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Unveiling the Impact of Diverse Morphology of Ionic Porous Organic Polymers with Mechanistic Insight on the Ultrafast and Selective Removal of Toxic Pollutants from Water

  • Writakshi Mandal
    Writakshi Mandal
    Department of Chemistry, Indian Institute of Science Education and Research (IISER) Pune, Dr. Homi Bhaba Road, Pashan, Pune 411008, India
  • Sahel Fajal
    Sahel Fajal
    Department of Chemistry, Indian Institute of Science Education and Research (IISER) Pune, Dr. Homi Bhaba Road, Pashan, Pune 411008, India
    More by Sahel Fajal
  • Samraj Mollick
    Samraj Mollick
    Department of Chemistry, Indian Institute of Science Education and Research (IISER) Pune, Dr. Homi Bhaba Road, Pashan, Pune 411008, India
  • Mandar M. Shirolkar
    Mandar M. Shirolkar
    Symbiosis Center for Nanoscience and Nanotechnology (SCNN), Symbiosis International (Deemed University) (SIU), Lavale, Pune 412115, Maharashtra, India
  • Yogeshwar D. More
    Yogeshwar D. More
    Department of Chemistry, Indian Institute of Science Education and Research (IISER) Pune, Dr. Homi Bhaba Road, Pashan, Pune 411008, India
  • Satyam Saurabh
    Satyam Saurabh
    Department of Chemistry, Indian Institute of Science Education and Research (IISER) Pune, Dr. Homi Bhaba Road, Pashan, Pune 411008, India
  • Debanjan Mahato
    Debanjan Mahato
    Department of Chemistry, Indian Institute of Science Education and Research (IISER) Pune, Dr. Homi Bhaba Road, Pashan, Pune 411008, India
  • , and 
  • Sujit K. Ghosh*
    Sujit K. Ghosh
    Department of Chemistry, Indian Institute of Science Education and Research (IISER) Pune, Dr. Homi Bhaba Road, Pashan, Pune 411008, India
    *Email: [email protected]. Phone: +91 20 2590 8076.
Cite this: ACS Appl. Mater. Interfaces 2022, 14, 17, 20042–20052
Publication Date (Web):April 24, 2022
https://doi.org/10.1021/acsami.2c02174
Copyright © 2022 American Chemical Society

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    Supporting Info (5)»

    Abstract

    Abstract Image

    In recent years, detoxification of contaminated water by different types of materials has received a great deal of attention. However, lack of methodical in-depth understanding of the role of various physical properties of such materials toward improved sorption performance limits their applicable efficiencies. In perspective, decontamination of oxoanion-polluted water by porous materials with different morphologies are unexplored due to a shortfall of proper synthetic strategies. Herein, systematic optimization of sequestration performance toward efficient decontamination of toxic oxoanion-polluted water has been demonstrated by varying the morphologies of an imidazolium-based cationic polymeric network [ionic porous organic polymers (iPOP-5)]. Detailed morphological evolution showed that the chemically stable ionic polymer exhibited several morphologies such as spherical, nanotube, and flakes. Among them, the flakelike material [iPOP-5(F)] showed ultrafast capture efficiency (up to ∼99 and >85% removal within less than 1 min) with high saturation capacities (301 and 610 mg g–1) toward chromate [Cr(VI)] and perrhenate [Re(VII)] oxoanions, respectively, in water. On the other hand, the spherical-shaped polymer [iPOP-5(S)] exhibited relatively slow removal kinetics (>5 min for complete removal) toward both Cr(VI) and Re(VII) oxoanions. Notably, iPOP-5(F) eliminated Cr(VI) and Re(VII) selectively even in the presence of excessive (∼100-fold) competing anions from both high- and low-concentration contaminated water. Further, the compound demonstrated efficient separation of those oxoanions in a wide pH range as well as in various water systems (such as potable, lake, river, sea, and tannery water) with superior regeneration ability. Moreover, as a proof of concept, a column exchange-based water treatment experiment by iPOP-5(F) has been performed to reduce the concentration of Cr(VI) and Re(VII) below the WHO permitted level. Mechanistic investigation suggested that the rare in situ exfoliation of flakes into thin nanosheets helps to achieve ultrafast capture efficiency. In addition, detailed theoretical binding energy calculations were executed in order to understand such rapid, selective binding of chromate and perrhenate oxoanions with iPOP-5(F) over other nonmetal-based anions.

    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsami.2c02174.

    • Detail synthesis protocols, structural characterization figures, FT-IR profile, TGA curves, solid-state NMR spectra, FESEM, TEM, and AFM images, EDX and mapping data, XPS data, oxoanion capture studies, and tables (PDF)

    • K2CrO4 capture experiment (MP4)

    • KReO4 capture experiment (MP4)

    • Interaction of CrO42– with iPOP-5 (MP4)

    • Interaction of ReO4 with iPOP-5 (MP4)

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    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 8 publications.

    1. Haiyue Peng, Bo Jiang, Feize Li, Junyuan Gong, Yingdan Zhang, Meng Yang, Ning Liu, Lijian Ma. Single-Crystal-Structure Directed Predesign of Cationic Covalent Organic Polymers for Rapidly Capturing 99TcO4–. Chemistry of Materials 2023, 35 (6) , 2531-2540. https://doi.org/10.1021/acs.chemmater.2c03812
    2. Lei Li, Meiyu Zhang, Kang Kang, Chengliang Xiao. Twofold Interpenetrated Cationic Metal–Organic Framework with Hydrophobic Channels for Effectively Trapping Toxic Oxo-Anions. Inorganic Chemistry 2022, 61 (49) , 19933-19943. https://doi.org/10.1021/acs.inorgchem.2c03196
    3. Writakshi Mandal, Sahel Fajal, Partha Samanta, Subhajit Dutta, Mandar M. Shirolkar, Yogeshwar D. More, Sujit K. Ghosh. Selective and Sensitive Recognition of Specific Types of Toxic Organic Pollutants with a Chemically Stable Highly Luminescent Porous Organic Polymer (POP). ACS Applied Polymer Materials 2022, 4 (11) , 8633-8644. https://doi.org/10.1021/acsapm.2c01538
    4. Shu-Qing Fu, Ming-Zhi Zhu, Boxin Xue, Pei-Nian Liu. Synergy between Ionic Capacity and Intrinsic Porosity in Imidazolium-Based Cationic Organic Polymers and Its Effect on Anionic Dye Adsorption. Macromolecules 2022, 55 (19) , 8784-8794. https://doi.org/10.1021/acs.macromol.2c01127
    5. Sohom Chandra, Atikur Hassan, Prince, Akhtar Alam, Neeladri Das. Rapid and Efficient Removal of Diverse Anionic Water Contaminants Using a Guanidium-Based Ionic Covalent Organic Network (iCON). ACS Applied Polymer Materials 2022, 4 (9) , 6630-6641. https://doi.org/10.1021/acsapm.2c00989
    6. Sribash Das, Gunanka Hazarika, Debasis Manna. Guanidine‐Functionalized Fluorescent sp 2 Carbon‐Conjugated Covalent Organic Framework for Sensing and Capture of Pd(II) and Cr(VI) Ions. Chemistry – A European Journal 2023, 29 (15) https://doi.org/10.1002/chem.202203595
    7. Rong Gao, Bohang An, Cen Zhou, Xiao Zhang. Synthesis of a Triazaisotruxene-Based Porous Organic Polymer and Its Application in Iodine Capture. Molecules 2022, 27 (24) , 8722. https://doi.org/10.3390/molecules27248722
    8. Atikur Hassan, Akhtar Alam, Sohom Chandra, Prince, Neeladri Das. Triptycene-based and imine linked porous uniform microspheres for efficient and reversible scavenging of iodine from various media: a systematic study. Environmental Science: Advances 2022, 1 (3) , 320-330. https://doi.org/10.1039/D2VA00024E

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