Zirconium-based metal-organic framework gels for selective luminescence sensing

Metal-organic gelation represents a promising approach to fabricate functional nanomaterials. Herein a series of Zr-carboxylate gels are synthesized from rigid pyrene, porphyrin and tetraphenyl ethylene-derived tetracarboxylate linkers, namely Zr-TBAPy (H₄TBAPy = 1,3,6,8-tetrakis(4-carboxylphenyl)pyrene), Zr-TCPE (H₄TCPE = 1,1,2,2-tetra(4-carboxylphenyl)ethylene), and Zr-TCPP (H₄TCPP = 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin). The gels are aggregated from metal-organic framework (MOF) nanoparticles. Zr-TBAPy gel consists of NU-901 nanoparticles, and Zr-TCPP gel consists of PCN-224 nanoparticles. The xerogels show high surface areas up to 1203 m² g^-1. MOF gel films are also anchored on the butterfly wing template to yield Zr-MOF/B composites. Zr-TBAPy and Zr-TCPE gels are luminescent for solution-phase sensing and vapour-phase sensing of volatile organic compounds, and exhibit a significant luminescence quenching effect for electron-deficient analytes. Arising from the high porosity and good dispersion of luminescent MOF gels, rapid and effective vapour-sensing of nitrobenzene and 2-nitrotoluene within 30 s has been achieved via Zr-TBAPy film or Zr-TBAPy/B.