10.1002/anie.201809762
Angewandte Chemie International Edition
COMMUNICATION
oxidation of benzaldehyde.[18c, 22] The mechanism underlying the
oxidation of benzyl alcohol by DGIST-1 is proposed in Figure 4(d)
(see also Eq. S1-6 in Part S10 of the SI for the overall mechanism).
As indicated, TCPP∙+ was generated by electron transfer from
1,3TCPP* to Ti4+, followed by electron transfer from benzyl alcohol
to TCPP∙+.[5b, 9a] The O2 present in the solution then accepted an
electron from a Ti3+ center to regenerate DGIST-1 through the
53, 7233-7240; c) G. Zhang, C. Liu, D.-L. Long, L. Cronin, C.-H. Tung, Y.
Wang, J. Am. Chem. Soc. 2016, 138, 11097-11100; d) J.-X. Liu, M.-Y.
Gao, W.-H. Fang, L. Zhang, J. Zhang, Angew. Chem. Int. Ed. 2016, 55,
5160-5165.
[5]
a) C. H. Hendon, D. Tiana, M. Fontecave, C. Sanchez, L. D’arras, C.
Sassoye, L. Rozes, C. Mellot-Draznieks, A. Walsh, J. Am. Chem. Soc.
2013, 135, 10942-10945; b) S. Yuan, T.-F. Liu, D. Feng, J. Tian, K. Wang,
J. Qin, Q. Zhang, Y.-P. Chen, M. Bosch, L. Zou, S. J. Teat, S. J. Dalgarno,
H.-C. Zhou, Chem. Sci. 2015, 6, 3926-3930; c) H. L. Nguyen, F. Gándara,
H. Furukawa, T. L. H. Doan, K. E. Cordova, O. M. Yaghi, J. Am. Chem.
Soc. 2016, 138, 4330-4333; d) S. Yuan, J.-S. Qin, H.-Q. Xu, J. Su, D.
Rossi, Y. Chen, L. Zhang, C. Lollar, Q. Wang, H.-L. Jiang, D. H. Son, H.
Xu, Z. Huang, X. Zou, H.-C. Zhou, ACS Cent. Sci. 2018, 4, 105-111.
a) H.-C. Zhou, J. R. Long, O. M. Yaghi, Chem. Rev. 2012, 112, 673-674;
b) W. Lu, Z. Wei, Z.-Y. Gu, T.-F. Liu, J. Park, J. Park, J. Tian, M. Zhang,
Q. Zhang, T. Gentle Iii, M. Bosch, H.-C. Zhou, Chem. Soc. Rev. 2014,
43, 5561-5593.
∙
− [9a]
∙
−
formation of O2
.
The generated O2 and 1O2 oxidized the
radical cationic benzyl alcohol or benzyl alcohol to benzaldehyde.
Based on the proposed mechanism, we determined that the high
photocatalytic activity of DGIST-1 originated from efficient energy
transfer and charge separation upon visible light irradiation.
Intriguingly, the twice recycled DGIST-1 exhibited a remarkably
consistent catalytic activity, thereby indicating the stability of this
framework (Figures S38 and S39). Indeed, the recyclabilities of
photocatalytic MOFs have rarely been reported to date.
[6]
[7]
a) H. L. Nguyen, New J. Chem. 2017, 41, 14030-14043; b) H. Assi, G.
Mouchaham, N. Steunou, T. Devic, C. Serre, Chem. Soc. Rev. 2017, 46,
3431-3452.
J. Gao, J. Miao, P.-Z. Li, W. Y. Teng, L. Yang, Y. Zhao, B. Liu, Q. Zhang,
Chem. Commun. 2014, 50, 3786-3788.
[8]
[9]
a) M. Dan-Hardi, C. Serre, T. Frot, L. Rozes, G. Maurin, C. Sanchez, G.
Férey, J. Am. Chem. Soc. 2009, 131, 10857-10859; b) Y. Fu, D. Sun, Y.
Chen, R. Huang, Z. Ding, X. Fu, Z. Li, Angew. Chem. Int. Ed. 2012, 51,
3364-3367; c) K. Khaletskaya, A. Pougin, R. Medishetty, C. Rösler, C.
Wiktor, J. Strunk, R. A. Fischer, Chem. Mater. 2015, 27, 7248-7257; d)
J.-D. Xiao, L. Han, J. Luo, S.-H. Yu, H.-L. Jiang, Angew. Chem. Int. Ed.
2018, 57, 1118-1118; e) X. Li, Y. Pi, Q. Hou, H. Yu, Z. Li, Y. Li, J. Xiao,
Chem. Commun. 2018, 15, 1917-1920; f) J. A. Mason, L. E. Darago, W.
W. Lukens, J. R. Long, Inorg. Chem. 2015, 54, 10096-10104; g) B.
Bueken, F. Vermoortele, D. E. P. Vanpoucke, H. Reinsch, C.-C. Tsou, P.
Valvekens, T. De Baerdemaeker, R. Ameloot, C. E. A. Kirschhock, V.
Van Speybroeck, J. M. Mayer, D. De Vos, Angew. Chem. Int. Ed. 2015,
54, 13912-13917.
In conclusion, a new synthetic route was presented for the
preparation of the Ti-carboxylate MOF (DGIST-1) based on
unique Ti-oxo chain clusters. The excellent photocatalytic activity
of DGIST-1 was confirmed by the application of this material in
1
∙
−
the generation of O2 and O2 and in the selective oxidation of
benzyl alcohol to benzaldehyde under visible light irradiation. This
discovery is expected to lead to greater structural diversity for Ti-
MOFs, thereby rendering them efficient materials for use in
various photocatalytic applications.
[10] a) Y. Lee, S. Kim, J. K. Kang, S. M. Cohen, Chem. Commun. 2015, 51,
5735-5738; b) L. Zou, D. Feng, T.-F. Liu, Y.-P. Chen, S. Yuan, K. Wang,
X. Wang, S. Fordham, H.-C. Zhou, Chem. Sci. 2016, 7, 1063-1069.
[11] R. J. Cogdell, A. T. Gardiner, L. Cronin, Philos. Trans. Royal Soc. A 2012,
370, 3819-3826.
Acknowledgements
[12] K. Hong, H. Chun, Inorg. Chem. 2013, 52, 9705-9707.
[13] A. Fateeva, P. A. Chater, C. P. Ireland, A. A. Tahir, Y. Z. Khimyak, P. V.
Wiper, J. R. Darwent, M. J. Rosseinsky, Angew. Chem. Int. Ed. 2012, 51,
7440-7444.
[14] a) F. G. Svensson, G. A. Seisenbaeva, V. G. Kessler, Eur. J. Inorg. Chem.
2017, 2017, 4117-4122; b) G. Fornasieri, L. Rozes, S. Le Calvé, B.
Alonso, D. Massiot, M. N. Rager, M. Evain, K. Boubekeur, C. Sanchez,
J. Am. Chem. Soc. 2005, 127, 4869-4878.
This work was supported by
a National Research
Foundation of Korea (NRF) grant funded by the Korean
government (No. NRF-2016R1C1B2009987 and No. NRF-
2016M2B2A9912217).
[15] X.-F. Zhang, Q. Xi, J. Zhao, J. Mater. Chem. 2010, 20, 6726-6733.
[16] C. C. Winterbourn, Nat. Chem. Biol. 2008, 4, 278.
[17] a) W. Zhang, B. Li, H. Ma, L. Zhang, Y. Guan, Y. Zhang, X. Zhang, P.
Jing, S. Yue, ACS Appl. Mater. Interfaces 2016, 8, 21465-21471; b) A.-
N. Meng, L.-X. Chaihu, H.-H. Chen, Z.-Y. Gu, Sci. Rep. 2017, 7, 6297.
[18] a) T. Zhou, Y. Xu, X. Wang, S. Huang, M. Xie, J. Xia, L. Huang, H. Xu,
H. Li, Catal. Sci. Technol. 2018, 8, 551-561; b) V. Gomez-Vidales, G.
Granados-Oliveros, A. Nieto-Camacho, M. Reyes-Solis, M. Jimenez-
Estrada, RSC Adv. 2014, 4, 1371-1377; c) Y.-Z. Chen, Z. U. Wang, H.
Wang, J. Lu, S.-H. Yu, H.-L. Jiang, J. Am. Chem. Soc. 2017, 139, 2035-
2044.
Keywords: Cluster compounds • Metal-organic frameworks •
Reactive oxygen species • Selective alcohol oxidation • Ti-oxo
chain cluster
[1]
a) A. Fujishima, K. Honda, Nature 1972, 238, 37; b) J. Schneider, M.
Matsuoka, M. Takeuchi, J. Zhang, Y. Horiuchi, M. Anpo, D. W.
Bahnemann, Chem. Rev. 2014, 114, 9919-9986; c) A. L. Linsebigler, G.
Lu, J. T. Yates, Chem. Rev. 1995, 95, 735-758; d) M. Ni, M. K. H. Leung,
D. Y. C. Leung, K. Sumathy, Renew. Sust. Energ. Rev. 2007, 11, 401-
425; e) J. Zhang, Q. Xu, Z. Feng, M. Li, C. Li, Angew. Chem. Int. Ed.
2008, 47, 1766-1769.
[19] a) M. Zhang, C. Chen, W. Ma, J. Zhao, Angew. Chem. Int. Ed. 2008, 47,
9730-9733; b) D. Dvoranová, Z. Barbieriková, V. Brezová, Molecules
2014, 19, 17279.
[20] a) J. E. Kroeze, T. J. Savenije, J. M. Warman, Adv. Mater. 2002, 14,
1760-1763; b) A. Kathiravan, R. Renganathan, S. Anandan, J. Colloid
Interface Sci. 2010, 348, 642-648; c) H. Saito, Y. Nosaka, J. Phys. Chem.
C 2014, 118, 15656-15663.
[21] X. Li, Z. Guo, C. Xiao, T. W. Goh, D. Tesfagaber, W. Huang, ACS Catal.
2014, 4, 3490-3497.
[22] a) S. Schünemann, M. van Gastel, H. Tüysüz, ChemSusChem 2018, 11,
2057-2061; b) A. Li, T. Wang, X. Chang, W. Cai, P. Zhang, J. Zhang, J.
Gong, Chem. Sci. 2016, 7, 890-895.
[2]
a) C. Burda, Y. Lou, X. Chen, A. C. S. Samia, J. Stout, J. L. Gole, Nano
Lett. 2003, 3, 1049-1051; b) S. Sakthivel, H. Kisch, Angew. Chem. Int.
Ed. 2003, 42, 4908-4911; c) S. G. Kumar, L. G. Devi, J. Phys. Chem. A
2011, 115, 13211-13241; d) M. Pelaez, N. T. Nolan, S. C. Pillai, M. K.
Seery, P. Falaras, A. G. Kontos, P. S. M. Dunlop, J. W. J. Hamilton, J. A.
Byrne, K. O'Shea, M. H. Entezari, D. D. Dionysiou, Appl. Catal., B 2012,
125, 331-349.
a) W.-H. Fang, L. Zhang, J. Zhang, Chem. Soc. Rev. 2018, 47, 404-421;
b) L. Rozes, C. Sanchez, Chem. Soc. Rev. 2011, 40, 1006-1030.
a) T. Frot, S. Cochet, G. Laurent, C. Sassoye, M. Popall, C. Sanchez, L.
Rozes, Eur. J. Inorg. Chem. 2010, 2010, 5650-5659; b) Y.-Y. Wu, X.-W.
Lu, M. Qi, H.-C. Su, X.-W. Zhao, Q.-Y. Zhu, J. Dai, Inorg. Chem. 2014,
[3]
[4]
This article is protected by copyright. All rights reserved.