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ChemComm
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DOI: 10.1039/C8CC00130H
COMMUNICATION
Journal Name
Zhang and D. R. MacFarlane, Angew. Chem. Int. Ed., 2015, 54
,
dissociation of -SO3H in reaction solution. Therefore, two
extreme structural models including complete dissociation
8420-8424; (g) A. Dhakshinamoorthy, M. Alvaro, P. Concepción,
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Chem. Soc., 2012, 134, 16948-16950.
-
(three -SO3 , Fig. 4 and Fig. S7a, ESI†) and iniꢀal dissociation
-
(two -SO3H and one -SO3 , Fig. S7b, ESI†) were built and
calculated to investigate the contribution of orbital energy
levels. Based on the calculated results of the both models, the
HOMO (the highest occupied molecular orbital) is dominated
2 (a) H.-C. Zhou, J. R. Long and O. M. Yaghi, Chem. Rev., 2012,
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Howarth, O. K. Farha and J. T. Hupp, Acc. Chem. Res., 2017, 50
,
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by the -SO3 group while the LUMO (the lowest unoccupied
805-813; (d) B. Li, H.-M. Wen, Y. Cui, W. Zhou, G. Qian and B.
Chen, Adv. Mater., 2016, 28, 8819-8860; (e) Q. Yang, Q. Xu and
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molecular orbital) is dominated by the Cr-oxo clusters (Fig. 4;
Fig. S8 and S9, ESI†). The release of one proton (H+) leaves one
-
negative charge localized at the -SO3 , making the orbital
-
energy level of -SO3 approximate to the HOMO. Thus, the
-
electrons in the -SO3 can be excited to the LUMO if sufficient
3 (a) B. Chen, S. Xiang and G. Qian, Acc. Chem. Res., 2010, 43
,
energy is provided by light. Based on the above results, we
may assume that, upon exposing MIL-101-SO3H to light, the
1115-1124; (b) J.-R. Li, J. Sculley and H.-C. Zhou, Chem. Rev.,
2012, 112, 869-932; (c) L. E. Kreno, K. Leong, O. K. Farha, M.
-
electrons at ground states of -SO3 are excited to the LUMO
Allendorf, R. P. Van Duyne and J. T. Hupp, Chem. Rev., 2012, 112
1105-1125; (d) P.-Q. Liao, W.-X. Zhang, J.-P. Zhang and X.-M.
Chen, Nat. Commun., 2015, , 8697; (e) Z. Hu, B. J. Deibert and J.
,
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and the holes are left on the -SO3 to form -SO3 (Fig. 4c), the
6
negative charge being no longer localized on it which is
beneficial to the release of proton. This result is somewhat like
the classical electron withdrawing effect of many groups,
leading to the proton liberation and acidity increase, which
would be maintained by continuous light irradiation.
In summary, a sulfonic acid group modified MOF, MIL-101-
SO3H, behaves as a solid Brønsted acid catalyst toward various
acid-catalyzed reactions. Particularly, we have demonstrated
the activity is dramatically enhanced, which exhibits even
higher activity than that of traditional strong acid H2SO4, under
light irradiation. As far as we know, this is not only the first
report on boosting acidity and acid-related reactivity over
MOFs by light irradiation, but also the first work on the higher
Brønsted acid activity of MOF-based materials than inorganic
strong acids. The superb activity should be attributed to the
Lewis acidity, substrate enrichment in MOF pores and
improved proton liberation by light-induced electron transfer
as well as the protons gathering inside the MOF cages, thus
greatly boosting the acid-engaged reactions. The exciting
results reported herein would pave the way to the
development of light-enhanced MOF catalysis in many
industrial processes.
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,
This work is supported by the NSFC (21725101, 21673213
and 21521001), the National Research Fund for Fundamental
Key Project (2014CB931803) and the Recruitment Program of
Global Youth Experts.
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Conflicts of interest
There are no conflicts to declare.
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4 | J. Name., 2012, 00, 1-3
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