skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Efficient Mercury Capture Using Functionalized Porous Organic Polymer

Abstract

The primary challenge in materials design and synthesis is achieving the balance between performance and economy for real-world application. Here, this issue is addressed by creating a thiol functionalized porous organic polymer (POP) using simple free radical polymerization techniques to prepare a cost-effective material with a high density of chelating sites designed for mercury capture and therefore environmental remediation. The resulting POP is able to remove aqueous and airborne mercury with uptake capacities of 1216 and 630 mg g -1, respectively. The material demonstrates rapid kinetics, capable of dropping the mercury concentration from 5 ppm to 1 ppb, lower than the US Environmental Protection Agency's drinking water limit (2 ppb), within 10 min. Furthermore, the material has the added benefits of recyclability, stability in a broad pH range, and selectivity for toxic metals. These results are attributed to the material's physical properties, which include hierarchical porosity, a high density of chelating sites, and the material's robustness, which improve the thiol availability to bind with mercury as determined by X-ray photoelectron spectroscopy and X-ray absorption fine structure studies. Finally, the work provides promising results for POPs as an economical material for multiple environmental remediation applications.

Authors:
 [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [2];  [3];  [3]; ORCiD logo [1]
  1. Univ. of South Florida, Tampa, FL (United States). Dept. of Chemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Univ. of South Florida, Tampa, FL (United States). Dept. of Electrical Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1394551
DOE Contract Number:  
AC05-00OR22725; AC02-76SF00515
Resource Type:
Journal Article
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 31; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; environmental remediation; heavy metal removal; mercury capture; porous organic polymers; thiol functionality

Citation Formats

Aguila, Briana, Sun, Qi, Perman, Jason A., Earl, Lyndsey D., Abney, Carter W., Elzein, Radwan, Schlaf, Rudy, and Ma, Shengqian. Efficient Mercury Capture Using Functionalized Porous Organic Polymer. United States: N. p., 2017. Web. doi:10.1002/adma.201700665.
Aguila, Briana, Sun, Qi, Perman, Jason A., Earl, Lyndsey D., Abney, Carter W., Elzein, Radwan, Schlaf, Rudy, & Ma, Shengqian. Efficient Mercury Capture Using Functionalized Porous Organic Polymer. United States. doi:10.1002/adma.201700665.
Aguila, Briana, Sun, Qi, Perman, Jason A., Earl, Lyndsey D., Abney, Carter W., Elzein, Radwan, Schlaf, Rudy, and Ma, Shengqian. Wed . "Efficient Mercury Capture Using Functionalized Porous Organic Polymer". United States. doi:10.1002/adma.201700665.
@article{osti_1394551,
title = {Efficient Mercury Capture Using Functionalized Porous Organic Polymer},
author = {Aguila, Briana and Sun, Qi and Perman, Jason A. and Earl, Lyndsey D. and Abney, Carter W. and Elzein, Radwan and Schlaf, Rudy and Ma, Shengqian},
abstractNote = {The primary challenge in materials design and synthesis is achieving the balance between performance and economy for real-world application. Here, this issue is addressed by creating a thiol functionalized porous organic polymer (POP) using simple free radical polymerization techniques to prepare a cost-effective material with a high density of chelating sites designed for mercury capture and therefore environmental remediation. The resulting POP is able to remove aqueous and airborne mercury with uptake capacities of 1216 and 630 mg g-1, respectively. The material demonstrates rapid kinetics, capable of dropping the mercury concentration from 5 ppm to 1 ppb, lower than the US Environmental Protection Agency's drinking water limit (2 ppb), within 10 min. Furthermore, the material has the added benefits of recyclability, stability in a broad pH range, and selectivity for toxic metals. These results are attributed to the material's physical properties, which include hierarchical porosity, a high density of chelating sites, and the material's robustness, which improve the thiol availability to bind with mercury as determined by X-ray photoelectron spectroscopy and X-ray absorption fine structure studies. Finally, the work provides promising results for POPs as an economical material for multiple environmental remediation applications.},
doi = {10.1002/adma.201700665},
journal = {Advanced Materials},
issn = {0935-9648},
number = 31,
volume = 29,
place = {United States},
year = {2017},
month = {6}
}

Works referenced in this record:

Efficient removal of elemental mercury (Hg 0 ) by SBA-15-Ag adsorbents
journal, January 2014

  • Xie, Yijun; Yan, Bin; Tian, Chong
  • J. Mater. Chem. A, Vol. 2, Issue 42
  • DOI: 10.1039/C4TA04147J

Sequestration of Heavy Metals from Water with Layered Metal Sulfides
journal, May 2009

  • Manos, Manolis J.; Kanatzidis, Mercouri G.
  • Chemistry - A European Journal, Vol. 15, Issue 19
  • DOI: 10.1002/chem.200900353

Design and fabrication of mesoporous heterogeneous basic catalysts
journal, January 2015

  • Sun, Lin-Bing; Liu, Xiao-Qin; Zhou, Hong-Cai
  • Chemical Society Reviews, Vol. 44, Issue 15
  • DOI: 10.1039/C5CS00090D

Taming a Mercurial Element
journal, September 2013


MoS 2 Nanosheets with Widened Interlayer Spacing for High-Efficiency Removal of Mercury in Aquatic Systems
journal, May 2016

  • Ai, Kelong; Ruan, Changping; Shen, Mengxia
  • Advanced Functional Materials, Vol. 26, Issue 30
  • DOI: 10.1002/adfm.201601338

One-Step Preparation of Thiol-Functionalized Porous Clay Heterostructures: Application to Hg(II) Binding and Characterization of Mass Transport Issues
journal, September 2009

  • Tchinda, Aurélien Jieumboué; Ngameni, Emmanuel; Kenfack, Ignas Tonlé
  • Chemistry of Materials, Vol. 21, Issue 18
  • DOI: 10.1021/cm8024022

Porous Semiconducting Gels and Aerogels from Chalcogenide Clusters
journal, July 2007


Modeling of sorption kinetics: the pseudo-second order equation and the sorbate intraparticle diffusivity
journal, March 2013


Ionic Covalent Organic Frameworks with Spiroborate Linkage
journal, December 2015

  • Du, Ya; Yang, Haishen; Whiteley, Justin Michael
  • Angewandte Chemie International Edition, Vol. 55, Issue 5
  • DOI: 10.1002/anie.201509014

Global Environmental Law and Treaty-Making on Hazardous Substances: The Minamata Convention and Mercury Abatement
journal, February 2014


The Cation−π Interaction
journal, August 1997

  • Ma, Jennifer C.; Dougherty, Dennis A.
  • Chemical Reviews, Vol. 97, Issue 5
  • DOI: 10.1021/cr9603744

Thiol-functionalised mesoporous silica-coated magnetite nanoparticles for high efficiency removal and recovery of Hg from water
journal, August 2012


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

Mercury(II) Ion Adsorption Behavior in Thiol-Functionalized Mesoporous Silica Microspheres
journal, April 2002

  • Bibby, Ashley; Mercier, Louis
  • Chemistry of Materials, Vol. 14, Issue 4
  • DOI: 10.1021/cm0112082

Advanced Photoemission Spectroscopy Investigations Correlated with DFT Calculations on the Self-Assembly of 2D Metal Organic Frameworks Nano Thin Films
journal, November 2016

  • Elzein, Radwan; Chang, Chun-Min; Ponomareva, Inna
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 45
  • DOI: 10.1021/acsami.6b10340

Reversible uptake of HgCl2 in a porous coordination polymer based on the dual functions of carboxylate and thioether
journal, January 2009

  • Zhou, Xiao-Ping; Xu, Zhengtao; Zeller, Matthias
  • Chemical Communications, Issue 36
  • DOI: 10.1039/b910265e

Ion-exchange resins bearing thiol groups to remove mercury.
journal, February 2000


Effects of Human Activity on Global Extinction Risk
journal, December 1995


Hybrid Mesoporous Materials with Functionalized Monolayers
journal, January 1998


Selective removal of mercury from aqueous solutions using thiolated cross-linked polyethylenimine
journal, April 2013


An Ambipolar Conducting Covalent Organic Framework with Self-Sorted and Periodic Electron Donor-Acceptor Ordering
journal, May 2012


Global threats to human water security and river biodiversity
journal, September 2010

  • Vörösmarty, C. J.; McIntyre, P. B.; Gessner, M. O.
  • Nature, Vol. 467, Issue 7315
  • DOI: 10.1038/nature09440

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

Metal-Organic Framework Templated Inorganic Sorbents for Rapid and Efficient Extraction of Heavy Metals
journal, October 2014


Conjugated Microporous Polymers with Dimensionality-Controlled Heterostructures for Green Energy Devices
journal, May 2015

  • Zhuang, Xiaodong; Gehrig, Dominik; Forler, Nina
  • Advanced Materials, Vol. 27, Issue 25
  • DOI: 10.1002/adma.201501786

Postsynthetically Modified Covalent Organic Frameworks for Efficient and Effective Mercury Removal
journal, February 2017

  • Sun, Qi; Aguila, Briana; Perman, Jason
  • Journal of the American Chemical Society, Vol. 139, Issue 7
  • DOI: 10.1021/jacs.6b12885

Low dose mercury toxicity and human health
journal, September 2005

  • Zahir, Farhana; Rizwi, Shamim J.; Haq, Soghra K.
  • Environmental Toxicology and Pharmacology, Vol. 20, Issue 2
  • DOI: 10.1016/j.etap.2005.03.007

Surface-Enhanced Raman Spectroscopy of Aromatic Thiols and Disulfides on Gold Electrodes
journal, June 1998

  • Szafranski, Cory A.; Tanner, Weslene; Laibinis, Paul E.
  • Langmuir, Vol. 14, Issue 13
  • DOI: 10.1021/la9702502

Removal of mercury by adsorption: a review
journal, December 2015

  • Yu, Jin-Gang; Yue, Bao-Yu; Wu, Xiong-Wei
  • Environmental Science and Pollution Research, Vol. 23, Issue 6
  • DOI: 10.1007/s11356-015-5880-x

Stable Covalent Organic Frameworks for Exceptional Mercury Removal from Aqueous Solutions
journal, February 2017

  • Huang, Ning; Zhai, Lipeng; Xu, Hong
  • Journal of the American Chemical Society, Vol. 139, Issue 6
  • DOI: 10.1021/jacs.6b12328

Ultrahigh Surface Area in Porous Solids
journal, September 2010


Nitrogen-Doped Holey Graphitic Carbon from 2D Covalent Organic Polymers for Oxygen Reduction
journal, March 2014


Thioether-Based Fluorescent Covalent Organic Framework for Selective Detection and Facile Removal of Mercury(II)
journal, February 2016

  • Ding, San-Yuan; Dong, Ming; Wang, Ya-Wen
  • Journal of the American Chemical Society, Vol. 138, Issue 9
  • DOI: 10.1021/jacs.5b10754

Evaluation of a robust, diimide-based, porous organic polymer (POP) as a high-capacity sorbent for representative chemical threats
journal, March 2011

  • Peterson, Gregory W.; Farha, Omar K.; Schindler, Bryan
  • Journal of Porous Materials, Vol. 19, Issue 2, p. 261-266
  • DOI: 10.1007/s10934-011-9468-7

Synthetic Control of the Pore Dimension and Surface Area in Conjugated Microporous Polymer and Copolymer Networks
journal, June 2008

  • Jiang, Jia-Xing; Su, Fabing; Trewin, Abbie
  • Journal of the American Chemical Society, Vol. 130, Issue 24
  • DOI: 10.1021/ja8010176

Human health effects of air pollution
journal, January 2008


Great Prospects for PAF-1 and its derivatives
journal, January 2015

  • Pei, Cuiying; Ben, Teng; Qiu, Shilun
  • Materials Horizons, Vol. 2, Issue 1
  • DOI: 10.1039/C4MH00163J

The mercury cycle: Preliminary communication
journal, August 1981

  • Brosset, Cyrill
  • Water, Air, and Soil Pollution, Vol. 16, Issue 2
  • DOI: 10.1007/BF01046859

Mercury Binding Sites in Thiol-Functionalized Mesostructured Silica
journal, June 2005

  • Billinge, Simon J. L.; McKimmy, Emily J.; Shatnawi, Mouath
  • Journal of the American Chemical Society, Vol. 127, Issue 23
  • DOI: 10.1021/ja0506859

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

Role of the ocean in the global mercury cycle: ROLE OF OCEAN IN GLOBAL HG CYCLE
journal, November 2002

  • Mason, R. P.; Sheu, G. -R.
  • Global Biogeochemical Cycles, Vol. 16, Issue 4
  • DOI: 10.1029/2001GB001440

Soluble Porous Coordination Polymers by Mechanochemistry: From Metal-Containing Films/Membranes to Active Catalysts for Aerobic Oxidation
journal, November 2014

  • Zhang, Pengfei; Li, Haiying; Veith, Gabriel M.
  • Advanced Materials, Vol. 27, Issue 2
  • DOI: 10.1002/adma.201403299

Carbon-Based Functional Materials Derived from Waste for Water Remediation and Energy Storage
journal, January 2017


H 2x Mn x Sn 3-x S 6 (x = 0.11-0.25): A Novel Reusable Sorbent for Highly Specific Mercury Capture Under Extreme pH Conditions
journal, April 2009

  • Manos, Manolis J.; Petkov, Valeri G.; Kanatzidis, Mercouri G.
  • Advanced Functional Materials, Vol. 19, Issue 7
  • DOI: 10.1002/adfm.200801563

Silica coated magnetite particles for magnetic removal of Hg2+ from water
journal, May 2010

  • Girginova, Penka I.; Daniel-da-Silva, Ana L.; Lopes, Cláudia B.
  • Journal of Colloid and Interface Science, Vol. 345, Issue 2
  • DOI: 10.1016/j.jcis.2010.01.087

Effective Mercury Sorption by Thiol-Laced Metal–Organic Frameworks: in Strong Acid and the Vapor Phase
journal, May 2013

  • Yee, Ka-Kit; Reimer, Nele; Liu, Jie
  • Journal of the American Chemical Society, Vol. 135, Issue 21
  • DOI: 10.1021/ja400212k

Functional Mesoporous Metal−Organic Frameworks for the Capture of Heavy Metal Ions and Size-Selective Catalysis
journal, December 2010

  • Fang, Qian-Rong; Yuan, Da-Qian; Sculley, Julian
  • Inorganic Chemistry, Vol. 49, Issue 24
  • DOI: 10.1021/ic101935f

Mesoporous organosilica adsorbents: nanoengineered materials for removal of organic and inorganic pollutants
journal, January 2010

  • Walcarius, Alain; Mercier, Louis
  • Journal of Materials Chemistry, Vol. 20, Issue 22
  • DOI: 10.1039/b924316j

XAS Study of Mercury(II) Ions Trapped in Mercaptan−Functionalized Mesostructured Silicate with a Wormhole Framework Structure
journal, September 2004

  • Chen, ; McKimmy, Emily J.; Pinnavaia, Thomas J.
  • Environmental Science & Technology, Vol. 38, Issue 18
  • DOI: 10.1021/es049689o

Sulfur-Functionalized Mesoporous Carbon
journal, October 2007

  • Shin, Y.; Fryxell, G. E.; Um, W.
  • Advanced Functional Materials, Vol. 17, Issue 15
  • DOI: 10.1002/adfm.200601230

Conjugated Microporous Poly(aryleneethynylene) Networks
journal, September 2007

  • Jiang, Jia-Xing; Su, Fabing; Trewin, Abbie
  • Angewandte Chemie International Edition, Vol. 46, Issue 45
  • DOI: 10.1002/anie.200701595

Synthesis and Metalation of Catechol-Functionalized Porous Organic Polymers
journal, March 2012

  • Weston, Mitchell H.; Farha, Omar K.; Hauser, Brad G.
  • Chemistry of Materials, Vol. 24, Issue 7
  • DOI: 10.1021/cm2034646

Abiotic reduction of mercury by humic substances in aquatic system — an important process for the mercury cycle
journal, April 1991

  • Allard, B.; Arsenie, I.
  • Water Air & Soil Pollution, Vol. 56, Issue 1
  • DOI: 10.1007/BF00342291

Mercury and Health
journal, September 2013


Hard and Soft Acids and Bases
journal, November 1963

  • Pearson, Ralph G.
  • Journal of the American Chemical Society, Vol. 85, Issue 22
  • DOI: 10.1021/ja00905a001

Selective sensing and efficient separation of Hg2+ from aqueous medium with a pyrene based amphiphilic ligand
journal, January 2012

  • Kar, Chirantan; Deb Adhikari, Manab; Ramesh, Aiyagari
  • RSC Advances, Vol. 2, Issue 24
  • DOI: 10.1039/c2ra21064a

Amorphous PAF-1: Guiding the Rational Design of Ultraporous Materials
journal, August 2014

  • Thomas, Jens M. H.; Trewin, Abbie
  • The Journal of Physical Chemistry C, Vol. 118, Issue 34
  • DOI: 10.1021/jp502336a

Catalytic DNA-Functionalized Self-Propelled Micromachines for Environmental Remediation
journal, September 2016


Mercury removal from aqueous solution and flue gas by adsorption on activated carbon fibres
journal, June 2006

  • Nabais, João Valente; Carrott, P. J. M.; Carrott, M. M. L. Ribeiro
  • Applied Surface Science, Vol. 252, Issue 17
  • DOI: 10.1016/j.apsusc.2005.11.034

Covalent Organic Frameworks for CO 2 Capture
journal, February 2016


Investigations into a thiol-impregnated CaCO 3 -based adsorbent for mercury removal: a full factorial design approach
journal, January 2015

  • Balasundaram, Karthik; Sharma, Mukesh
  • RSC Advances, Vol. 5, Issue 90
  • DOI: 10.1039/C5RA10902G

The Minamata Convention on Mercury: Attempting to address the global controversy of dental amalgam use and mercury waste disposal
journal, February 2014


Adsorption of gaseous elemental mercury with activated carbon impregnated with ferric chloride
journal, January 2015

  • Wang, Xue Qian; Wang, Ping; Ning, Ping
  • RSC Advances, Vol. 5, Issue 32
  • DOI: 10.1039/C5RA01011J

Conjugated Microporous Polymers
journal, March 2009


Functionalized Monolayers on Ordered Mesoporous Supports
journal, May 1997


Robust Aqua Material: A Pressure-Resistant Self-Assembled Membrane for Water Purification
journal, January 2017

  • Cohen, Erez; Weissman, Haim; Shimoni, Eyal
  • Angewandte Chemie International Edition, Vol. 56, Issue 8
  • DOI: 10.1002/anie.201610288

Functional Materials: From Hard to Soft Porous Frameworks
journal, October 2010

  • Thomas, Arne
  • Angewandte Chemie International Edition, Vol. 49, Issue 45, p. 8328-8344
  • DOI: 10.1002/anie.201000167

Sulfur-doped porous carbons: Synthesis and applications
journal, March 2014


High-performance Hg 2+ removal from ultra-low-concentration aqueous solution using both acylamide- and hydroxyl-functionalized metal–organic framework
journal, January 2015

  • Luo, Feng; Chen, Jing Li; Dang, Li Long
  • Journal of Materials Chemistry A, Vol. 3, Issue 18
  • DOI: 10.1039/C5TA01669J

Highly Efficient Heterogeneous Hydroformylation over Rh-Metalated Porous Organic Polymers: Synergistic Effect of High Ligand Concentration and Flexible Framework
journal, April 2015

  • Sun, Qi; Dai, Zhifeng; Liu, Xiaolong
  • Journal of the American Chemical Society, Vol. 137, Issue 15
  • DOI: 10.1021/jacs.5b02122