Highly Stable Zr(IV)-Based Metal–Organic Frameworks for the Detection and Removal of Antibiotics and Organic Explosives in Water

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• 作者：Bin Wang ; Xiu-Liang Lv ; Dawei Feng ; Lin-Hua Xie ; Jian Zhang ; Ming Li ; Yabo Xie ; Jian-Rong Li ; Hong-Cai Zhou
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：May 18, 2016
• 年：2016
• 卷：138
• 期：19
• 页码：6204-6216
• 全文大小：850K
• 年卷期：0
• ISSN：1520-5126

文摘

Antibiotics and organic explosives are among the main organic pollutants in wastewater; their detection and removal are quite important but challenging. As a new class of porous materials, metal–organic frameworks (MOFs) are considered as a promising platform for the sensing and adsorption applications. In this work, guided by a topological design approach, two stable isostructural Zr(IV)-based MOFs, Zr₆O₄(OH)₈(H₂O)₄(CTTA)_8/3 (BUT-12, H₃CTTA = 5′-(4-carboxyphenyl)-2′,4′,6′-trimethyl-[1,1′:3′,1″-terphenyl]-4,4″-dicarboxylic acid) and Zr₆O₄(OH)₈(H₂O)₄(TTNA)_8/3 (BUT-13, H₃TTNA = 6,6′,6″-(2,4,6-trimethylbenzene-1,3,5-triyl)tris(2-naphthoic acid)) with the the-a topological structure constructed by D_4h 8-connected Zr₆ clusters and D_3h 3-connected linkers were designed and synthesized. The two MOFs are highly porous with the Brunauer–Emmett–Teller surface area of 3387 and 3948 m² g^–1, respectively. Particularly, BUT-13 features one of the most porous water-stable MOFs reported so far. Interestingly, these MOFs represent excellent fluorescent properties, which can be efficiently quenched by trace amounts of nitrofurazone (NZF) and nitrofurantoin (NFT) antibiotics as well as 2,4,6-trinitrophenol (TNP) and 4-nitrophenol (4-NP) organic explosives in water solution. They are responsive to NZF and TNP at parts per billion (ppb) levels, which are among the best performing luminescent MOF-based sensing materials. Simultaneously, both MOFs also display high adsorption abilities toward these organic molecules. It was demonstrated that the adsorption plays an important role in the preconcentration of analytes, which can further increase the fluorescent quenching efficiency. These results indicate that BUT-12 and -13 are favorable materials for the simultaneous selective detection and removal of specific antibiotics and organic explosives from water, being potentially useful in monitoring water quality and treating wastewater.