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ChemComm
Page 4 of 5
DOI: 10.1039/C7CC09767K
COMMUNICATION
Journal Name
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Q. Sun, Z. Dai, X. Liu, N. Sheng, F. Deng, X. Meng and F. S.
Xiao, J. Am. Chem. Soc., 2015, 137, 5204-5209.
Q. Sun, B. Aguila, G. Verma, X. Liu, Z. Dai, F. Deng, X. Meng,
F.-S. Xiao and S. Ma, Chem, 2016, 1, 628-639.
S. Das, P. Heasman, T. Ben and S. Qiu, Chem. Rev., 2017, 117
1515-1563.
W. Zhang, B. Aguila and S. Ma, J. Mater. Chem. A, 2017,
8795-8824.
T. Ben, H. Ren, S. Ma, D. Cao, J. Lan, X. Jing, W. Wang, J. Xu, F.
Deng, J. M. Simmons, S. Qiu and G. Zhu, Angew. Chem. Int.
Ed., 2009, 48, 9457-9460.
be due to the gradual disappearance of some guest molecules
in the pores of the PAF. After 5 cycles, the catalytic activity of
PAF70-thiourea became very stable. Surprisingly, after 36
cycles, there was absolutely no loss of catalytic activity of the
catalyst. Notably, the FT-IR spectra (Fig. S8, ESI.†) and nitrogen
adsorption–desorption isotherms (Fig. S9, ESI.†) of the fresh
PAF70-thiourea and the recycled catalyst after 36 cycles were
almost the same, indicating that PAF70-thiourea remained
unchanged after 36 cycles. In other words, as catalyst in the
current system, PAF70-thiourea is completely recyclable and
reusable. Considering the complexity of the reaction system,
this complete recyclability is very rare and exciting.
,
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,
10 C. Pei, T. Ben and S. Qiu, Mater. Horiz., 2015, 2, 11-21.
11 S. Demir, N. K. Brune, J. F. Van Humbeck, J. A. Mason, T. V.
Plakhova, S. Wang, G. Tian, S. G. Minasian, T. Tyliszczak, T.
Yaita, T. Kobayashi, S. N. Kalmykov, H. Shiwaku, D. K. Shuh
and J. R. Long, ACS Cent. Sci., 2016, 2, 253-265.
12 K. Konstas, J. W. Taylor, A. W. Thornton, C. M. Doherty, W. X.
Lim, T. J. Bastow, D. F. Kennedy, C. D. Wood, B. J. Cox, J. M.
In conclusion, an amine-tagged hierarchical PAF material
(PAF70-NH2) was task-specifically designed and successfully
obtained. It had narrowly distributed mesopores. Benefitting
from the intrinsic stability of the very robust framework,
PAF70-NH2 showed ultra-stability, which together with the
amine-anchor in the large enough mesopores endow PAF70-
NH2 with high potential for binding large-sized active sites
through post-functionalization. Then, by binding to the amine
anchor, the relatively large-sized thiourea unit was easily
covalently introduced into the pores of PAF70-NH2, affording
Hill, A. J. Hill and M. R. Hill, Angew. Chem. Int. Ed., 2012, 51
6639-6642.
,
13 B. Li, Y. Zhang, R. Krishna, K. Yao, Y. Han, Z. Wu, D. Ma, Z. Shi,
T. Pham, B. Space, J. Liu, P. K. Thallapally, J. Liu, M.
Chrzanowski and S. Ma, J. Am. Chem. Soc., 2014, 136, 8654-
8660.
14 B. Li, Y. Zhang, D. Ma, Z. Shi and S. Ma, Nat Commun, 2014, 5,
5537.
15 C. H. Lau, K. Konstas, C. M. Doherty, S. Kanehashi, B. Ozcelik,
,
PAF70-thiourea. PAF70-thiourea could catalyze NBS-mediated
S. E. Kentish, A. J. Hill and M. R. Hill, Chem. Mater., 2015, 27
4756-4762.
oxidation of alcohols and showed higher catalytic activity than
its homogeneous counterpart. More importantly, PAF70-
thiourea demonstrated complete recyclability, that is, it could
undergo at least 36 cycles without any activity loss in the
current catalysis system. In addition, the size selectivity of our
catalysis system further confirmed the existence of the
narrowly distributed mesopores in PAF70-NH2. This study fully
demonstrates the advantages of PAF materials and presents
an enticing prospect of using mesoporous PAFs as ultrastable
platform for immobilizing organocatalysts usually with
relatively large sizes. The work using PAF70-NH2 for additional
applications such as immobilization of organometallic catalysts
and molecular switches is ongoing. It is expected that our
study will further promote the development of mesoporous
PAF materials and their application in catalysis and other
fields.
16 Z. Yan, Y. Yuan, Y. Tian, D. Zhang and G. Zhu, Angew. Chem.
Int. Ed., 2015, 54, 12733-12737.
17 B. Li, Y. Zhang, D. Ma, Z. Xing, T. Ma, Z. Shi, X. Ji and S. Ma,
Chem. Sci., 2016, 7, 2138-2144.
18 H. Zhao, Z. Jin, H. Su, J. Zhang, X. Yao, H. Zhao and G. Zhu,
Chem. Commun., 2013, 49, 2780-2782.
19 C. H. Lau, K. Konstas, A. W. Thornton, A. C. Liu, S. Mudie, D. F.
Kennedy, S. C. Howard, A. J. Hill and M. R. Hill, Angew. Chem.
Int. Ed., 2015, 54, 2669-2673.
20 C. Gu, N. Huang, J. Gao, F. Xu, Y. Xu and D. Jiang, Angew.
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22 E. Merino, E. Verde-Sesto, E. M. Maya, A. Corma, M. Iglesias
and F. Sánchez, Appl. Catal. A: Gen., 2014, 469, 206-212.
23 Y. Zhang, B. Li and S. Ma, Chem. Commun., 2014, 50, 8507-
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24 A. Maximov, A. Zolotukhina, L. Kulikov, Y. Kardasheva and E.
Karakhanov, Reac. Kinet. Mech. Cat., 2016, 117, 729-743.
25 E. Rangel-Rangel, E. Verde-Sesto, A. M. Rasero-Almansa, M.
This work was supported by National Basic Research
Program of China (973 Program, grant no. 2014CB931804) and
National Natural Science Foundation of China (NSFC Project,
grant nos. 21302061 and 21531003).
Iglesias and F. Sánchez, Catal. Sci. Technol., 2016, 6, 6037-
6045.
26 E. Verde-Sesto, E. Merino, E. Rangel-Rangel, A. Corma, M.
Iglesias and F. Sánchez, ACS Sustainable Chem. Eng., 2016, 4,
1078-1084.
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and S. Kaskel, Soft Matter, 2010, , 3918.
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29 H. J. Jeon, J. H. Choi, Y. Lee, K. M. Choi, J. H. Park and J. K.
Conflicts of interest
6
There are no conflicts to declare.
Kang, Adv. Energy Mater., 2012, 2, 225-228.
30 C. G. Stuckwisch, G. G. Hammer and N. F. Blau, J. Org. Chem.,
1957, 22, 1678-1680.
31 J.-C. Fan, Z.-C. Shang, J. Liang, X.-H. Liu and Y. Liu, J. Phys. Org.
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Notes and references
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3936.
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Y. Xu, S. Jin, H. Xu, A. Nagai and D. Jiang, Chem. Soc. Rev.,
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32 C. B. Tripathi and S. Mukherjee, J. Org. Chem., 2012, 77
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Q. Sun, Z. Dai, X. Meng and F.-S. Xiao, Chem. Soc. Rev., 2015,
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33 Y. Luan, N. Zheng, Y. Qi, J. Tang and G. Wang, Catal. Sci.
Technol., 2014, 4, 925-929.
4 | J. Name., 2012, 00, 1-3
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