Dual-Functional Proton-Conducting and pH-Sensing Polymer Membrane Benefiting from a Eu-MOF

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.