TY - JOUR
T1 - A Ca2+ MOF combining highly efficient sorption and capability for voltammetric determination of heavy metal ions in aqueous media
AU - Pournara, Anastasia D.
AU - Margariti, Antigoni
AU - Tarlas, Georgios D.
AU - Kourtelaris, Andreas
AU - Petkov, Valeri
AU - Kokkinos, Christos
AU - Economou, Anastasios
AU - Papaefstathiou, Giannis S.
AU - Manos, Manolis J.
N1 - Funding Information:
AP would like to thank the State Scholarships foundation (IKY) for a post-doctoral research scholarship, funded by the Action “Supporting Post-Academic Researchers” from the resources of the NF “Human Resources Development, Education and Lifelong Learning” with Priority Axes 6, 8, and 9 and co-funded by the European Social Fund – ESF and the Greek State. This work was partially supported by the Special Account for Research Grants (SARG) of the National and Kapodistrian University of Athens (UoA). The work was also supported in part by DOE grant DE-SC0006877. The Bodossaki Foundation is gratefully acknowledged for donating the TGA to UoA.
Publisher Copyright:
© 2019 The Royal Society of Chemistry.
PY - 2019
Y1 - 2019
N2 - We recently discovered that a Ca2+ two-dimensional framework, namely [Ca(H4L)(DMA)2]·2DMA (Ca-MOF), was capable of exchanging the Ca2+ ions with Cu2+ almost quantitatively in a matter of seconds in aqueous solution. Herein, we report that Ca-MOF exhibits the capability of both removal and voltammetric determination of heavy metal ions in aqueous media. Ca-MOF shows one of the highest Pb2+ sorption capacities (∼522 mg g-1) reported for MOFs. More importantly, a column filled with Ca-MOF (1% wt) particles dispersed in silica sand (99% wt) can quantitatively remove traces of Pb2+ (∼100 ppb) from a relatively large volume of a wastewater simulant solution (containing a large excess of competitive ions). Ca-MOF is also highly efficient for sorption of Cd2+, Ni2+ and Zn2+, even in the presence of several competitive cations. Actually, the Cd2+ sorption capacity (∼220 mg g-1) of Ca-MOF is one of the largest reported for MOFs. Furthermore, detailed Ni2+ and Zn2+ sorption studies of MOFs have not been described prior to this work. The mechanism of the M2+ (M2+ = Pb2+, Cd2+, Ni2+, Zn2+) exchange process was elucidated based on a series of spectroscopic, analytical and X-ray diffraction methods. In addition, a simple ready-to-use electrochemical sensor based on modified graphite paste with Ca-MOF was fabricated and successfully utilized for the determination of Pb2+, Cd2+, Cu2+ and Zn2+ at μg L-1 levels in aqueous solutions by anodic stripping voltammetry (ASV). Overall, this work demonstrates, for the first time, a dual function of a MOF as a sorbent and as an electrochemical sensor for heavy metal ions, thus opening a new window for materials with application in both environmental remediation and monitoring.
AB - We recently discovered that a Ca2+ two-dimensional framework, namely [Ca(H4L)(DMA)2]·2DMA (Ca-MOF), was capable of exchanging the Ca2+ ions with Cu2+ almost quantitatively in a matter of seconds in aqueous solution. Herein, we report that Ca-MOF exhibits the capability of both removal and voltammetric determination of heavy metal ions in aqueous media. Ca-MOF shows one of the highest Pb2+ sorption capacities (∼522 mg g-1) reported for MOFs. More importantly, a column filled with Ca-MOF (1% wt) particles dispersed in silica sand (99% wt) can quantitatively remove traces of Pb2+ (∼100 ppb) from a relatively large volume of a wastewater simulant solution (containing a large excess of competitive ions). Ca-MOF is also highly efficient for sorption of Cd2+, Ni2+ and Zn2+, even in the presence of several competitive cations. Actually, the Cd2+ sorption capacity (∼220 mg g-1) of Ca-MOF is one of the largest reported for MOFs. Furthermore, detailed Ni2+ and Zn2+ sorption studies of MOFs have not been described prior to this work. The mechanism of the M2+ (M2+ = Pb2+, Cd2+, Ni2+, Zn2+) exchange process was elucidated based on a series of spectroscopic, analytical and X-ray diffraction methods. In addition, a simple ready-to-use electrochemical sensor based on modified graphite paste with Ca-MOF was fabricated and successfully utilized for the determination of Pb2+, Cd2+, Cu2+ and Zn2+ at μg L-1 levels in aqueous solutions by anodic stripping voltammetry (ASV). Overall, this work demonstrates, for the first time, a dual function of a MOF as a sorbent and as an electrochemical sensor for heavy metal ions, thus opening a new window for materials with application in both environmental remediation and monitoring.
UR - http://www.scopus.com/inward/record.url?scp=85068195668&partnerID=8YFLogxK
U2 - 10.1039/c9ta03337h
DO - 10.1039/c9ta03337h
M3 - Article
VL - 7
SP - 15432
EP - 15443
JO - Journal of Materials Chemistry A
JF - Journal of Materials Chemistry A
SN - 2050-7488
IS - 25
ER -