Abstract
AbstractA Co‐based metal–organic framework (MOF) was investigated as a catalytic material in the aerobic epoxidation of olefins in DMF and exhibited, based on catalyst mass, a remarkably high catalytic activity compared with the Co‐doped zeolite catalysts that are typically used in this reaction. The structure of STA‐12(Co) is similar to that of STA‐12(Ni), as shown by XRD Rietveld refinement and is stable up to 270 °C. For the epoxidation reaction, significantly different selectivities were obtained depending on the substrate. Although styrene was epoxidized with low selectivity due to oligomerization, (E)‐stilbene was converted with high selectivities between 80 and 90 %. Leaching of Co was low and the reaction was found to proceed mainly heterogeneously. The catalyst was reusable with only a small loss of activity. The catalytic epoxidation of stilbene with the MOF featured an induction period, which was, interestingly, considerably reduced by styrene/stilbene co‐epoxidation. This could be traced back to the formation of benzaldehyde promoting the reaction. Detailed parameter and catalytic studies, including in situ EPR and EXAFS spectroscopy, were performed to obtain an initial insight into the reaction mechanism.
References
63
Referenced
116
{'key': 'e_1_2_7_1_2', 'volume-title': 'Ullmann’s Encyclopedia of Industrial Chemistry', 'year': '2003'}
/ Ullmann’s Encyclopedia of Industrial Chemistry (2003){'key': 'e_1_2_7_2_2', 'first-page': '51', 'volume': '87', 'author': 'McCoy M.', 'year': '2009', 'journal-title': 'Chem. Eng. News'}
/ Chem. Eng. News by McCoy M. (2009)10.1081/CR-100100262
10.1002/ange.19971090506
10.1002/anie.199704771
10.1021/cr010333u
10.1038/nature04190
10.1038/nature07194
10.1016/j.cattod.2008.04.026
10.1016/j.jcat.2009.03.010
10.1002/1521-3765(20000602)6:11<2011::AID-CHEM2011>3.0.CO;2-L
10.1023/A:1022659817183
10.1016/j.molcata.2009.09.009
10.1039/b314864e
10.1080/00958970801986817
10.1016/j.molcata.2007.07.020
10.1016/j.molcata.2007.03.009
10.1134/S0023158409020098
10.1007/s10562-009-9943-9
10.1016/j.jcat.2004.12.017
10.1016/j.molcata.2007.04.029
10.1016/j.apcata.2009.04.003
10.1007/s10562-007-9273-8
10.1016/j.jcat.2006.11.018
10.1007/s11244-010-9518-4
10.1002/ange.200806063
10.1002/anie.200806063
10.1039/b807080f
10.1039/b804680h
10.1016/j.jcat.2007.06.004
10.1039/b810414j
10.1039/b902954k
10.1039/c0cc01506g
10.1021/ic902459f
10.1021/ja804703w
10.1016/j.jcat.2009.12.002
10.1002/chem.201003173
10.1016/j.jcat.2008.02.011
10.1007/s11243-009-9188-x
10.1021/cg700796m
10.1166/jnn.2010.1493
10.1002/zaac.200800158
10.1002/ange.200901241
10.1002/anie.200901241
10.1021/ja804936z
- G. M. Pearce Ph. D. Thesis University of St. Andrews (UK) 2009.
{'key': 'e_1_2_7_44_2', 'volume-title': 'General Structure Analysis System (GSAS)', 'author': 'Larson A. C.', 'year': '1994'}
/ General Structure Analysis System (GSAS) by Larson A. C. (1994)- M. T. Wharmby G. M. Pearce J. P. S. Mowat J. M. Griffin S. E. Ashbrook P. A. Wright L.‐H. Schilling A. Lieb N. Stock S. Chavan S. Bordiga E. Garcia G. Pirngruber M. Vreeke L. Gora unpublished results.
10.1002/chem.200901510
10.1016/j.molcata.2010.01.014
10.1007/BF00548996
10.1021/ic0102945
10.1021/j100281a008
10.1021/ic034798
{'key': 'e_1_2_7_52_2', 'volume-title': 'Lehrbuch der Anorganischen Chemie', 'author': 'Holleman A. F.', 'year': '1995'}
/ Lehrbuch der Anorganischen Chemie by Holleman A. F. (1995)10.1016/j.jcat.2006.09.005
10.1021/ja01000a017
10.1021/ja01036a017
10.1021/ja00712a017
10.1021/ic00092a020
10.1039/a903099i
10.1021/ja00991a010
10.1016/j.jssc.2009.07.019
Dates
Type | When |
---|---|
Created | 13 years, 8 months ago (Dec. 12, 2011, 8:53 a.m.) |
Deposited | 1 year, 10 months ago (Oct. 16, 2023, 8:35 p.m.) |
Indexed | 2 weeks, 2 days ago (Aug. 5, 2025, 8:40 a.m.) |
Issued | 13 years, 8 months ago (Dec. 12, 2011) |
Published | 13 years, 8 months ago (Dec. 12, 2011) |
Published Online | 13 years, 8 months ago (Dec. 12, 2011) |
Published Print | 13 years, 7 months ago (Jan. 16, 2012) |
@article{Beier_2011, title={Aerobic Epoxidation of Olefins Catalyzed by the Cobalt‐Based Metal–Organic Framework STA‐12(Co)}, volume={18}, ISSN={1521-3765}, url={http://dx.doi.org/10.1002/chem.201101223}, DOI={10.1002/chem.201101223}, number={3}, journal={Chemistry – A European Journal}, publisher={Wiley}, author={Beier, Matthias J. and Kleist, Wolfgang and Wharmby, Michael T. and Kissner, Reinhard and Kimmerle, Bertram and Wright, Paul A. and Grunwaldt, Jan‐Dierk and Baiker, Alfons}, year={2011}, month=dec, pages={887–898} }