Issue 11, 2016

Metal–organic frameworks with a large breathing effect to host hydroxyl compounds for high anhydrous proton conductivity over a wide temperature range from subzero to 125 °C

Abstract

It is important but still challenging to develop high-performance proton conducting materials for proton exchange membrane fuel cells (PEMFCs), as such materials should meet the following requirements: stable proton-transport pathway over a wide temperature range, high conductivity at work temperature, and small activation energy Ea to maintain high conductivity at start temperature. Here, we firstly demonstrated that flexible metal–organic frameworks (FMOFs) are good hosts to seek out better proton carriers for such high-performance proton conducting materials. A FMOF [Zn3(tz)2(bdc)2]n (FJU-31, Htz = 1H-1,2,3-triazole, H2bdc = terephthalic acid) with high thermal stability up to 400 °C, which can be readily synthesized from the Zn5(tz)6(NO3)4 precursor and H2bdc, has been employed to host various organic hydroxyls as new proton carriers. Three resulting FMOFs Zn3(tz)2(bdc)2@G (FJU-31@G, G = hydroquinone (Hq), cyclohexanol (Ch) or butanol (Bu)) show large breathing effect amplitudes up to 65% and guest-related single-crystal to single-crystal structural transformations by temperature stimulus. Most importantly, FJU-31@Hq hosting hydroquinone with a high melting point and small pKa exhibits a high anhydrous proton conductivity of 2.65 × 10−4 S cm−1, low activation energy Ea of 0.18 eV, and the widest temperature range from −40 to 125 °C for stable proton conduction among the crystalline porous materials.

Graphical abstract: Metal–organic frameworks with a large breathing effect to host hydroxyl compounds for high anhydrous proton conductivity over a wide temperature range from subzero to 125 °C

Supplementary files

Article information

Article type
Paper
Submitted
31 Dec 2015
Accepted
14 Feb 2016
First published
16 Feb 2016

J. Mater. Chem. A, 2016,4, 4062-4070

Metal–organic frameworks with a large breathing effect to host hydroxyl compounds for high anhydrous proton conductivity over a wide temperature range from subzero to 125 °C

Y. Ye, X. Wu, Z. Yao, L. Wu, Z. Cai, L. Wang, X. Ma, Q. Chen, Z. Zhang and S. Xiang, J. Mater. Chem. A, 2016, 4, 4062 DOI: 10.1039/C5TA10765B

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