Issue 6, 2022

Porosity regulation of metal–organic frameworks for high proton conductivity by rational ligand design: mono- versus disulfonyl-4,4′-biphenyldicarboxylic acid

Abstract

Porous crystalline metal–organic frameworks (MOFs) bearing sulfonic groups (–SO3H) are receiving increasing attention as solid-state proton conductors because the –SO3H group can not only enhance the proton concentration, but also form hydrogen bonding networks for high proton conductivity. A large number of 1,4-phenyldicarboxylic acids or biphenyldicarboxylic acids bearing two –SO3H groups have been applied for the synthesis of proton-conducting MOFs. Surprisingly, 4,4′-biphenyldicarboxylic acid bearing one –SO3H group has never been explored for the construction of proton-conducting materials. Herein, we first designed and synthesized 2-sulfonyl-4,4′-biphenyldicarboxylic acid (H3L). By applying this ligand to react with lanthanide salts, a series of three-dimensional MOFs, (Me2NH2)2(H3O)[LnL2]·8H2O (Ln = Eu (1), Gd (2), Tb (3)) have been prepared. Due to the presence of the uncoordinated –SO3H group and the encapsulation of high concentrations of dimethylammonium and hydronium cations in the cavity, the MOFs 1–3 show a high proton conductivity (8.83 × 10−3 S cm−1) at 95 °C and 60% relative humidity (RH). More importantly, this high proton conductivity can be maintained over 72 hours without any significant decrease at low RH.

Graphical abstract: Porosity regulation of metal–organic frameworks for high proton conductivity by rational ligand design: mono- versus disulfonyl-4,4′-biphenyldicarboxylic acid

Supplementary files

Article information

Article type
Research Article
Submitted
24 12 2021
Accepted
28 1 2022
First published
28 1 2022

Inorg. Chem. Front., 2022,9, 1134-1142

Porosity regulation of metal–organic frameworks for high proton conductivity by rational ligand design: mono- versus disulfonyl-4,4′-biphenyldicarboxylic acid

S. Zhang, Y. Xie, M. Yang and D. Zhu, Inorg. Chem. Front., 2022, 9, 1134 DOI: 10.1039/D1QI01610E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements