title: 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 I41/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 Hg2+, 19.7 ppb Pb2+) and demonstrates high selectivity for heavy metals over light metals, with detection ratios of 167.4 and 209.5 for Hg2+/Ca2+and Hg2+/Mg2+, respectively. Mixed-metal adsorption experiments also show that LMOF-263 selectively adsorbs Hg2+over other heavy metal ions in addition to light metals. The Pb2+KSVvalue for LMOF-263 (55,017 M-1) is the highest among LMOFs reported to date, and the Hg2+KSVvalue is the second highest (459,446 M-1). LMOF-263 exhibits a maximum adsorption capacity of 380 mg Hg2+/g. The Hg2+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 Hg2+and LMOF-263. No other MOFs have demonstrated such a high performance in both the detection and the capture of Hg2+from aqueous solution.
authors.affiliation: Department of Chemistry and Chemical Biology, Rutgers University , 610 Taylor Road, Piscataway, New Jersey 08854, United States.
authors.forename: Nathan D
authors.initials: ND
authors.lastname: Rudd
authors.affiliation: Department of Chemistry and Chemical Biology, Rutgers University , 610 Taylor Road, Piscataway, New Jersey 08854, United States.
authors.forename: Hao
authors.initials: H
authors.lastname: Wang
authors.affiliation: Department of Materials Science and Engineering, University of Texas at Dallas , 800 West Campbell Road, Richardson, Texas 75080, United States.
authors.forename: Erika M A
authors.initials: EM
authors.lastname: Fuentes-Fernandez
authors.affiliation: Advanced Light Source, Lawrence Berkeley National Laboratory , 1 Cyclotron Road, Berkeley, California 94720, United States.
authors.forename: Simon J
authors.initials: SJ
authors.lastname: Teat
authors.affiliation: Department of Chemistry, Biochemistry and Physics, Rider University , 2083 Lawrenceville Road, Lawrenceville, New Jersey 08648, United States.
authors.forename: Feng
authors.initials: F
authors.lastname: Chen
authors.affiliation: Department of Chemistry and Chemical Biology, Rutgers University , 610 Taylor Road, Piscataway, New Jersey 08854, United States.
authors.forename: Gene
authors.initials: G
authors.lastname: Hall
authors.affiliation: Department of Materials Science and Engineering, University of Texas at Dallas , 800 West Campbell Road, Richardson, Texas 75080, United States.
authors.forename: Yves J
authors.initials: YJ
authors.lastname: Chabal
authors.affiliation: Department of Chemistry and Chemical Biology, Rutgers University , 610 Taylor Road, Piscataway, New Jersey 08854, United States.
authors.forename: Jing
authors.initials: J
authors.lastname: Li
keywords: heavy metal adsorption; heavy metal detection; isoreticular series; ligand-based emission; luminescent metal−organic framework