TY - JOUR
T1 - Efficient Removal of Per- And Polyfluoroalkyl Substances from Water with Zirconium-Based Metal-Organic Frameworks
AU - Li, Rui
AU - Alomari, Shefa
AU - Stanton, Robert
AU - Wasson, Megan C.
AU - Islamoglu, Timur
AU - Farha, Omar K.
AU - Holsen, Thomas M.
AU - Thagard, Selma Mededovic
AU - Trivedi, Dhara J.
AU - Wriedt, Mario
N1 - Funding Information:
M.W. gratefully acknowledges the National Science Foundation CAREER Program (Award no. 1752771) for support of this research. R.S. and D.J.T. acknowledge support from the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant number TG-CHE190008. R.L. thanks Dr. Daniel Andreescu for the assistance in FTIR characterization. M.C.W. is supported by the NSF Graduate Research Fellowship under grant DGE-1842165. O.K.F. and T.I. gratefully acknowledge the support of the Nanoporous Materials Genome Center, funded by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences Program (award DE-FG02-17ER16362). T.M.H. acknowledges the support of the Center for Air and Aquatic Resources Engineering and Sciences (CAARES), which is accredited to perform PFAS analysis by the Department of Defense Environmental Laboratory Accreditation Program (DoD ELAP).
Publisher Copyright:
© 2021 American Chemical Society. All rights reserved.
PY - 2021/5/11
Y1 - 2021/5/11
N2 - Per- and polyfluoroalkyl substances (PFASs) are an emerging class of contaminants raising increased levels of concern due to their toxic, bioaccumulative, and persistent nature. Current solutions for removing PFAS from contaminated water rely on adsorption-based methods where commonly used sorbents, for example, activated carbons and ion-exchange resins, exhibit low adsorption capacity and a long equilibration time. Motivated by the generally deficient performance of these current materials, this work addresses the need for the discovery of advanced sorbents for high capacity and efficient PFAS removal. The zirconium-based metal-organic framework (MOF) NU-1000 was characterized for the adsorption of three perfluorosulfonic acids (PFSAs, C4-C8) and six perfluorinated carboxylic acids (PFCAs, C1-C9) from aqueous solutions. The results indicate that NU-1000 exhibits outstanding adsorption capacities of 400-620 mg/g for PFSAs and 201-604 mg/g for PFCAs coupled with ultrafast adsorption kinetics featuring equilibrium times of <1 min. Complementary density functional theory calculations reveal that the PFAS@MOF adsorption mechanism is dominated by a combination of hydrogen bonding, electrostatic, and hydrophobic non-covalent PFAS-MOF interactions. Excellent regeneration and reusability characteristics were found, particularly nearly quantitative removal and recovery rates of NU-1000 after five consecutive adsoption and desorption cycles of PFAS. Additional adsorption testing using PFAS-contaminated groundwater samples obtained from U.S. Air Force bases revealed impressive PFAS removal rates of 75-98% within 10 min regardless of the presence of co-contaminants. To the best of our knowledge, the suite of herein presented PFAS sorption characteristics - capacity, kinetics, regeneration, and reusability - significantly outperforms other current sorbents, rendering NU-1000 as a promising platform for the rapid and effective removal of PFAS from aqueous media.
AB - Per- and polyfluoroalkyl substances (PFASs) are an emerging class of contaminants raising increased levels of concern due to their toxic, bioaccumulative, and persistent nature. Current solutions for removing PFAS from contaminated water rely on adsorption-based methods where commonly used sorbents, for example, activated carbons and ion-exchange resins, exhibit low adsorption capacity and a long equilibration time. Motivated by the generally deficient performance of these current materials, this work addresses the need for the discovery of advanced sorbents for high capacity and efficient PFAS removal. The zirconium-based metal-organic framework (MOF) NU-1000 was characterized for the adsorption of three perfluorosulfonic acids (PFSAs, C4-C8) and six perfluorinated carboxylic acids (PFCAs, C1-C9) from aqueous solutions. The results indicate that NU-1000 exhibits outstanding adsorption capacities of 400-620 mg/g for PFSAs and 201-604 mg/g for PFCAs coupled with ultrafast adsorption kinetics featuring equilibrium times of <1 min. Complementary density functional theory calculations reveal that the PFAS@MOF adsorption mechanism is dominated by a combination of hydrogen bonding, electrostatic, and hydrophobic non-covalent PFAS-MOF interactions. Excellent regeneration and reusability characteristics were found, particularly nearly quantitative removal and recovery rates of NU-1000 after five consecutive adsoption and desorption cycles of PFAS. Additional adsorption testing using PFAS-contaminated groundwater samples obtained from U.S. Air Force bases revealed impressive PFAS removal rates of 75-98% within 10 min regardless of the presence of co-contaminants. To the best of our knowledge, the suite of herein presented PFAS sorption characteristics - capacity, kinetics, regeneration, and reusability - significantly outperforms other current sorbents, rendering NU-1000 as a promising platform for the rapid and effective removal of PFAS from aqueous media.
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U2 - 10.1021/acs.chemmater.1c00324
DO - 10.1021/acs.chemmater.1c00324
M3 - Article
AN - SCOPUS:85105043524
SN - 0897-4756
VL - 33
SP - 3276
EP - 3285
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 9
ER -