Porous metal–organic frameworks (MOFs) have demonstrated a great potential in proton conduction and luminescence sensing due to functionalized nodes, ligands and channels, or pores. Herein, we prepared a hydrothermally stable Eu-MOF that also resisted acid and base using a bifunctional organic ligand containing carboxylic acid groups, which are easily coordinated to Eu ions, and Eu-phobic tetrazolyl groups as potential proton-hopping sites. The hydrogen bond network, which was constructed by the uncoordinated anionic tetrazolium and the coordinated and free water molecules, endowed this Eu-MOF with the highest proton conductivity of 4.45 × 10–2 S/cm at 373 K and 93% relative humidity. The proton conductivity of the Nafion membrane containing this Eu-MOF increased 1.74 times. More interestingly, the hybrid membrane displayed luminescence pH sensing because the changeable protonation levels of uncoordinated tetrazolium groups along with the pH tuned the emission of embedded Eu-MOFs. Such a dual-functional MOF-based hybrid membrane including proton conduction and pH sensing is reported for the first time, which could open an avenue to the more practical application for functional MOFs.

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doi 10.1287/mnsc.1050.044

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The design and preparation of proton-conducting metal–organic frameworks (MOFs) with superconductivity are of significance for the proton-exchange membrane fuel cell (PEMFC). Introducing functional structural defects to enhance proton conductivity is a good approach. Here, we synthesized a series of UiO-66 (first synthesized in the University of Oslo) with missing-linker defects and investigated the effect of defect numbers on the proton conductivity of the samples. Among them, 60-UiO-66-1.8 (60 represents the synthesis temperature and 1.8 the number of defects) prepared with 3-mercaptopropionic acid as a modulator has the best proton conductivity, which is 3 × 10–2 S cm–1 at 100 °C and under 98% relative humidity (RH). The acidic sites induced by missing-linker defects further promote the chemisorption of ammonia molecules, resulting in the formation of a richer hydrogen-bond network and hence boosting the proton conductivity to 1.04 × 10–1 S cm–1 at 80 °C, which is one of the highest values among the reported MOF-based proton conductor. Therefore, this work provides a new strategy for enhancing proton conduction in MOF-based materials.