TY - JOUR
T1 - Highly Efficient Luminescent Metal-Organic Framework for the Simultaneous Detection and Removal of Heavy Metals from Water
AU - Rudd, Nathan D.
AU - Wang, Hao
AU - Fuentes-Fernandez, Erika M.A.
AU - Teat, Simon J.
AU - Chen, Feng
AU - Hall, Gene
AU - Chabal, Yves J.
AU - Li, Jing
N1 - Funding Information:
We are grateful for the financial support from the Department of Energy, Basic Energy Sciences, Division of Materials Sciences and Engineering through Grant No. DE-FG02-08ER-46491. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02- 05CH11231. We would also like to thank Horiba Scientific for the loan of the XGT-1000WR EDXRF spectrometer. N.R. would like to especially thank Ben Deibert and Baiyan Li for their extensive and valued discussions.
PY - 2016/11/9
Y1 - 2016/11/9
N2 - 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+ KSV value for LMOF-263 (55,017 M-1) is the highest among LMOFs reported to date, and the Hg2+ KSV value 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.
AB - 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+ KSV value for LMOF-263 (55,017 M-1) is the highest among LMOFs reported to date, and the Hg2+ KSV value 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.
KW - heavy metal adsorption
KW - heavy metal detection
KW - isoreticular series
KW - ligand-based emission
KW - luminescent metal-organic framework
UR - http://www.scopus.com/inward/record.url?scp=84994744888&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84994744888&partnerID=8YFLogxK
U2 - 10.1021/acsami.6b10890
DO - 10.1021/acsami.6b10890
M3 - Article
AN - SCOPUS:84994744888
VL - 8
SP - 30294
EP - 30303
JO - ACS applied materials & interfaces
JF - ACS applied materials & interfaces
SN - 1944-8244
IS - 44
ER -