Issue 1, 2022

UiO-67-derived bithiophene and bithiazole MIXMOFs for luminescence sensing and removal of contaminants of emerging concern in wastewater

Abstract

Solvent-assisted ligand exchange in the zirconium metal–organic framework (MOF) UiO-67 [Zr6O4(OH)4(PhPh)6; H2PhPh = biphenyl-4,4′-dicarboxylic acid] with the heterocyclic linkers H2TpTp (2,2′-bithiophene-5,5′-dicarboxylic acid) and H2TzTz (2,2′-bithiazole-5,5′-dicarboxylic acid) in an equimolar [Zr6] : linker ratio led to the corresponding MIXMOFs UiO-67-TpTp [Zr6O4(OH)4(PhPh)5(TpTp)] and UiO-67-TzTz [Zr6O4(OH)4(PhPh)5(TzTz)]. Both MOFs have been thoroughly characterized in the solid state. They show the same structural topology and crystal structure of UiO-67, as confirmed by powder X-ray diffraction. Their BET specific surface area is lower than that of their parent material (1700 and 1310 m2 g−1 for UiO-67-TpTp and UiO-67-TzTz, respectively, vs. 1877 m2 g−1 for UiO-67), while the thermal stability of UiO-67 (Tdec = 819 K) is maintained. The “diluted” inclusion, in the UiO-67 3D framework, of luminescent heterocyclic linkers emitting in the blue-green visible region induces luminescence in the final MOFs (emission λmax = 442 and 420 nm for UiO-67-TpTp and UiO-67-TzTz, respectively), preventing self-quenching effects caused by the proximity of the emitters in the crystal structure. Both MOFs have been tested as sensors for contaminants of emerging concern (CECs) in water: an emission intensity increase has been observed when suspended in contact with diclofenac sodium, fluoxetine, ibuprofen and sulfamethoxazole. In particular, UiO-67-TzTz has shown a linearly increasing trend for a specific concentration range (up to 30–40 μM for diclofenac, fluoxetine and ibuprofen; up to 100 μM for sulfamethoxazole). UiO-67-TzTz also behaves as an adsorbent vs. diclofenac, with a maximum adsorption capacity (Xm) of 62.5 mg g−1. These findings pave the way to the practical utilization of UiO-67-TzTz as a multifunctional material (i.e. CECs luminescent sensor and adsorbent at one time) for environmental remediation.

Graphical abstract: UiO-67-derived bithiophene and bithiazole MIXMOFs for luminescence sensing and removal of contaminants of emerging concern in wastewater

Supplementary files

Article information

Article type
Research Article
Submitted
20 Sep 2021
Accepted
09 Nov 2021
First published
10 Nov 2021

Inorg. Chem. Front., 2022,9, 90-102

UiO-67-derived bithiophene and bithiazole MIXMOFs for luminescence sensing and removal of contaminants of emerging concern in wastewater

G. Mercuri, M. Moroni, S. Galli, C. Piccirillo, A. Capodilupo, G. Tuci, G. Giambastiani and A. Rossin, Inorg. Chem. Front., 2022, 9, 90 DOI: 10.1039/D1QI01184G

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