Title: Efficient Removal of Per- and Polyfluoroalkyl Substances from Water with Zirconium-Based Metal–Organic Frameworks

Abstract

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. Here, 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 obtainedmore » 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.« less

Authors:

Li, Rui ^[1]; Alomari, Shefa ^[1]; Stanton, Robert ^[1]; Wasson, Megan C.  ^[2];

• Search DOE PAGES for author "Wasson, Megan C."
• Search DOE PAGES for ORCID "0000-0002-9384-2033"

Islamoglu, Timur  ^[2];

• Search DOE PAGES for author "Islamoglu, Timur"
• Search DOE PAGES for ORCID "0000-0003-3688-9158"

Farha, Omar K.  ^[2];

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• Search DOE PAGES for ORCID "0000-0002-9904-9845"

Holsen, Thomas M. ^[1]; Thagard, Selma Mededovic  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-6371-4751"

Trivedi, Dhara J.  ^[1];

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• Search DOE PAGES for ORCID "0000-0002-8151-3929"

Wriedt, Mario  ^[1]

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• Search DOE PAGES for ORCID "0000-0003-3118-9507"

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+ Show Author Affiliations

1. Clarkson Univ., Potsdam, NY (United States)
2. Northwestern Univ., Evanston, IL (United States)

Publication Date:

Mon Apr 19 00:00:00 EDT 2021

Research Org.:

Univ. of Minnesota, Minneapolis, MN (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES); NSF Graduate Research Fellowship

OSTI Identifier:

1786325

Grant/Contract Number:  

SC0008688; FG02-17ER16362; TG-CHE190008; DGE-1842165

Resource Type:

Accepted Manuscript

Journal Name:

Chemistry of Materials

Additional Journal Information:

Journal Volume: 33; Journal Issue: 9; Journal ID: ISSN 0897-4756

Publisher:

American Chemical Society (ACS)

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; Adsorption; Metal organic frameworks; Molecular mechanics; Regeneration; Groundwaters