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Title: Efficient extraction of inorganic selenium from water by a Zr metal–organic framework: investigation of volumetric uptake capacity and binding motifs

Abstract

Strict monitoring and control of selenium concentrations in freshwater supplies is critical to safeguarding human health and aquatic life. A handful of previously investigated sorbents exhibit noteworthy gravimetric (mg g -1) Se uptake capacities; however, often display insufficient volumetric (mg cm -3) capacities, thereby requiring large volumes of material for commercial implementation. In this paper, in pursuit of mitigating this material inefficiency, we investigated the selenite (SeO 3 2-) and selenate (SeO 4 2-) affinity of MOF-808, a Zr-based metal–organic framework with a high density of potential Se oxyanion binding sites. MOF-808 recorded exceptional volumetric and gravimetric Se oxyanion capacities of 133 mg g -1 (127 mg cm -3) and 118 mg g -1 (112 mg cm -3) for aqueous selenite and selenate, respectively. Single-crystal X-ray diffraction studies revealed that selenite and selenate can bind at the MOF node via two distinct binding motifs, an η 2μ 2 motif in which the oxyanion coordinates to two different metal atoms in a single node, and a μ 2 motif in which the oxyanion interacts with only a single metal atom. Finally and furthermore, powder X-ray diffraction (PXRD) patterns and N 2 adsorption/desorption isotherms confirm the retention of bulk crystallinity and porositymore » after the uptake of Se oxyanions.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [1]; ORCiD logo [3]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  2. Concordia Univ., Montreal, QC (Canada). Dept. of Chemistry and Biochemistry
  3. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry. Dept. of Chemical and Biological Engineering; King Abdulaziz Univ., Jeddah (Saudi Arabia). Dept. of Chemistry
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)
OSTI Identifier:
1468444
Alternate Identifier(s):
OSTI ID: 1463190
Grant/Contract Number:  
NA0003763; ECCS-1542205
Resource Type:
Accepted Manuscript
Journal Name:
CrystEngComm
Additional Journal Information:
Journal Volume: 20; Journal Issue: 40; Journal ID: ISSN 1466-8033
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Drout, Riki J., Howarth, Ashlee J., Otake, Ken-ichi, Islamoglu, Timur, and Farha, Omar K. Efficient extraction of inorganic selenium from water by a Zr metal–organic framework: investigation of volumetric uptake capacity and binding motifs. United States: N. p., 2018. Web. doi:10.1039/c8ce00992a.
Drout, Riki J., Howarth, Ashlee J., Otake, Ken-ichi, Islamoglu, Timur, & Farha, Omar K. Efficient extraction of inorganic selenium from water by a Zr metal–organic framework: investigation of volumetric uptake capacity and binding motifs. United States. doi:10.1039/c8ce00992a.
Drout, Riki J., Howarth, Ashlee J., Otake, Ken-ichi, Islamoglu, Timur, and Farha, Omar K. Tue . "Efficient extraction of inorganic selenium from water by a Zr metal–organic framework: investigation of volumetric uptake capacity and binding motifs". United States. doi:10.1039/c8ce00992a. https://www.osti.gov/servlets/purl/1468444.
@article{osti_1468444,
title = {Efficient extraction of inorganic selenium from water by a Zr metal–organic framework: investigation of volumetric uptake capacity and binding motifs},
author = {Drout, Riki J. and Howarth, Ashlee J. and Otake, Ken-ichi and Islamoglu, Timur and Farha, Omar K.},
abstractNote = {Strict monitoring and control of selenium concentrations in freshwater supplies is critical to safeguarding human health and aquatic life. A handful of previously investigated sorbents exhibit noteworthy gravimetric (mg g-1) Se uptake capacities; however, often display insufficient volumetric (mg cm-3) capacities, thereby requiring large volumes of material for commercial implementation. In this paper, in pursuit of mitigating this material inefficiency, we investigated the selenite (SeO32-) and selenate (SeO42-) affinity of MOF-808, a Zr-based metal–organic framework with a high density of potential Se oxyanion binding sites. MOF-808 recorded exceptional volumetric and gravimetric Se oxyanion capacities of 133 mg g-1 (127 mg cm-3) and 118 mg g-1 (112 mg cm-3) for aqueous selenite and selenate, respectively. Single-crystal X-ray diffraction studies revealed that selenite and selenate can bind at the MOF node via two distinct binding motifs, an η2μ2 motif in which the oxyanion coordinates to two different metal atoms in a single node, and a μ2 motif in which the oxyanion interacts with only a single metal atom. Finally and furthermore, powder X-ray diffraction (PXRD) patterns and N2 adsorption/desorption isotherms confirm the retention of bulk crystallinity and porosity after the uptake of Se oxyanions.},
doi = {10.1039/c8ce00992a},
journal = {CrystEngComm},
number = 40,
volume = 20,
place = {United States},
year = {2018},
month = {8}
}

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Works referenced in this record:

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    Works referencing / citing this record:

    An Isoreticular Series of Metal-Organic Frameworks with Dendritic Hexacarboxylate Ligands and Exceptionally High Gas-Uptake Capacity
    journal, June 2010

    • Yuan, Daqiang; Zhao, Dan; Sun, Daofeng
    • Angewandte Chemie International Edition, Vol. 49, Issue 31, p. 5357-5361
    • DOI: 10.1002/anie.201001009

    Adsorption of selenite and selenate ions onto thiourea-formaldehyde resin
    journal, May 2011

    • Gezer, Nisa; Gülfen, Mustafa; Aydın, Ali Osman
    • Journal of Applied Polymer Science, Vol. 122, Issue 2
    • DOI: 10.1002/app.34246

    Water Purification: Adsorption over Metal-Organic Frameworks
    journal, February 2016

    • Li, Siqing; Chen, Yifa; Pei, Xiaokun
    • Chinese Journal of Chemistry, Vol. 34, Issue 2
    • DOI: 10.1002/cjoc.201500761

    Metal-organic frameworks (MOFs) in water filtration membranes for desalination and other applications
    journal, June 2018


    Experimental and theoretical study on selenate uptake to zirconium metal–organic frameworks: Effect of defects and ligands
    journal, December 2017


    Role of assisted natural remediation in environmental cleanup
    journal, October 2004


    Adsorption mechanisms of selenium oxyanions at the aluminum oxide/water interface
    journal, November 2006


    Adsorptive removal of Sb(V) from water using a mesoporous Zr-based metal–organic framework
    journal, September 2018


    Superior capability of MgAl2O4 for selenite removal from contaminated groundwater during its reconstruction of layered double hydroxides
    journal, April 2017


    Adsorption mechanism of selenate and selenite on the binary oxide systems
    journal, September 2009


    Adsorption of selenite and selenate by nanocrystalline aluminum oxide, neat and impregnated in chitosan beads
    journal, March 2014


    Postsynthetic Tuning of Metal–Organic Frameworks for Targeted Applications
    journal, February 2017


    Efficient Capture of Perrhenate and Pertechnetate by a Mesoporous Zr Metal–Organic Framework and Examination of Anion Binding Motifs
    journal, January 2018


    Efficient and Selective Uptake of TcO 4 by a Cationic Metal–Organic Framework Material with Open Ag + Sites
    journal, March 2017

    • Sheng, Daopeng; Zhu, Lin; Xu, Chao
    • Environmental Science & Technology, Vol. 51, Issue 6
    • DOI: 10.1021/acs.est.7b00339

    Selenium Sequestration in a Cationic Layered Rare Earth Hydroxide: A Combined Batch Experiments and EXAFS Investigation
    journal, July 2017

    • Zhu, Lin; Zhang, Linjuan; Li, Jie
    • Environmental Science & Technology, Vol. 51, Issue 15
    • DOI: 10.1021/acs.est.7b02006

    Metal–Organic Framework Materials as Chemical Sensors
    journal, September 2011

    • Kreno, Lauren E.; Leong, Kirsty; Farha, Omar K.
    • Chemical Reviews, Vol. 112, Issue 2, p. 1105-1125
    • DOI: 10.1021/cr200324t

    Carbon Dioxide Capture in Metal–Organic Frameworks
    journal, September 2011

    • Sumida, Kenji; Rogow, David L.; Mason, Jarad A.
    • Chemical Reviews, Vol. 112, Issue 2, p. 724-781
    • DOI: 10.1021/cr2003272

    Introduction to Metal–Organic Frameworks
    journal, September 2011

    • Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M.
    • Chemical Reviews, Vol. 112, Issue 2, p. 673-674
    • DOI: 10.1021/cr300014x

    Removal of selenate from water by chemical reduction
    journal, January 1988

    • Murphy, Andrew P.
    • Industrial & Engineering Chemistry Research, Vol. 27, Issue 1
    • DOI: 10.1021/ie00073a033

    Superacidity in Sulfated Metal–Organic Framework-808
    journal, September 2014

    • Jiang, Juncong; Gándara, Felipe; Zhang, Yue-Biao
    • Journal of the American Chemical Society, Vol. 136, Issue 37
    • DOI: 10.1021/ja507119n

    High Efficiency Adsorption and Removal of Selenate and Selenite from Water Using Metal–Organic Frameworks
    journal, June 2015

    • Howarth, Ashlee J.; Katz, Michael J.; Wang, Timothy C.
    • Journal of the American Chemical Society, Vol. 137, Issue 23
    • DOI: 10.1021/jacs.5b03904

    Rapid Simultaneous Removal of Toxic Anions [HSeO 3 ] , [SeO 3 ] 2– , and [SeO 4 ] 2– , and Metals Hg 2+ , Cu 2+ , and Cd 2+ by MoS 4 2– Intercalated Layered Double Hydroxide
    journal, August 2017

    • Ma, Lijiao; Islam, Saiful M.; Xiao, Chengliang
    • Journal of the American Chemical Society, Vol. 139, Issue 36
    • DOI: 10.1021/jacs.7b07123

    Identifying the Recognition Site for Selective Trapping of 99 TcO 4 in a Hydrolytically Stable and Radiation Resistant Cationic Metal–Organic Framework
    journal, October 2017

    • Zhu, Lin; Sheng, Daopeng; Xu, Chao
    • Journal of the American Chemical Society, Vol. 139, Issue 42
    • DOI: 10.1021/jacs.7b08632

    Design and synthesis of an exceptionally stable and highly porous metal-organic framework
    journal, November 1999

    • Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe
    • Nature, Vol. 402, Issue 6759, p. 276-279
    • DOI: 10.1038/46248

    Science and technology for water purification in the coming decades
    journal, March 2008

    • Shannon, Mark A.; Bohn, Paul W.; Elimelech, Menachem
    • Nature, Vol. 452, Issue 7185, p. 301-310
    • DOI: 10.1038/nature06599

    A series of isoreticular chiral metal–organic frameworks as a tunable platform for asymmetric catalysis
    journal, July 2010

    • Ma, Liqing; Falkowski, Joseph M.; Abney, Carter
    • Nature Chemistry, Vol. 2, Issue 10
    • DOI: 10.1038/nchem.738

    Porous metal–organic-framework nanoscale carriers as a potential platform for drug delivery and imaging
    journal, December 2009

    • Horcajada, Patricia; Chalati, Tamim; Serre, Christian
    • Nature Materials, Vol. 9, Issue 2
    • DOI: 10.1038/nmat2608

    Hydrogen storage in metal–organic frameworks
    journal, January 2009

    • Murray, Leslie J.; Dincă, Mircea; Long, Jeffrey R.
    • Chemical Society Reviews, Vol. 38, Issue 5, p. 1294-1314
    • DOI: 10.1039/b802256a

    Selective gas adsorption and separation in metal–organic frameworks
    journal, January 2009

    • Li, Jian-Rong; Kuppler, Ryan J.; Zhou, Hong-Cai
    • Chemical Society Reviews, Vol. 38, Issue 5, p. 1477-1504
    • DOI: 10.1039/b802426j

    Metal–organic framework materials as catalysts
    journal, January 2009

    • Lee, JeongYong; Farha, Omar K.; Roberts, John
    • Chemical Society Reviews, Vol. 38, Issue 5, p. 1450-1459
    • DOI: 10.1039/b807080f

    Selenate Removal from Sulfate Containing Aqueous Solutions
    journal, October 2005


    Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage
    journal, January 2002

    • Eddaoudi, Mohamed; Kim, Jaheon; Rosi, Nathaniel
    • Science, Vol. 295, Issue 5554, p. 469-472
    • DOI: 10.1126/science.1067208

    Selective Selenate Adsorption on Cationated Amino-Functionalized MCM-41
    journal, November 2003

    • Yokoi, Toshiyuki; Tatsumi, Takashi; Yoshitake, Hideaki
    • Bulletin of the Chemical Society of Japan, Vol. 76, Issue 11
    • DOI: 10.1246/bcsj.76.2225