Functionalized Porous Aromatic Frameworks as High‐Performance Adsorbents for the Rapid Removal of Boric Acid from Water

This study demonstrates that functionalized, highly porous polymers are promising for the adsorptive capture of boric acid, a neutral contaminant that is difficult to remove from seawater using conventional reverse osmosis membranes. Appending N‐methyl‐d‐glucamine (NMDG) to the pore walls of high‐surface‐area porous aromatic frameworks (PAFs) yields the adsorbents PAF‐1‐NMDG and P2‐NMDG in a simple two‐step synthesis. The boron‐selective PAFs demonstrate adsorption capacities that are up to 70% higher than those of a commercial boron‐selective resin, Amberlite IRA743, and markedly faster adsorption rates, owing to their higher NMDG loadings and greater porosities relative to the resin. Remarkably, PAF‐1‐NMDG is able to reduce the boron concentration in synthetic seawater from 2.91 to <0.5 ppm in less than 3 min at an adsorbent loading of only 0.3 mg mL−1. The boron adsorption rate constants of both frameworks, determined via a pseudo‐second‐order rate model, represent the highest values reported in the literature—in most cases orders of magnitude higher than those of other boron‐selective adsorbents. The frameworks can also be readily regenerated via mild acid/base treatment and maintain constant boron adsorption capacities for at least 10 regeneration cycles. These results highlight the numerous advantages of PAFs over traditional porous polymers in water treatment applications.

[1]  Zhi Gao,et al.  Ammoniating Covalent Organic Framework (COF) for High‐Performance and Selective Extraction of Toxic and Radioactive Uranium Ions , 2019, Advanced science.

[2]  Christopher J. Chang,et al.  Iron detection and remediation with a functionalized porous polymer applied to environmental water samples , 2019, Chemical science.

[3]  J. Chen,et al.  99TcO4− remediation by a cationic polymeric network , 2018, Nature Communications.

[4]  Ye Yuan,et al.  Molecularly Imprinted Porous Aromatic Frameworks and Their Composite Components for Selective Extraction of Uranium Ions , 2018, Advanced materials.

[5]  Arne Thomas,et al.  Trends and challenges for microporous polymers. , 2017, Chemical Society reviews.

[6]  J. Long,et al.  Highly effective ammonia removal in a series of Brønsted acidic porous polymers: investigation of chemical and structural variations , 2017, Chemical science.

[7]  Wenbin Lin,et al.  Functionalized Porous Aromatic Framework for Efficient Uranium Adsorption from Aqueous Solutions. , 2017, ACS applied materials & interfaces.

[8]  Nan Zhang,et al.  Pyrocatechol-modified resins for boron recovery from water: Synthesis, adsorption and isotopic separation studies , 2017 .

[9]  P. Bai,et al.  Metal–Organic Framework UiO-66 as an Efficient Adsorbent for Boron Removal from Aqueous Solution , 2017 .

[10]  H. Yang,et al.  Nitrogen-doped graphene oxide for effectively removing boron ions from seawater. , 2017, Nanoscale.

[11]  M. Terenina,et al.  Alkylation of phenol with olefins in the presence of catalysts based on mesoporous aromatic frameworks , 2017, Russian Chemical Bulletin.

[12]  Cheri M Ackerman,et al.  Copper Capture in a Thioether-Functionalized Porous Polymer Applied to the Detection of Wilson’s Disease , 2016, Journal of the American Chemical Society.

[13]  Nicholas K. Brune,et al.  Extraction of Lanthanide and Actinide Ions from Aqueous Mixtures Using a Carboxylic Acid-Functionalized Porous Aromatic Framework , 2016, ACS central science.

[14]  P. Bai,et al.  Boron removal from aqueous solutions by adsorption — A review , 2016 .

[15]  Jay R. Werber,et al.  The Critical Need for Increased Selectivity, Not Increased Water Permeability, for Desalination Membranes , 2016 .

[16]  A. Hoekstra,et al.  Four billion people facing severe water scarcity , 2016, Science Advances.

[17]  N. Hilal,et al.  Boron removal from water with fractionized Amberlite IRA743 resin , 2015 .

[18]  M. Nasef,et al.  Tuning N-methyl-D-glucamine density in a new radiation grafted poly(vinyl benzyl chloride)/nylon-6 fibrous boron-selective adsorbent using the response surface method , 2015 .

[19]  M. Arda,et al.  Boron removal from seawater: State-of-the-art review , 2015 .

[20]  M. Nasef,et al.  Polymer-based chelating adsorbents for the selective removal of boron from water and wastewater: A review , 2014 .

[21]  Zhan Shi,et al.  Mercury nano-trap for effective and efficient removal of mercury(II) from aqueous solution , 2014, Nature Communications.

[22]  M. Bryjak,et al.  Boron removal by liquid‐phase polymer‐based retention technique using poly(glycidyl methacrylate N‐methyl D‐glucamine) , 2013 .

[23]  Yan-xin Wang,et al.  Boron sorption from aqueous solution by hydrotalcite and its preliminary application in geothermal water deboronation , 2013, Environmental Science and Pollution Research.

[24]  Guangshan Zhu,et al.  Target synthesis of a novel porous aromatic framework and its highly selective separation of CO(2)/CH(4). , 2013, Chemical communications.

[25]  Jifu Zheng,et al.  Ultrathin films of organic networks as nanofiltration membranes via solution-based molecular layer deposition. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[26]  Richard W. Baker,et al.  Membrane Technology and Applications: Baker/Membrane Technology and Applications , 2012 .

[27]  R. Krishna,et al.  Polyamine-tethered porous polymer networks for carbon dioxide capture from flue gas. , 2012, Angewandte Chemie.

[28]  Shilun Qiu,et al.  Selective adsorption of carbon dioxide by carbonized porous aromatic framework (PAF) , 2012 .

[29]  Aaron W Thornton,et al.  Lithiated porous aromatic frameworks with exceptional gas storage capacity. , 2012, Angewandte Chemie.

[30]  I. Ali New generation adsorbents for water treatment. , 2012, Chemical reviews.

[31]  A. Hoekstra,et al.  Global Monthly Water Scarcity: Blue Water Footprints versus Blue Water Availability , 2012, PloS one.

[32]  Rajamani Krishna,et al.  Sulfonate-grafted porous polymer networks for preferential CO2 adsorption at low pressure. , 2011, Journal of the American Chemical Society.

[33]  Huijun Zhao,et al.  Targeted synthesis of a porous aromatic framework with a high adsorption capacity for organic molecules , 2011 .

[34]  Nidal Hilal,et al.  Boron removal from saline water: A comprehensive review , 2011 .

[35]  Nalan Kabay,et al.  Boron in seawater and methods for its separation — A review , 2010 .

[36]  Rajamani Krishna,et al.  Porous Polymer Networks: Synthesis, Porosity, and Applications in Gas Storage/Separation , 2010 .

[37]  M. Qureshi,et al.  Global water crisis and future food security in an era of climate change , 2010 .

[38]  M. Arda,et al.  Effect of temperature on seawater desalination-water quality analyses for desalinated seawater for its use as drinking and irrigation water , 2010, Environmental geochemistry and health.

[39]  Wenchuan Wang,et al.  Targeted synthesis of a porous aromatic framework with high stability and exceptionally high surface area. , 2009, Angewandte Chemie.

[40]  Andreas N. Angelakis,et al.  Water resources management in Crete and in the Aegean Islands, with emphasis on the utilization of non-conventional water sources , 2009 .

[41]  Benny D. Freeman,et al.  Reverse osmosis desalination: water sources, technology, and today's challenges. , 2009, Water research.

[42]  Ü. Gemici,et al.  High arsenic and boron concentrations in groundwaters related to mining activity in the Bigadic borate deposits (Western Turkey) , 2008 .

[43]  J. Georgiadis,et al.  Science and technology for water purification in the coming decades , 2008, Nature.

[44]  M. Antonietti,et al.  Microporous networks of high-performance polymers: Elastic deformations and gas sorption properties , 2008 .

[45]  Yonglan Xu,et al.  Technologies for Boron Removal , 2008 .

[46]  Yi Zhang,et al.  Synthesis of N-methylglucamine modified macroporous poly(GMA-co-TRIM) and its performance as a boron sorbent , 2007 .

[47]  Adriana Bruggeman,et al.  Non-conventional water resources and opportunities for water augmentation to achieve food security in water scarce countries , 2007 .

[48]  V. Gupta,et al.  Advances in water treatment by adsorption technology , 2006, Nature Protocols.

[49]  R. Bell,et al.  Advances in plant and animal boron nutrition , 2007 .

[50]  G. Vonmedeazza Water desalination as a long-term sustainable solution to alleviate global freshwater scarcity? A North-South approach, , 2004 .

[51]  Christopher Bellona,et al.  Factors affecting the rejection of organic solutes during NF/RO treatment--a literature review. , 2004, Water research.

[52]  P. Gleick Global Freshwater Resources: Soft-Path Solutions for the 21st Century , 2003, Science.

[53]  D. Sparks,et al.  ATR-FTIR spectroscopic studies of boric acid adsorption on hydrous ferric oxide , 2003 .

[54]  Bjarne Nicolaisen,et al.  Developments in membrane technology for water treatment , 2003 .

[55]  C. Hunt Dietary boron: An overview of the evidence for its role in immune function , 2003 .

[56]  S. Şahin A mathematical relationship for the explanation of ion exchange for boron adsorption , 2002 .

[57]  C. Vörösmarty,et al.  Global water resources: vulnerability from climate change and population growth. , 2000, Science.

[58]  Y. Ho,et al.  Pseudo-second order model for sorption processes , 1999 .

[59]  Y. Miyazaki,et al.  Complexation of boric acid with the N-methyl-D-glucamine group in solution and in crosslinked polymer , 1998 .

[60]  D. Roe,et al.  Effects of riboflavin on boric acid toxicity. , 1972, Journal of pharmaceutical sciences.

[61]  S. Eaton EFFECTS OF BORON DEFICIENCY AND EXCESS ON PLANTS. , 1940, Plant Physiology.