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The homogeneous reaction carried out under the same
conditions in the presence of free MnIJac)2 at 40 °C confirmed
that conversion of cyclohexene was much lower [38.3% con-
version using 0.001 mmol of MnIJac)2] than that with ZIF-90-
S[Mn] (Table 3). The present hybrid material 3 produced
comparable cyclohexene conversion but lower epoxide selec-
tivity than that reported for the manganeseIJII) acetylacetonate
complex bound to IRMOF-3 under identical reaction condi-
tions.45 In contrast, in the case of styrene, the former gave a
slightly higher yield of epoxide than the latter. Considering
the weak structural stability of IRMOF-3 recently reported,56–58
ZIF-90-S[Mn] may prove to be a practical alternative for liquid
phase epoxidation reactions.
6 R. Chen, J. Yao, Q. Gu, S. Smeets, C. Baerlocher, H. Gu,
D. Zhu, W. Morris, O. M. Yaghi and H. Wang, Chem.
Commun., 2013, 49, 9500.
7 F. X. LlabrésiXamena, O. Casanova, R. G. Tailleur, H. Garcia
and A. Corma, J. Catal., 2008, 255, 220.
8 C. Chizallet, S. Lazare, D. Bazer-Bachi, F. Bonnier, V. Lecocq,
E. Soyer, A. A. Quoineaud and N. Bats, J. Am. Chem. Soc.,
2010, 132, 12365.
9 H. Y. Cho, J. Kim, S. N. Kim and W. S. Ahn, Microporous
Mesoporous Mater., 2013, 169, 1180.
10 T. T. Dang, Y. Zhu, J. S. Y. Ngiam, S. C. Ghosh, A. Chen and
A. M. Seayad, ACS Catal., 2013, 3, 1406.
11 S. Bhattacharjee, M. S. Jang, H. J. Kwon and W. S. Ahn,
Catal. Surv. Asia, 2014, 18, 101.
Conclusions
12 A. Huang, W. Dou and J. Caro, J. Am. Chem. Soc., 2010, 132,
15562.
A thiol-functionalized ZIF-90 (ZIF-90-SH) was prepared via
condensation between the free aldehyde group of ZIF-90 and
the amine group of 2-mercaptoethylamine to form an imine,
which was followed by the introduction of catalytically active
manganeseIJII) acetate to furnish a hybrid material (ZIF-90-
S[Mn]). The structure of the parent ZIF-90 was retained after
post-synthesis functionalization. ZIF-90-SH was found to be
an efficient adsorbent for the removal of HgIJII) from an aque-
ous solution at ambient temperature. The material exhibited
an adsorption capacity of approximately 22.4 mg g−1. The
material was effective in the treatment of low-concentrations
of HgIJII) (10.0–0.1 mg L−1) resulting in 96–98% removal of
HgIJII) from aqueous solution. The new hybrid material, ZIF-
90-SijMn], showed good activity and selectivity in the epoxida-
tion of cyclohexene, cyclooctene and styrene using molecular
oxygen as the oxidant and in the presence of trimethyl-
acetaldehyde. This solid catalyst could be recycled several
times without a significant loss of activity or selectivity. The
present study highlights the potential of the post-synthesis
modification of MOFs to create new functionalities for the syn-
thesis of fine chemicals and for environmental applications.
13 A. Huang and J. Caro, Angew. Chem., Int. Ed., 2011, 50, 4979.
14 S. M. Cohen, Chem. Rev., 2012, 112, 970.
15 A. Hung, N. Wang, C. Kong and J. Caro, Angew. Chem., Int.
Ed., 2012, 51, 10551.
16 T. X. Yang and T. S. Chung, J. Mater. Chem. A, 2013, 1, 6081.
17 J. A. Thompson, N. A. Brunelli, R. P. Lively, J. R. Johnson,
C. W. Jones and S. Nair, J. Phys. Chem. C, 2013, 117, 8198.
18 A. Huang, Q. Liu, N. Wang and J. Caro, Microporous
Mesoporous Mater., 2014, 192, 18.
19 O. Karagiaridi, M. B. Lalonde, W. Bury, A. A. Sarjeant,
O. K. Farha and J. T. Hupp, J. Am. Chem. Soc., 2012, 134, 18790.
20 W. Morris, C. J. Doonan, H. Furukawa, R. Banerjee and
O. M. Yaghi, J. Am. Chem. Soc., 2008, 130, 12626.
21 J. C. Clifton, in Mercury Exposure and Public health, Pediatr.
Clin. North Am., 2007, 54, 237.
22 US EPA, National Primary Drinking Water, Standards, US
Environmental Protection Agency, Washington, DC, 2001;
J. A. Ritter and J. A. Bibler, Water Sci. Technol., 1992, 25, 165.
23 A. Dabrowski, Z. Hubicki, P. Podkoŝcielny and E. Robens,
Chemosphere, 2004, 56, 91.
24 M. Huebra, M. P. Elizalde and A. Almela, Hydrometallurgy,
2003, 68, 33.
25 P. Kumar and V. V. Guliants, Microporous Mesoporous
Mater., 2010, 132, 1.
26 V. K. Gupta, P. J. M. Carrott and M. M. L. Ribeiro Carrott,
Environ. Sci. Technol., 2009, 39, 783.
27 R. R. Navarro, K. Sumi, N. Fujii and M. Matsumura, Water
Res., 1996, 30, 2488.
Acknowledgements
This study was supported by a National Research Foundation
of Korea (NRF) grant funded by the Korean Government
(MEST) (no. 2013005862).
Notes and references
28 A. Denizli, K. Kesenci, Y. Arica and E. Piskin, React. Funct.
Polym., 2000, 44, 235.
29 S. H. M. Evangelista, E. Deoliveira, G. R. Castro, L. F. Zara
and A. G. S. Prado, Surf. Sci., 2007, 601, 2194.
30 H. Parham, B. Zargar and R. Shiralipour, J. Hazard. Mater.,
2012, 205, 94.
1 K. S. Park, Z. Ni, A. P. Cté, J. Y. Choi, R. Huang, F. J. Uribe-
Romo, H. K. Chae, M. O'Keeffe and O. M. Yaghi, Proc. Natl.
Acad. Sci. U. S. A., 2006, 103, 10186.
2 R. Banerjee, A. Phan, B. Wang, C. Knobler, H. Furukawa,
M. O'Keeffe and O. M. Yaghi, Science, 2008, 319, 939.
3 B. Wang, A. P. Cté, H. Furukawa, M. O'Keeffe and
O. M. Yaghi, Nature, 2008, 453, 207.
31 D. M. Saad, E. M. Cukrowska and H. Tutu, Appl. Water Sci.,
2013, 3, 527.
4 A. Phan, C. J. Doonan, F. J. Uribe-Romo, C. B. Knobler,
M. O'Keeffe and O. M. Yaghi, Acc. Chem. Res., 2010, 43, 58.
5 R. Banerjee, H. Furukawa, D. Britt, C. Knobler, M. O'Keeffe
and O. M. Yaghi, J. Am. Chem. Soc., 2009, 131, 3875.
32 A. Mehdinia, M. Akbari, T. B. Kayyal and M. Azad, Environ.
Sci. Pollut. Res., 2015, 22, 2155.
33 F. Ke, L. G. Qiu, Y. P. Yuan, F. M. Peng, X. Jiang, A. J. Xie,
Y. H. Shen and J. F. Zhu, J. Hazard. Mater., 2011, 196, 36.
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