Phenolic nitroaromatics detection by fluorinated metal-organic frameworks: Barrier elimination for selective sensing of specific group of nitroaromatics

Mao-Lin Hu; Monika Joharian; Sayed Ali Akbar Razavi; Ali Morsali; Deng-Ze Wu; Alireza Azhdari Tehrani; Jun Wang; Peter C Junk; Zhi-Fang Guo

doi:10.1016/j.jhazmat.2020.124501

Phenolic nitroaromatics detection by fluorinated metal-organic frameworks: Barrier elimination for selective sensing of specific group of nitroaromatics

J Hazard Mater. 2021 Mar 15:406:124501. doi: 10.1016/j.jhazmat.2020.124501. Epub 2020 Dec 3.

Authors

Mao-Lin Hu¹, Monika Joharian², Sayed Ali Akbar Razavi², Ali Morsali³, Deng-Ze Wu⁴, Alireza Azhdari Tehrani², Jun Wang⁵, Peter C Junk⁵, Zhi-Fang Guo⁵

Affiliations

¹ College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, People's Republic of China. Electronic address: maolin-hu@yahoo.com.
² Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, Tehran, Iran.
³ Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, Tehran, Iran. Electronic address: morsali_a@modares.ac.ir.
⁴ College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035, People's Republic of China. Electronic address: wudengze@wzu.edu.cn.
⁵ College of Science & Engineering, James Cook University, Townsville, QLD 4811, Australia.

PMID: 33321315
DOI: 10.1016/j.jhazmat.2020.124501

Abstract

Many piesce of research have been performed to detect nitroaromatic-compounds (NACs) by metal-organic frameworks (MOFs). Despite extensive studies, there are still significant challenges like selective detection of specific NAC group in presence of other NACs. Here, we have integrated two functionalization strategies through decoration of pore-walls of the MOFs with trifluoromethyl groups and extension in π-conjugated system. Based on this idea, trifluoromethyl TMU-44 (with the formula [Zn₂(hfipbb)₂(L1)]_n.DMF, H₂hfipbb = 4,4'-(hexafluoroisopropylidene) bis(benzoic acid), L1 = N,N'-bis-pyridin-4-ylmethylene-benzene-1,4-diamine) and TMU-45 (with formula [Zn₂(hfipbb)₂(L2)]_n.DMF, L2 = N,N'-bis-pyridin-4-ylmethylene-naphthalene-1,5-diamine) frameworks have been synthesized. The aromatic skeleton of TMU-44 is based on phenyl rings while TMU-45 aromatic skeleton is extended by replacement of phenyl with naphthyl core. Measurements reveal that these MOFs are highly sensitive to phenolic NACs especially 2,4,6-trinitrophenol (TNP) with high quenching efficiency of 90% for TMU-44 (K_SV = 10,652 M^-1, LOD = 6.9 ppm) and 99% for TMU-45 (K_SV = 34,741 M^-1, LOD = 2.07 ppm). The proposed detection mechanism can be associated with hydrogen bonding between OH group of phenolic NACs and trifluoromethyl groups of TMU-MOFs as well as π(rich)∙∙∙π(deficient) interaction between π-conjugated backbone of TMU-frameworks and π-deficient ring of NACs.

Keywords: 2,4,6-Trinitropenol; Fluorinated metal-organic frameworks; Luminescent; Phenolic nitroaromatics; Photoluminescence sensor; Trifluoromethyl.

Publication types

Research Support, Non-U.S. Gov't