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Title: Rapid, Selective Heavy Metal Removal from Water by a Metal–Organic Framework/Polydopamine Composite

Abstract

Drinking water contamination with heavy metals, particularly lead, is a persistent problem worldwide with grave public health consequences. Existing purification methods often cannot address this problem quickly and economically. Here we report a cheap, water stable metal–organic framework/polymer composite, Fe-BTC/PDA, that exhibits rapid, selective removal of large quantities of heavy metals, such as Pb2+ and Hg2+, from real world water samples. In this work, Fe-BTC is treated with dopamine, which undergoes a spontaneous polymerization to polydopamine (PDA) within its pores via the Fe3+ open metal sites. The PDA, pinned on the internal MOF surface, gains extrinsic porosity, resulting in a composite that binds up to 1634 mg of Hg2+ and 394 mg of Pb2+ per gram of composite and removes more than 99.8% of these ions from a 1 ppm solution, yielding drinkable levels in seconds. Further, the composite properties are well-maintained in river and seawater samples spiked with only trace amounts of lead, illustrating unprecedented selectivity. Remarkably, no significant uptake of competing metal ions is observed even when interferents, such as Na+, are present at concentrations up to 14 000 times that of Pb2+. The material is further shown to be resistant to fouling when tested in high concentrationsmore » of common organic interferents, like humic acid, and is fully regenerable over many cycles.« less

Authors:
 [1];  [1];  [2];  [1];  [1];  [3];  [4]; ORCiD logo [1]
  1. Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), CH-1051 Sion, Switzerland
  2. Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), CH-1051 Sion, Switzerland, Department of Chemical and Biomolecular Engineering, University of California, Berkeley, Berkeley, California 94720, United States
  3. The Molecular Foundry, Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  4. Interdisciplinary Center for Electron Microscopy, École Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Swiss National Science Foundation (SNSF); German Research Foundation (DFG)
OSTI Identifier:
1426013
Alternate Identifier(s):
OSTI ID: 1494086; OSTI ID: 1508765; OSTI ID: 1508766
Grant/Contract Number:  
AC02-05CH11231; PYAPP2_160581; SPP 1570
Resource Type:
Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Name: ACS Central Science Journal Volume: 4 Journal Issue: 3; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Sun, Daniel T., Peng, Li, Reeder, Washington S., Moosavi, Seyed Mohamad, Tiana, Davide, Britt, David K., Oveisi, Emad, and Queen, Wendy L. Rapid, Selective Heavy Metal Removal from Water by a Metal–Organic Framework/Polydopamine Composite. United States: N. p., 2018. Web. doi:10.1021/acscentsci.7b00605.
Sun, Daniel T., Peng, Li, Reeder, Washington S., Moosavi, Seyed Mohamad, Tiana, Davide, Britt, David K., Oveisi, Emad, & Queen, Wendy L. Rapid, Selective Heavy Metal Removal from Water by a Metal–Organic Framework/Polydopamine Composite. United States. https://doi.org/10.1021/acscentsci.7b00605
Sun, Daniel T., Peng, Li, Reeder, Washington S., Moosavi, Seyed Mohamad, Tiana, Davide, Britt, David K., Oveisi, Emad, and Queen, Wendy L. Wed . "Rapid, Selective Heavy Metal Removal from Water by a Metal–Organic Framework/Polydopamine Composite". United States. https://doi.org/10.1021/acscentsci.7b00605.
@article{osti_1426013,
title = {Rapid, Selective Heavy Metal Removal from Water by a Metal–Organic Framework/Polydopamine Composite},
author = {Sun, Daniel T. and Peng, Li and Reeder, Washington S. and Moosavi, Seyed Mohamad and Tiana, Davide and Britt, David K. and Oveisi, Emad and Queen, Wendy L.},
abstractNote = {Drinking water contamination with heavy metals, particularly lead, is a persistent problem worldwide with grave public health consequences. Existing purification methods often cannot address this problem quickly and economically. Here we report a cheap, water stable metal–organic framework/polymer composite, Fe-BTC/PDA, that exhibits rapid, selective removal of large quantities of heavy metals, such as Pb2+ and Hg2+, from real world water samples. In this work, Fe-BTC is treated with dopamine, which undergoes a spontaneous polymerization to polydopamine (PDA) within its pores via the Fe3+ open metal sites. The PDA, pinned on the internal MOF surface, gains extrinsic porosity, resulting in a composite that binds up to 1634 mg of Hg2+ and 394 mg of Pb2+ per gram of composite and removes more than 99.8% of these ions from a 1 ppm solution, yielding drinkable levels in seconds. Further, the composite properties are well-maintained in river and seawater samples spiked with only trace amounts of lead, illustrating unprecedented selectivity. Remarkably, no significant uptake of competing metal ions is observed even when interferents, such as Na+, are present at concentrations up to 14 000 times that of Pb2+. The material is further shown to be resistant to fouling when tested in high concentrations of common organic interferents, like humic acid, and is fully regenerable over many cycles.},
doi = {10.1021/acscentsci.7b00605},
journal = {ACS Central Science},
number = 3,
volume = 4,
place = {United States},
year = {Wed Mar 14 00:00:00 EDT 2018},
month = {Wed Mar 14 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acscentsci.7b00605

Citation Metrics:
Cited by: 268 works
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Figures / Tables:

Figure 1 Figure 1: Characterization of Fe-BTC/PDA. (Left) Polyhedral view of a large cage in the Fe-BTC with PDA embedded inside the channels. The purple sphere represents the void space inside of the cage prior to the dopamine addition. (Top) The simulated XRD pattern of Fe-BTC (black) compared to the synchrotron XRDmore » data (λ = 0.50084 Å) of Fe-BTC (red) and Fe-BTC/PDA-19 (blue). (Bottom) X-ray photoelectron spectroscopy data obtained from the N 1s spectrum of FeBTC/PDA-19.« less

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Works referenced in this record:

Strong CO2 Binding in a Water-Stable, Triazolate-Bridged Metal−Organic Framework Functionalized with Ethylenediamine
journal, July 2009

  • Demessence, Aude; D’Alessandro, Deanna M.; Foo, Maw Lin
  • Journal of the American Chemical Society, Vol. 131, Issue 25, p. 8784-8786
  • DOI: 10.1021/ja903411w

Comparison of Porous Iron Trimesates Basolite F300 and MIL-100(Fe) As Heterogeneous Catalysts for Lewis Acid and Oxidation Reactions: Roles of Structural Defects and Stability
journal, August 2012

  • Dhakshinamoorthy, Amarajothi; Alvaro, Mercedes; Horcajada, Patricia
  • ACS Catalysis, Vol. 2, Issue 10
  • DOI: 10.1021/cs300345b

Thiol grafted imine-based covalent organic frameworks for water remediation through selective removal of Hg( ii )
journal, January 2017

  • Merí-Bofí, Laura; Royuela, Sergio; Zamora, Félix
  • Journal of Materials Chemistry A, Vol. 5, Issue 34
  • DOI: 10.1039/C7TA05588A

Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer
journal, December 2015

  • Alsbaiee, Alaaeddin; Smith, Brian J.; Xiao, Leilei
  • Nature, Vol. 529, Issue 7585
  • DOI: 10.1038/nature16185

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

Cancer Mortality in a Chinese Population Exposed to Hexavalent Chromium in Drinking Water
journal, January 2008


Seven chemical separations to change the world
journal, April 2016

  • Sholl, David S.; Lively, Ryan P.
  • Nature, Vol. 532, Issue 7600
  • DOI: 10.1038/532435a

Competition and complexation of heavy metal ions and humic acid on zeolitic MCM-22 and activated carbon
journal, June 2008

  • Terdkiatburana, T.; Wang, Shaobin; Tadé, M. O.
  • Chemical Engineering Journal, Vol. 139, Issue 3
  • DOI: 10.1016/j.cej.2007.08.005

Polymerization reactions in porous coordination polymers
journal, January 2009

  • Uemura, Takashi; Yanai, Nobuhiro; Kitagawa, Susumu
  • Chemical Society Reviews, Vol. 38, Issue 5
  • DOI: 10.1039/b802583p

A mesoporous poly-melamine-formaldehyde polymer as a solid sorbent for toxic metal removal
journal, January 2013

  • Tan, Mei Xuan; Sum, Yin Ngai; Ying, Jackie Y.
  • Energy & Environmental Science, Vol. 6, Issue 11
  • DOI: 10.1039/c3ee42216j

Heavy Metal Toxicity and the Environment
book, January 2012


Fe 3+ -induced oxidation and coordination cross-linking in catechol–chitosan hydrogels under acidic pH conditions
journal, January 2015

  • Guo, Zhongwei; Ni, Kefeng; Wei, Dongzhi
  • RSC Advances, Vol. 5, Issue 47
  • DOI: 10.1039/C5RA03851K

A Nanoselenium Sponge for Instantaneous Mercury Removal to Undetectable Levels
journal, March 2017

  • Ahmed, Snober; Brockgreitens, John; Xu, Ke
  • Advanced Functional Materials, Vol. 27, Issue 17
  • DOI: 10.1002/adfm.201606572

Large scale fluorine-free synthesis of hierarchically porous iron(III) trimesate MIL-100(Fe) with a zeolite MTN topology
journal, July 2012


Characterization of Polydopamine Thin Films Deposited at Short Times by Autoxidation of Dopamine
journal, June 2013

  • Zangmeister, Rebecca A.; Morris, Todd A.; Tarlov, Michael J.
  • Langmuir, Vol. 29, Issue 27
  • DOI: 10.1021/la400587j

Anaerobic oxidation of dopamine by iron(III)
journal, January 1997

  • El-Ayaan, Usama; Herlinger, Erwin; Jameson, Reginald F.
  • Journal of the Chemical Society, Dalton Transactions, Issue 16
  • DOI: 10.1039/a701054k

Arsenic and other trace elements contamination in groundwater and a risk assessment study for the residents in the Kandal Province of Cambodia
journal, April 2009

  • Luu, Thi Thu Giang; Sthiannopkao, Suthipong; Kim, Kyoung-Woong
  • Environment International, Vol. 35, Issue 3
  • DOI: 10.1016/j.envint.2008.07.013

Selective and Efficient Removal of Mercury from Aqueous Media with the Highly Flexible Arms of a BioMOF
journal, August 2016

  • Mon, Marta; Lloret, Francesc; Ferrando-Soria, Jesús
  • Angewandte Chemie International Edition, Vol. 55, Issue 37
  • DOI: 10.1002/anie.201606015

A Hybrid Solid with Giant Pores Prepared by a Combination of Targeted Chemistry, Simulation, and Powder Diffraction
journal, August 2004

  • Férey, Gérard; Serre, Christian; Mellot-Draznieks, Caroline
  • Angewandte Chemie International Edition, Vol. 43, Issue 46
  • DOI: 10.1002/anie.200460592

Metal–Organic Framework Materials with Ultrahigh Surface Areas: Is the Sky the Limit?
journal, August 2012

  • Farha, Omar K.; Eryazici, Ibrahim; Jeong, Nak Cheon
  • Journal of the American Chemical Society, Vol. 134, Issue 36, p. 15016-15021
  • DOI: 10.1021/ja3055639

Cooperative insertion of CO2 in diamine-appended metal-organic frameworks
journal, March 2015

  • McDonald, Thomas M.; Mason, Jarad A.; Kong, Xueqian
  • Nature, Vol. 519, Issue 7543
  • DOI: 10.1038/nature14327

Metal-Mediated Cross-Linking in the Generation of a Marine-Mussel Adhesive
journal, January 2004

  • Sever, Mary J.; Weisser, Jaime T.; Monahan, Jennifer
  • Angewandte Chemie International Edition, Vol. 43, Issue 4
  • DOI: 10.1002/anie.200352759

Efficient removal and highly selective adsorption of Hg 2+ by polydopamine nanospheres with total recycle capacity
journal, September 2014


Enhanced Binding Affinity, Remarkable Selectivity, and High Capacity of CO2 by Dual Functionalization of a rht-Type Metal-Organic Framework
journal, December 2011

  • Li, Baiyan; Zhang, Zhijuan; Li, Yi
  • Angewandte Chemie International Edition, Vol. 51, Issue 6
  • DOI: 10.1002/anie.201105966

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Water Detoxification by a Substrate-Bound Catecholamine Adsorbent
journal, September 2012


Mercury nano-trap for effective and efficient removal of mercury(II) from aqueous solution
journal, November 2014

  • Li, Baiyan; Zhang, Yiming; Ma, Dingxuan
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6537

Mussel-Inspired Surface Chemistry for Multifunctional Coatings
journal, October 2007


Global Freshwater Resources: Soft-Path Solutions for the 21st Century
journal, November 2003


Applications of water stable metal–organic frameworks
journal, January 2016

  • Wang, Chenghong; Liu, Xinlei; Keser Demir, Nilay
  • Chemical Society Reviews, Vol. 45, Issue 18
  • DOI: 10.1039/C6CS00362A

Selective Chromium(VI) Ligands Identified Using Combinatorial Peptoid Libraries
journal, November 2013

  • Knight, Abigail S.; Zhou, Effie Y.; Pelton, Jeffrey G.
  • Journal of the American Chemical Society, Vol. 135, Issue 46
  • DOI: 10.1021/ja408788t

Impact of humic/fulvic acid on the removal of heavy metals from aqueous solutions using nanomaterials: A review
journal, January 2014


Polydopamine and Its Derivative Materials: Synthesis and Promising Applications in Energy, Environmental, and Biomedical Fields
journal, February 2014

  • Liu, Yanlan; Ai, Kelong; Lu, Lehui
  • Chemical Reviews, Vol. 114, Issue 9
  • DOI: 10.1021/cr400407a

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

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.