Benzothiazolium-functionalizedNU-1000: a versatile material for carbon dioxide adsorption and cyanide luminescence sensing

Lapo Luconi, Giorgio Mercuri, Timur Islamoglu, Andrea Fermi*, Giacomo Bergamini, Giuliano Giambastiani, Andrea Rossin

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

19 Scopus citations


A tailor-made benzothiazolium bromide salt functionality (BzTz) is introducedviasolvent-assisted ligand incorporation (SALI) into the mesoporous Zr-based metal-organic frameworkNU-1000. The resultingNU-1000-BzTzcomposite has been thoroughly characterized in the solid state. The functional group loading has been determined through1H NMR analysis of the digested sample (5% HF-DMSO-d6): a maximum value of 1.7BzTzligand per [Zr6] node is achieved. The material preserves its pristine crystallinity after SALI, as witnessed by powder X-ray diffraction. The functionalized MOF has a slightly lower thermal stability than its parent material (Tdec= 780vs.800 K, respectively). The N2adsorption isotherm collected at 77 K disclosed that its BET specific surface area (1530 m2g−1) is lower than that of prisitineNU-1000(2140 m2g−1), because of the space taken and weight added by the dangling benzothiazolium groups inside the pores. A total CO2uptake of 2.0 mmol g−1(8.7 wt% CO2) has been calculated from the CO2adsoprtion isotherm collected atT= 298 K andpCO2= 1 bar. Despite the lower BET area,NU-1000-BzTzshows an increased thermodynamic affinity for CO2(isosteric heat of adsorptionQst= 25 kJ mol−1) if compared withNU-1000(Qst= 17 kJ mol−1), confirming that the presence of a polar functional group in the MOF pores improves the interaction with carbon dioxide. Finally,NU-1000-BzTzhas been exploited as a luminescent sensor for polluting anions (CN, SCN, OCN, and SeCNas sodium or potassium salts) in aqueous solutions, after bromide exchange. A marked reversible blue shift of its emission band from 490 to 450 nm is observed in all cases, with the associated emission color change from light green to blue under a UV lamp. The detection limit of CN(1.08 × 10−6M) is much lower than that measured for the other “stick-like” anions considered in this study. The process occurs efficiently even in the presence of other competing ions ( ordinary tap water), opening promising application perspectives in cyanide luminescence sensing in drinking water.

Original languageEnglish (US)
Pages (from-to)7492-7500
Number of pages9
JournalJournal of Materials Chemistry C
Issue number22
StatePublished - Jun 14 2020

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Chemistry


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