Dalton Transactions
COMMUNICATION
DOI: 10.1039/C4DT0258
Journal Na2Bme
as the adsorbed water was not fully desorbed when looking at 7 J. Canivet, A. Fateeva, Y. Guo, B. Coasne and D. Farrusseng, Chem.
relative pressures near P0 ~ 0 (Fig. 4 and Fig. S21). This Soc. Rev., 2014, 43, 5594.
observation led us to suspect that both MOFs decomposed over 8 F. Jeremias, D. Frohlich, C. Janiak and S. K. Henninger, New J. Chem.,
the course of the water sorption measurements. The measured 2014, 38, 1846.
P
/
PXRD patterns of the collected samples, after water sorption, 9 Y. I. Aristov, Appl. Therm. Eng., 2013, 50, 1610.
showed very broad diffraction peaks, which indicated a loss in 10 H. Reinsch, M. A. van der Veen, B. Gil, B. Marszalek, T. Verbiest, D.
crystallinity and, thus, instability of UiOꢀ67 and UiOꢀ67ꢀ(NH2)2
in water (Fig. S4). After the water sorption measurements, the 11 H. Furukawa, F. Gándara, Y.ꢀB. Zhang, J. Jiang, W. L. Queen, M. R.
collected materials were almost nonporous based on N2 Hudson, and O. M. Yaghi, J. Am. Chem. Soc., 2014, 136, 4369.
sorption measurements (Fig. S12). Thus, the observed large 12 J. Canivet, J. Bonnefoy, C. Daniel, A. Legrand, B. Coasne and D.
hysteresis in the isotherms, shown in Fig. 4, is ascribed to Farrusseng, New J. Chem., 2014, 38, 3102.
framework decomposition involving ligand replacement with 13 G. Akiyama, R. Matsuda, H. Sato, A. Hori, M. Takata and S.
de Vos and N. Stock, Chem. Mater., 2013, 25, 17.
3
0
water molecules.
Kitagawa, Microporous Mesoporous Mater., 2012, 157, 89.
In conclusion, the –NH functionalization of UiOꢀ67 was 14 A. Khutia, H. U. Rammelberg, T. Schmidt, S. Henninger and C. Janiak,
2
very effective in shifting the sigmoidal water vapour adsorption
curve down to lower relative pressures and positioning the 15 G. E. Cmarik, M. Kim, S. M. Cohen and K. S. Walton, Langmuir
steepest uptake region at P0 = 0.1–0.3. Although UiOꢀ67ꢀ 2012, 28, 15606.
NH ) was degraded after the water sorption measurement, this 16 J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S.
Chem. Mater., 2013, 25, 790.
,
P
/
(
2
2
work indicates that the water adsorption properties of MOFs
Bordiga, K. P. Lillerud, J. Am. Chem. Soc., 2008, 130, 13850.
can be fineꢀtuned through amineꢀfunctionalization of 17 Q. Yang, V. Guillerm, F. Ragon, A. D. Wiersum, P. L. Llewellyn, C.
framework surfaces in mediumꢀsized pore (ca. 2 nm) walls.
Zhong, T. Devic, C. Serrec and G. Maurin, Chem. Commun., 2012,
, 9831.
18 F. Jeremias, V. Lozan, S. K. Henninger and C. Janiak, Dalton Trans.,
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9 J. B. DeCoste, G. W. Peterson, H. Jasuja, T. G. Glover, Y. Huang and
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4
8
Acknowledgements
2
This research was supported by the Energy Efficiency &
Resources of the Korea Institute of Energy Technology
Evaluation and Planning (KETEP) grant funded by the Korea
government Ministry of Knowledge Economy (No.
1
2
1
0 M. J. Katz, Z. J. Brown, Y. J. Colón, P. W. Siu, K. A. Scheidt, R. Q.
Snurr, J. T. Hupp and O. K. Farha, Chem. Commun., 2013, 49, 9449.
1 S. J. Garibay, Dissertation, UC San Diego, 2011.
2
0122010100120) (Y.J.K). We thank Pohang Accelerator
2
2
2
Laboratory (PAL) in Korea for the Xꢀray data collection of
UiOꢀ67 at the 2DꢀSMC beamline.
2 S. J. Garibay and S. M. Cohen, Chem. Commun., 2010, 46, 7700.
3 S. Chavan, J. G. Vitillo, D. Gianolio, O. Zavorotynska, B. Civalleri, S.
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†
Electronic Supplementary Information (ESI) available: general 28. The structural model of UiOꢀ67 was refined without the modulators
procedures, materials syntheses, PXRD patterns, Xꢀray crystallographic
for simplicity.
1
information, HꢀNMR spectra, TGA curves, N
2
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