US EPA

7939943 

Journal Article 

A Zr-Based Metal-Organic Framework with a DUT-52 Structure Containing a Trifluoroacetamido-Functionalized Linker for Aqueous Phase Fluorescence Sensing of the Cyanide Ion and Aerobic Oxidation of Cyclohexane 

Gogoi, C; Nagarjun, N; Roy, S; Mostakim, SK; Volkmer, D; Dhakshinamoorthy, A; Biswas, S 

2021 

Yes 

Inorganic Chemistry
ISSN: 0020-1669
EISSN: 1520-510X 

60 

7 

4539-4550 

English 

33703899 

10.1021/acs.inorgchem.0c03472 

WOS:000637850300041 

https://www.scopus.com/inward/record.uri?eid=2-s2.0-85103465375&doi=10.1021%2facs.inorgchem.0c03472&partnerID=40&md5=cb01972d2e58714975a0482364614e77
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A zirconium (Zr) metal-organic framework having a DUT-52 (DUT stands for Dresden University of Technology) structure with face-centered cubic topology and bearing the rigid 1-(2,2,2-trifluoroacetamido) naphthalene-3,7-dicarboxylic acid (H2NDC-NHCOCF3) ligand was prepared, and its solid structure was characterized with the help of the X-ray powder diffraction (XRPD) technique. Other characterization methods like thermogravimetric analysis (TGA) and Fourier transform infrared (FT-IR) spectroscopy were applied to verify the phase purity of the compound. In order to get the solvent-free compound (1'), 1 was stirred with methanol for overnight and subsequently heated at 100 °C overnight under vacuum. As-synthesized (1) and activated (1') compounds are thermally stable up to 300 °C. The Brunsuer Emmett-Teller (BET) surface area of 1' was found to be 1105 m2 g-1. Fluorescence titration experiments showed that 1' exhibits highly selective and sensitive fluorescence turn-on behavior toward cyanide (CN-) anion. The interference experiments suggested that other anions did not interfere in the detection of CN-. Moreover, a very short response time (2 min) was shown by probe 1' for CN- detection. The detection limit was found to be 0.23 μM. 1' can also be effectively used for CN- detection in real water samples. The mechanism for the selective detection of CN- was investigated systematically. Furthermore, the aerobic oxidation of cyclohexane was performed with 1' under mild reaction conditions, observing higher activity than the analogous DUT-52 solid under identical conditions. These experiments clearly indicate the benefits of hydrophobic cavities of 1' in achieving higher conversion of cyclohexane and cyclohexanol/cyclohexanone selectivity. Catalyst stability was proved by two consecutive reuses and comparing the structural integrity of 1' before and after reuses by the XRPD study.