Highly Efficient Luminescent Metal–Organic Framework for the Simultaneous Detection and Removal of Heavy Metals from Water

Abstract

We have designed and synthesized an isoreticular series of luminescent metal–organic frameworks (LMOFs) by incorporating a strongly emissive molecular fluorophore and functionally diverse colinkers into Zn-based structures. The three-dimensional porous networks of LMOF-261, -262, and -263 represent a unique/new type of nets, classified as a 2-nodal, (4,4)-c net (mot-e type) with 4-fold, class IIIa interpenetration. All compounds crystallize in a body-centered tetragonal crystal system (space group I 4 1 /a). A systematic study has been implemented to analyze their interactions with heavy metals. LMOF-263 exhibits impressive water stability, high porosity, and strong luminescence, making it an excellent candidate as a fluorescent chemical sensor and adsorbent for aqueous contaminants. It is extremely responsive to toxic heavy metals at a parts per billion level (3.3 ppb Hg 2+, 19.7 ppb Pb 2+ ) and demonstrates high selectivity for heavy metals over light metals, with detection ratios of 167.4 and 209.5 for Hg 2+ /Ca 2+ and Hg 2+ /Mg 2+, respectively. Mixed-metal adsorption experiments also show that LMOF-263 selectively adsorbs Hg 2+ over other heavy metal ions in addition to light metals. The Pb 2+ K SV value for LMOF-263 (55,017 M –1 ) is the highest among LMOFs reported to date, and the Hg 2+ K SV value is the second highest (459,446 M –1 ). LMOF-263 exhibits a maximum adsorption capacity of 380 mg Hg 2+ /g. The Hg 2+ adsorption process follows pseudo-second-order kinetics, removing 99.1% of the metal within 30 min. An in situ XPS study provides insight to help understand the interaction mechanism between Hg 2+ and LMOF-263. No other MOFs have demonstrated such a high performance in both the detection and the capture of Hg 2+ from aqueous solution.