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Hybrid Polyoxotungstate/MIL-101 Materials: Synthesis, Characterization, and Catalysis of H2O2-Based Alkene Epoxidation
Abstract
Polyoxotungstates [PW(4)O(24)](3-) (PW(4)) and [PW(12)O(40)](3-) (PW(12)) have been inserted into nanocages of the metal organic framework MIL-101. The hybrid materials PW(x)/MIL-101 (x = 4 or 12) containing 5-14 wt % of polyoxotungstate have been obtained and characterized by elemental analysis, N(2) adsorption, FT-IR, Raman, and (31)P NMR MAS spectroscopic techniques. Their catalytic performance was assessed in the selective oxidation of alkenes with aqueous hydrogen peroxide under mild reaction conditions ([H(2)O(2)] = 0.1-0.2 M, 50 degrees C, MeCN). PW(x)/MIL-101 enclosing 5 wt % of polyoxotungstate demonstrated fairly good catalytic activities in the epoxidation of various alkenes (3-carene, limonene, alpha-pinene, cyclohexene, cyclooctene, 1-octene), the turnover frequencies (TOF) and alkene conversions were close to the corresponding parameters achieved with homogeneous PW(x). For the oxidation of substrates with aromatic groups (styrene, cis- and trans-stilbenes), a higher level of olefin conversion was attained using PW(12)/MIL-101. Moreover, confinement of PW(12) within MIL-101 nanocages allowed us to reach higher epoxide selectivities at higher alkene conversions. The hybrid PW(x)/MIL-101 materials were stable to leaching, behaved as true heterogeneous catalysts, were easily recovered by filtration, and reused several times with the maintenance of the catalytic performance.
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Citations
Cites
Metal-organic framework materials as catalysts
Lee, J., Farha, O. K., Roberts, J., Scheidt, K. A., Nguyen, S. T., & Hupp, J. T. (2009) · Chemical Society Reviews · doi:10.1039/b807080f · Cited by 7,969
Cited by
Metal–organic framework composites
Zhu, Q.-L., & Xu, Q. (2014) · Chem. Soc. Rev. · doi:10.1039/c3cs60472a · Cited by 2,286
Metal–organic frameworks meet metal nanoparticles: synergistic effect for enhanced catalysis
Yang, Q., Xu, Q., & Jiang, H.-L. (2017) · Chemical Society Reviews · doi:10.1039/c6cs00724d · Cited by 1,892
Bromberg, L., Diao, Y., Wu, H., Speakman, S. A., & Hatton, T. A. (2012) · Chemistry of Materials · doi:10.1021/cm2034382 · Cited by 444
Heterogeneous Catalysis by Polyoxometalates in Metal–Organic Frameworks
Samaniyan, M., Mirzaei, M., Khajavian, R., Eshtiagh-Hosseini, H., & Streb, C. (2019) · ACS Catalysis · doi:10.1021/acscatal.9b03439 · Cited by 389
Bhattacharjee, S., Chen, C., & Ahn, W.-S. (2014) · RSC Adv. · doi:10.1039/c4ra11259h · Cited by 301
Metal organic frameworks as heterogeneous catalysts for the production of fine chemicals
Dhakshinamoorthy, A., Opanasenko, M., Čejka, J., & Garcia, H. (2013) · Catalysis Science & Technology · doi:10.1039/c3cy00350g · Cited by 296
Taking organic reactions over metal-organic frameworks as heterogeneous catalysis
Hu, M.-L., Safarifard, V., Doustkhah, E., Rostamnia, S., Morsali, A., Nouruzi, N., Beheshti, S., & Akhbari, K. (2018) · Microporous and Mesoporous Materials · doi:10.1016/j.micromeso.2017.07.057 · Cited by 283
Metadata
- Authors
- Maksimchuk, N. V., Kovalenko, K. A., Arzumanov, S. S., Chesalov, Y. A., Melgunov, M. S., Stepanov, A. G., Fedin, V. P., & Kholdeeva, O. A.
- Venue
- Inorganic Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 2010-02-18
- Volume
- 49
- Issue
- 6
- Pages
- 2920-2930
- ISSN
- 0020-1669 (ISSN-L)
- 1520-510X
- OpenAlex
- W1974312340
- Cited by
- 245
- References
- 1
- FWCI
- 10.19
- Type
- journal article
- Language
- en
- Open access
- closed
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