp J, Artiaga R, Corpas-Iglesias F, et al. Synthesis and characterization of a new aluminum-based compound [J]. Dalton Trans, 2009, 32: 6299-6308
    [3] [3] Sun Z, Zhao H D, Tong H, et al. Formation and structure of [Al133-OH)6( μ2-OH)6( μ2-OH)12(H2O)24]Cl15·13H2O [J]. Chinese J Struct Chem, 2006, 25(10): 1217-1227
    [4] [4] Gatlin J T, Mensinger Z L, Zakharov L N, et al. Facile synthesis of the tridecameric Al13 nanocluster Al133-OH)62-OH)18(H2O)24(NO3)15 [J]. Inorg Chem, 2008, 47: 1267-1269
    [5] [6] Qian Z S, Feng H, Yang W J, et al. Theoretical investigation of water exchange on the nanometer-sized polyoxocation AlO4Al12(OH)24(H2O)127+ (Keggin-Al13) in aqueous solution [J]. J Am Chem Soc, 2008, 130(44): 14402-14403
    [6] [7] Qian Z S, Feng H, Zhang Z J, et al. Theoretical exploration of the water exchange mechanism of the polyoxocation GaO4Al12(OH)24(H2O)127+ in aqueous solution [J]. Geochim Cosmochim Acta, 2009, 73: 1588-1596
    [7] [8] Jin X Y, Yang W J, Tang J, et al. Insight into the structural characteristics of core-links and flat-aluminum tridecamers: A density functional theory study [J]. Dalton Trans, 2012, 41: 1027-1032
    [8] [9] Evans R J, Rustad J R, Casey W H. Calculating geochemical reaction pathways - Exploration of the inner-sphere water exchange mechanism in Al(H2O)63++nH2O with ab initio calculations and molecular dynamics [J]. J Phys Chem A, 2008, 112(17): 4125-4140
    [9] [10] Qian Z S, Feng H, Yang W J, et al. Density functional studies on the structural characteristics, 27Al NMR chemical shifts and the water exchange reactions of Al30O8(OH)56(H2O)2618+ (Al30) in aqueous solution [J]. Geochim Cosmochim Acta, 2010, 74: 1230-1237
    [10] [11] Jin X Y, Qian Z S, Lu B M, et al. Density functional theory study on aqueous aluminum-fluoride complexes: Exploration of the intrinsic relationship between water-exchange rate constants and structural parameters for monomer aluminum complexes [J]. Environ Sci Technol, 2011, 45(1): 288-293
    [11] [12] Nordin J P, Sullivan D J, Phillips B L, et al. An 17O NMR study of the exchange of water on AlOH(H2O)52+(aq) [J]. Inorg Chem, 1998, 37: 4760-4763
    [12] [13] Swaddle T W, Rosenqvist J, Yu P, et al. Kinetic evidence for five-coordination in AlOH2+ ion [J]. Science, 2005, 308(5727): 1450-1453
    [13] [14] Hanauer H, Puchta R, Clark T, et al. Searching for stable, five-coordinate aquated Al(Ⅲ) species. Water exchange mechanism and effect of pH [J]. Inorg Chem, 2007, 46: 1112-1122
    [14] [15] Ruiz J M, McAdon M H, Garcés J M. Aluminum complexes as models for broensted acid sites in zeolites: Structure and energetics of [Al(OH)4]-, [Al(H2O)6]3+, and intermediate monomeric species [Al(OH)x(H2O)n-x·mH2O]3-x obtained by hydrolysis [J]. J Phys Chem B, 1997, 101: 1733-1744
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  • 收稿日期:  2013-02-27
金晓艳, 严喻, 杨文静, 唐杰, 毕树平. 平面型十三聚合铝形态水交换反应的密度泛函研究[J]. 环境化学, 2013, 32(7): 1123-1128. doi: 10.7524/j.issn.0254-6108.2013.07.002
引用本文: 金晓艳, 严喻, 杨文静, 唐杰, 毕树平. 平面型十三聚合铝形态水交换反应的密度泛函研究[J]. 环境化学, 2013, 32(7): 1123-1128. doi: 10.7524/j.issn.0254-6108.2013.07.002
JIN Xiaoyan, YAN Yu, YANG Wenjing, TANG Jie, BI Shuping. Density functional theory study for exploring the water-exchange reactions of Flat aluminum tridecamers[J]. Environmental Chemistry, 2013, 32(7): 1123-1128. doi: 10.7524/j.issn.0254-6108.2013.07.002
Citation: JIN Xiaoyan, YAN Yu, YANG Wenjing, TANG Jie, BI Shuping. Density functional theory study for exploring the water-exchange reactions of Flat aluminum tridecamers[J]. Environmental Chemistry, 2013, 32(7): 1123-1128. doi: 10.7524/j.issn.0254-6108.2013.07.002

平面型十三聚合铝形态水交换反应的密度泛函研究

  • 1.  南京大学化学化工学院, 南京, 210093;
  • 2.  阜阳师范学院化学化工学院, 阜阳, 236037
基金项目:

国家自然科学基金(21177054)资助和安徽省高校省级优秀青年人才基金(2012SQRL117)资助.

摘要: 采用密度泛函DFT量子化学计算,初步探讨了平面型十三聚合铝(F-Al13)的水交换反应. 在B3LYP/6-31G水平下模拟了气相体系中全水合F-Al1315+与脱质子形态(F-Al139+和F-Al133+)中-OH2(1)键合水位点的水交换反应; 比较了F-Al13和K-Al13两种不同十三聚合铝形态的水交换反应特点; 讨论了不同铝形态(二聚铝Al2、三聚铝Al3、Al6六元环以及Al7 Anderson内核等)水交换反应研究对于阐明F-Al13形成机制的重要意义.

English Abstract

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