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Design and synthesis of hybrid solids based on the tetravanadate core toward improved catalytic properties |
Yan-Hong Niu, Song Yang, Ji-Kun Li, Yan-Qing Xu, Chang-Wen Hu |
Key Laboratory of Cluster Science, Ministry of Education of China, Beijing Key Laboratory of Photoelectronic/Electrophotonic, School of Chemistry, Beijing Institute of Technology, Beijing 100081, China |
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Abstract Five inorganic-organic hybrid vanadates based on tetravanadate cores, transition metals and N-donor ligands have been designed and synthesized under hydrothermal conditions, namely, [Zn(eIM)3]2V4O12(1),[Zn(pIM)3]2V4O12·H2O(2),[Zn(ipIM)3]2V4O12(3),[Co(eIM)3]2V4O12·H2O(4),[Cu(eIM)2(H2O)]2V4O12(5) (eIM=1-ethylimidazole, pIM=1-propylimidazole, ipIM=isopropylimidazole). All compounds were fully characterized by single-crystal XRD, powder XRD, elemental analysis, TGA, and FT-IR spectroscopy. The hybrid zinc vanadates (1-3) and cobalt vanadate (4) exhibit interesting 2D folded structures and the hybrid copper vanadate (5) presents a 1D chain configuration. All compounds can catalyze olefin epoxidation reactions when using TBHP (TBHP=tert-butyl hydroperoxide) as an oxidant in acetonitrile. The introduction of transition metal ions into tetravanadate cores not only improved the catalytic activity but also fulfilled the heterogeneous catalytic behavior. 1-5 all exhibit extraordinary efficiency in converting olefins to the corresponding epoxides with high conversion and selectivity (particularly, conv. up to 97.1%, sele. up to 100% for 1). Leaching test was also carried out to prove the heterogeneous behavior.
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Received: 26 October 2015
Published: 13 January 2016
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Fund:This work was financially supported by the National Natural Science Foundation of China (Nos. 21173021, 21231002, 21271025 and 21276026), 973 Program (No. 2014CB932103), the 111 Project (No. B07012) and Beijing Higher Education Youth Elite Teacher Project (No. 1209). |
Corresponding Authors:
Yan-Qing Xu, Chang-Wen Hu
E-mail: xyq@bit.edu.cn;cwhu@bit.edu.cn
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|
[1] |
B.M. Trost, The atom economy-a search for synthetic efficiency, Science 254(1991) 1471-1477.
|
[2] |
M. Tonigold, Y. Lu, D. Volkmer, et al., Heterogeneous catalytic oxidation by MFU-1:a cobalt(Ⅱ)-containing metal-organic framework, Angew. Chem. Int. Ed. 48(2009) 7546-7550.
|
[3] |
J. Rich, E. Manrique, I. Romero, et al., Catalytic activity of chloro and triflate manganese(Ⅱ) complexes in epoxidation reactions:reusable catalytic systems for alkene epoxidation, Eur. J. Inorg. Chem. 2014(2014) 2663-2670.
|
[4] |
S. Caron, J.A. Ragan, D.H.B. Ripin, et al., Large-scale oxidations in the pharmaceutical industry, Chem. Rev. 106(2006) 2943-2989.
|
[5] |
B.S. Lane, K. Burgess, Metal-catalyzed epoxidations of alkenes with hydrogen peroxide, Chem. Rev. 103(2003) 2457-2474.
|
[6] |
M. Herbert, E. Alvarez, A. Galindo, et al., Olefin epoxidation by hydrogen peroxide catalysed by molybdenum complexes in ionic liquids and structural characterisation of the proposed intermediate dioxoperoxomolybdenum species, Chem. Commun. 46(2010) 5933-5935.
|
[7] |
C.J. Thibodeaux, W.C. Chang, H.W. Liu, Enzymatic chemistry of cyclopropane, epoxide, and aziridine biosynthesis, Chem. Rev. 112(2012) 1681-1709.
|
[8] |
K. Girijesh, K. Gulshan, G. Rajeev, Manganese- and cobalt-based coordination networks as promising heterogeneous catalysts for olefin epoxidation reactions, Inorg. Chem. 54(2015) 2603-2615.
|
[9] |
S.T. Oyama, in:S.T. Oyama (Ed.), Mechanisms in Homogeneous and Heterogeneous Epoxidation Catalysis, Elsevier, Amsterdam, 2008, pp. 1-99.
|
[10] |
J. Hagen, Industrial Catalysis:A Practical Approach, Wiley-VCH, Weinheim, 1999.
|
[11] |
J.M. Breen, W. Schmitt, Hybrid organic-inorganic polyoxometalates:functionalization of VIV/VV nanosized clusters to produce molecular capsules, Angew. Chem. Int. Ed. 120(2008) 7010-7014.
|
[12] |
E. Antonova, C. Näther, P. Köerler, W. Bensch, Die organische funktionalisierung von polyoxovanadaten:Sb-N-Bindungen und Ladungskontrolle, Angew. Chem. Int. Ed. 123(2011) 790-793.
|
[13] |
P. Köerler, B. Tsukerblat, A. Müller, Structure-related frustrated magnetism of nanosized polyoxometalates:aesthetics and properties in harmony, Dalton Trans. 39(2010) 21-36.
|
[14] |
B.K. Chen, Y.N. Chi, C.W. Hu, et al., Three new imidazole-functionalized hexanuclear oxidovanadium clusters with exceptional catalytic oxidation properties for alcohols, Chem. Eur. J. 19(2013) 4408-4413.
|
[15] |
E.S. Larrea, J.L. Mesa, M.I. Arriortua, et al., M(C6H16N3)2(VO3)4 as heterogeneous catalysts. Study of three new hybrid vanadates of cobalt(Ⅱ), nickel(Ⅱ) and copper(Ⅱ) with 1-(2-aminoethyl)piperazonium, Dalton Trans. 40(2011) 12690-12698.
|
[16] |
R.F. de Luis, M.K. Urtiage, M.I. Arriortua, et al., Thermal response, catalytic activity, and color change of the first hybrid vanadate containing bpe guest molecules, Inorg. Chem. 52(2013) 2615-2626.
|
[17] |
H. Lin, P.A. Maggard, Synthesis and structures of a new series of silver-vanadate hybrid solids and their optical and photocatalytic properties, Inorg. Chem. 47(2008) 8044-8052.
|
[18] |
Y. Hu, F. Luo, F. Dong, Design synthesis and photocatalytic activity of a novel lilaclike silver-vanadate hybrid solid based on dicyclic rings of[V4O12]4- with {Ag7}7+ cluster, Chem. Commun. 47(2011) 761-763.
|
[19] |
L. Luo, P.A. Maggard, Effect of ligand coordination on the structures and visiblelight photocatalytic activity of manganese vanadate hybrids, Cryst. Growth Des. 13(2013) 5282-5288.
|
[20] |
J.K. Li, X.Q. Huang, Y.N. Chi, C.W. Hu, Four alkoxohexavanadate-based Pd-Polyoxovanadates as robust heterogeneous catalysts for oxidation of benzyl-alkanes, Inorg. Chem. 54(2015) 1454-1461.
|
[21] |
S.J. Wu, Z.G. Lin, C.W. Hu, et al., Synthesis, structure and characterization of three different dimension inorganic-organic hybrid vanadates:[Co2(mIM)5(-H2O)2]V4O12[Ni2(mIM)7(H2O)]V4O12·H2O and[Cd(eIM)2(H2O)]V2O6, CrystEng-Comm 17(2015) 1625-1630.
|
[22] |
J.K. Li, X.Q. Huang, C.W. Hu, et al., Controllable synthesis, characterization, and catalytic properties of three inorganic-organic hybrid copper vanadates in the highly selective oxidation of sulfides and alcohols, Cryst. Growth Des. 15(2015) 1907-1914.
|
[23] |
G. Kummar, G. Kummar, R. Gupta, Manganese- and cobalt-based coordination networks as promising heterogeneous catalysts for olefin epoxidation reactions, Inorg. Chem. 54(2015) 2603-2615.
|
[24] |
L. Tabrizi, H. Chiniforoshan, P. Mcardle, A cobalt(Ⅱ) complex with anionic and neutral N-donor ligands:synthesis, crystal structure, and application as a heterogeneous catalyst for olefin epoxidation with tert-BuOOH, J. Coord. Chem. 68(2015) 980-992.
|
[25] |
J.K. Gao, L.L. Bai, Q.H. Zhang, et al., Co6(μ3-OH)6 cluster based coordination polymer as an effective heterogeneous catalyst for aerobic epoxidation of alkenes, Dalton Trans. 43(2014) 2559-2565.
|
[26] |
M. Sankaralingam, M. Palaniandavar, Tuning the olefin epoxidation by manganese(Ⅲ) complexes of bisphenolate ligands:effect of Lewis basicity of ligands on reactivity, Dalton Trans. 43(2014) 538-550.
|
[27] |
G.M. Sheldrick, SHELXTL NT/v. 6.14, Bruker Analytical X-ray Systems, Madison, Wisconsin, 2000.
|
[28] |
G.M. Sheldrick, SHELXS-97:Program for Crystal Structure Solution, Göttingen University, Göttingen, Germany, 1997.
|
[29] |
J. Forster, B. Rösner, M.M. Khusniyarov, C. Streb, Tuning the light absorption of a molecular vanadium oxide system for enhanced photooxidation performance, Chem. Commun. 47(2011) 3114-3116.
|
|
|
|