Solid-State NMR Studies of TBA3[VW5O19] and TBA4[PVW11O40]

doi:10.11938/cjmr20150302

Abstract

Abstract:

Polyoxometalates (POMs) are metal cluster compounds formed by transition metal atoms with d⁰ or d¹ electron configuration via edge or corner polycondensation. Because of their unique molecular structures and physical/chemical properties, POMs have been widely used in functional materials, catalytic chemistry and medicinal chemistry etc. Vanadium-substituted POMs often have high catalytic activities for hydrocarbon oxidation, and such activities are mainly related to the number of vanadium atom and the electron environment these atoms are in. Solid-state NMR, as one of the most important methods to characterize solid acid materials, has been widely applied to study POMs. In this paper, butanyl cations and vanadium atoms in Lindqvist and Keggin oxopolytungstates were characterized by ¹³C and ⁵¹V solid state NMR spectroscopy to obtain information on the local environment these cations and vanadium centers are in. Such information is important for understanding the oxidation catalytic mechanism. It is concluded that ⁵¹V solid state NMR spectroscopy can be a quick, convenient and nondestructive tool to study the local environment for vanadium atoms and the bulk morphologies of POMs.

Key words: polyoxometalates, solid-state NMR, ⁵¹V magic-angle-spinning spectroscopy, Lindqvist, Keggin

CLC Number:

O482.53

DING Li-hong1,2，LIU Xiao-long2，WANG Qiang2，LIU Wen-tao1，ZHU Cheng-shen1，ZHENG An-min2，DENG Feng2*. Solid-State NMR Studies of TBA₃[VW₅O₁₉] and TBA₄[PVW₁₁O₄₀][J]. Chinese Journal of Magnetic Resonance, 2015, 32(3): 409-418.

References

[1] Wang En-bo(王恩波), Hu Chang-wen(胡长文), Xu Lin(许林). Introduction of Polyoxometalates Chemistry(多酸化学导论) [M]. Beijing(北京): Chemicel Industry Press(化学工业出版社出版), 1984. 4.

[2] Yang C, Jin Q, Zhang H, et al. Tetra-(tetraalkylammonium)octamolybdate catalysts for selective oxidation of sulfides to sulfoxides with hydrogen peroxide[J]. Green Chem, 2009, 11: 1 401－1 405.

[3] Johson B J S, Schroden R C, Zhuand C C, et al. Synthesis and characterization of 2D and 3D structures from organic derivatives of polyoxometalate clusters: Role of organic moiety, counterion and solvent[J]. Inorg Chem, 2001, 40(23): 5 972－5 978.

[4] Chen X, Xu Z, Okuhara T. Liquid-phase esterification of acrylic acid with 1-butanol catalyzed by solid acid catalysts[J]. Appl Catal A, 1999, 180(1－2): 261－265.

[5] Bareyt S, Piligkos S, Hasenknopf B, et al. Highly efficient peptide bond formation to functionalized wells-Dawson type polyoxotungstates[J]. Angew Chem Int Ed, 2003, 42(29): 3 404－3 406.

[6] Carrier X, Caillerie J B, Lambert J F. The support as a chemical reagent in the preparation of Wox/y-Al₂O₃ catalysts formation and deposition of aluminotungstic heteropolyanions[J]. J Am Chem Soc, 1999, 121(14): 3 377－3 381.

[7] Lu M, Wei Y G, Xu B B, et al. Hydrid molecular dumbbells: Bridging polyoxometalate clusters with an organic p-conjugated rod[J]. Angew Chem Int Ed, 2002, 41(9): 1 566－1 568.

[8] Mizumo N, Misono M. Heterogeneous catalysis [J]. Chem Rev, 1998, 98(1): 199－205.

[9] Xu Jun(徐君), Deng Feng(邓风). NMR studies on solid acids and crystallization of molecular sieves (固体酸催化剂及分子筛晶化过程的核磁共振研究)[J]. Chinese J Magn Reson(波谱学杂志), 2007, 24(3): 368－370.

[10] Yu Zhi-wu(喻志武), Zheng An-min(郑安民), Deng Feng(邓风), et al. Acidity characterization of solid acid catalysts by solid-state NMR spectroscopy: A review on recent progresses(固体核磁共振研究固体酸催化剂酸性进展)[J]. Chinese J Magn Reson(波谱学杂志), 2010, 27(4): 485－515.

[11] Lindqvist I. The structure of the hexanjobate ion in 7Na₂O.6NB₂O₅.32H₂O[J]. Arkiv Kemi, 1952, 5: 247

[12] Dmitrenko O, Huang W L, Polenova T E, et al. Effect of cations in infrared and computational analysis of vanadium-containing six-coordinate oxotungstates[J]. J Phys Chem B, 2003, 107(31): 7 747－7 752.

[13] Derat E, Kumar D, Neumann R, et al. Catalysts for monooxygenations made from polyoxometalate: An iron(V)-oxo derivative of the lindqvist anion[J]. Inorg Chem, 2006, 45(21): 8 655－8 663.

[14] Li J. Electronic structures, (d-p)p conjugation effects, and spectroscopic properties of polyoxometalates: M6O192- (M=Cr, Mo, W) [J]. J Clust Sci, 2002, 13(1): l37－l63.

[15] Yang X, Waters T, Wang X B. Photoelectron spectroscopy of free polyoxoanions Mo₆O₁₉^2–in the gas phase[J]. J Phys Chem A, 2004, 108(46): 10 089－10 093.

[16] Keggin J K. The structure and formula of 12-phosphotungstic acid[J]. Proc Roy Soc A, 1934, 144: 75－100.

[17] Nomiya K, Nemoto Y, Hasegawa T, et al. Multicenter active sites of vanadium-substituted polyoxometalate catalysts on benzene hydroxylation with hydrogen peroxide and two reaction types with and without an induction period[J]. J Mol Catal A: Chemical, 2000, 152: 55－68.

[18] Nomiya K, Hashino K, Nemoto Y, et al. Oxidation of toluene and nitrobenzene with 30% aqueous hydrogen peroxide catalyzed by vanadium(V)-substituted polyoxometalates[J]. J Mol Catal A, 2001, 176: 79－86.

[19] Huang W, Todaro L, Yap G, et al. ⁵¹V magic angle spinning NMR spectroscopy of Keggin Anions [PV_nW_12-nO₄₀]^(3+n)-: Effect of counteraction and vadadium substitution on fine structure constants[J]. J Am Chem Soc, 2004, 126: 11 564－ 11 573.

Engelhardt G, Michel D. High-Resolution Solid-State NMR of Silicates and Zeolites[M]. Chichester: Wiley, 1987.

Solid-State NMR Studies of TBA₃[VW₅O₁₉] and TBA₄[PVW₁₁O₄₀]

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