Issue 5, 2015

Tailoring the water adsorption properties of MIL-101 metal–organic frameworks by partial functionalization

Abstract

MIL-101 and MIL-101–NH2 were partially modified to incorporate various functional groups that are capable of forming hydrogen bonds with water. Specifically, MIL-101–NH2 was partially functionalized with –NHCONHCH2CH3 (–UR2), –NHCOCHCHCOOH (–Mal), or –NH(CH2)3SO3H (–3SO3H) and MIL-101 was partially functionalized with –COOH in order to investigate the effect of these groups on the water sorption properties when compared to the pristine versions. The MIL-101 derivatives were synthesized by either post-synthetic modification of MIL-101–NH2 or through direct synthesis using a mixed linker strategy. The ratios of the incorporated functional groups were determined by 1H-NMR analyses and the porosity changes were revealed by N2 gas adsorption measurements at 77 K. Water sorption isotherms at 298 K conclude that the incorporation of –3SO3H enhances the water vapour uptake capacity at a low relative pressure (P/P0 = 0.30), whereas –UR2 and –Mal retard water adsorption in MIL-101–NH2. The partial incorporation of –COOH in MIL-101 exhibits a steeper water uptake at lower pressure (P/P0 = 0.40) than MIL-101–NH2. Interestingly, a greater –COOH content within the MIL-101 framework reduces the water uptake capacity. These results indicate that even partial functionalization of MIL-101 induces noticeably large changes in the water adsorption properties.

Graphical abstract: Tailoring the water adsorption properties of MIL-101 metal–organic frameworks by partial functionalization

Supplementary files

Article information

Article type
Paper
Submitted
18 Sep 2014
Accepted
01 Dec 2014
First published
01 Dec 2014

J. Mater. Chem. A, 2015,3, 2057-2064

Author version available

Tailoring the water adsorption properties of MIL-101 metal–organic frameworks by partial functionalization

N. Ko, P. G. Choi, J. Hong, M. Yeo, S. Sung, K. E. Cordova, H. J. Park, J. K. Yang and J. Kim, J. Mater. Chem. A, 2015, 3, 2057 DOI: 10.1039/C4TA04907A

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