Efficient Capture and Effective Sensing of Cr2O72- from Water Using a Zirconium Metal-Organic Framework.

Highly efficient decontamination of heavily toxic Cr2O72- from water remains a serious task for public health and ecosystem protection. An easily regenerative and reused sorbent with suitable porosity may address this task. Herein, a series of water-stable and ecofriendly metal-organic frameworks (MOFs) with large surface areas were assessed for their ability to adsorb and separate Cr2O72- from aqueous solutions. Among these tested MOFs, NU-1000 shows an extraordinary capability to efficiently capture (within 3 min) Cr2O72- with a sorption capacity of up to 76.8 mg/g, which is the largest one for the neutral MOF-based Cr2O72- sorbents. NU-1000 also shows remarkable selectivity for Cr2O72- capture and can effectively reduce the Cr(VI) concentration from 24 ppm to 60 ppb, which is below the acceptable limit for the drinking water standard (100 ppb by the U.S. Environmental Protection Agency). Moreover, this adsorbent can be easily regenerated by Soxhlet extraction with an acidic methanol solution (2.5 M HCl) and can be reused at least three times without a significant loss of it adsorption ability. More intriguingly, NU-1000 can also serve as an efficient photoluminescent probe for the selective detection of Cr2O72- in aqueous media. The Cr2O72- detection limit is as low as 1.8 μM, and the linear range is from 1.8 to 340 μM. Our work shows that NU-1000 is a unique material combining both efficient sorption and exceptional fluorescent sensing of Cr2O72- in aqueous media.

[1]  Yu Tian,et al.  Efficient removal of chromium from water by Mn3O4@ZnO/Mn3O4 composite under simulated sunlight irradiation: Synergy of photocatalytic reduction and adsorption , 2017 .

[2]  Stavros A. Diamantis,et al.  All in one porous material: Exceptional sorption and selective sensing of hexavalent chromium by using a Zr4+ MOF , 2017 .

[3]  J. Korak,et al.  Regeneration of pilot-scale ion exchange columns for hexavalent chromium removal. , 2017, Water research.

[4]  C. Su,et al.  Ultrafast water sensing and thermal imaging by a metal-organic framework with switchable luminescence , 2017, Nature Communications.

[5]  Christina T. Lollar,et al.  Enzyme-MOF (metal-organic framework) composites. , 2017, Chemical Society reviews.

[6]  Tahir Cagin,et al.  Construction of hierarchically porous metal–organic frameworks through linker labilization , 2017, Nature Communications.

[7]  Linbing Sun,et al.  Metal-Organic Frameworks for Heterogeneous Basic Catalysis. , 2017, Chemical reviews.

[8]  Z. Chai,et al.  Hydrolytically Stable Luminescent Cationic Metal Organic Framework for Highly Sensitive and Selective Sensing of Chromate Anions in Natural Water Systems. , 2017, ACS applied materials & interfaces.

[9]  C. Su,et al.  Dynamic Spacer Installation for Multirole Metal-Organic Frameworks: A New Direction toward Multifunctional MOFs Achieving Ultrahigh Methane Storage Working Capacity. , 2017, Journal of the American Chemical Society.

[10]  D. Young,et al.  Luminescent Zn(II) Coordination Polymers for Highly Selective Sensing of Cr(III) and Cr(VI) in Water. , 2017, Inorganic chemistry.

[11]  Zhiliang Liu,et al.  Ultrastable 1D Europium Complex for Simultaneous and Quantitative Sensing of Cr(III) and Cr(VI) Ions in Aqueous Solution with High Selectivity and Sensitivity. , 2017, Inorganic chemistry.

[12]  R. Cao,et al.  Boosting Oxidative Desulfurization of Model and Real Gasoline over Phosphotungstic Acid Encapsulated in Metal–Organic Frameworks: The Window Size Matters , 2017 .

[13]  Bao‐Long Li,et al.  An unusual porous cationic metal-organic framework based on a tetranuclear hydroxyl-copper(ii) cluster for fast and highly efficient dichromate trapping through a single-crystal to single-crystal process. , 2017, Chemical communications.

[14]  Shuhong Yu,et al.  Singlet Oxygen-Engaged Selective Photo-Oxidation over Pt Nanocrystals/Porphyrinic MOF: The Roles of Photothermal Effect and Pt Electronic State. , 2017, Journal of the American Chemical Society.

[15]  Hai‐Long Jiang,et al.  A Modulator-Induced Defect-Formation Strategy to Hierarchically Porous Metal-Organic Frameworks with High Stability. , 2017, Angewandte Chemie.

[16]  Shuangquan Zang,et al.  Cr(VI) removal via anion exchange on a silver-triazolate MOF. , 2017, Journal of hazardous materials.

[17]  Yaoyu Wang,et al.  Two 3D Isostructural Ln(III)-MOFs: Displaying the Slow Magnetic Relaxation and Luminescence Properties in Detection of Nitrobenzene and Cr2O72. , 2016, Inorganic chemistry.

[18]  Shengyun Liao,et al.  An amino-decorated dual-functional metal–organic framework for highly selective sensing of Cr(III) and Cr(VI) ions and detection of nitroaromatic explosives , 2016 .

[19]  Hai‐Long Jiang,et al.  Porphyrinic Metal–Organic Framework Catalyzed Heck-Reaction: Fluorescence “Turn-On” Sensing of Cu(II) Ion , 2016 .

[20]  Qiang Zhang,et al.  Flexible Zirconium Metal-Organic Frameworks as Bioinspired Switchable Catalysts. , 2016, Angewandte Chemie.

[21]  Xinxin Li,et al.  A durable luminescent ionic polymer for rapid detection and efficient removal of toxic Cr2O72 , 2016 .

[22]  Xin-Xiong Li,et al.  Imidazolium-Based Porous Organic Polymers: Anion Exchange-Driven Capture and Luminescent Probe of Cr2O7(2.). , 2016, ACS applied materials & interfaces.

[23]  Aamod V. Desai,et al.  A Water-Stable Cationic Metal-Organic Framework as a Dual Adsorbent of Oxoanion Pollutants. , 2016, Angewandte Chemie.

[24]  Bin Zhao,et al.  Two solvent-stable MOFs as a recyclable luminescent probe for detecting dichromate or chromate anions , 2016 .

[25]  A. Morsali,et al.  Metal-Organic Framework Based on Isonicotinate N-Oxide for Fast and Highly Efficient Aqueous Phase Cr(VI) Adsorption. , 2016, Inorganic chemistry.

[26]  G. Armatas,et al.  Rapid, green and inexpensive synthesis of high quality UiO-66 amino-functionalized materials with exceptional capability for removal of hexavalent chromium from industrial waste , 2016 .

[27]  Hong-Cai Zhou,et al.  Zr-based metal-organic frameworks: design, synthesis, structure, and applications. , 2016, Chemical Society reviews.

[28]  Zhonghua Zhu,et al.  Uncommon Pyrazoyl-Carboxyl Bifunctional Ligand-Based Microporous Lanthanide Systems: Sorption and Luminescent Sensing Properties. , 2016, Inorganic chemistry.

[29]  J. Hupp,et al.  Efficient extraction of sulfate from water using a Zr-metal-organic framework. , 2016, Dalton transactions.

[30]  G. Armatas,et al.  Selective capture of hexavalent chromium from an anion-exchange column of metal organic resin–alginic acid composite† †Electronic supplementary information (ESI) available: Synthesis procedures, experimental details of physical measurements, SEM images, thermal analysis, CO2 sorption data and pore s , 2015, Chemical science.

[31]  Yuanjing Cui,et al.  A porous Zr-cluster-based cationic metal-organic framework for highly efficient Cr2O7(2-) removal from water. , 2015, Chemical communications.

[32]  Xiaoyue Xu,et al.  Two Amino-Decorated Metal-Organic Frameworks for Highly Selective and Quantitatively Sensing of Hg(II) and Cr(VI) in Aqueous Solution. , 2015, Inorganic chemistry.

[33]  Michael J. Katz,et al.  High efficiency adsorption and removal of selenate and selenite from water using metal-organic frameworks. , 2015, Journal of the American Chemical Society.

[34]  Michael J. Katz,et al.  Destruction of chemical warfare agents using metal-organic frameworks. , 2015, Nature materials.

[35]  Ling Wu,et al.  MIL-53(Fe) as a highly efficient bifunctional photocatalyst for the simultaneous reduction of Cr(VI) and oxidation of dyes. , 2015, Journal of hazardous materials.

[36]  Shiai Xu,et al.  A facile route for the synthesis of mesoporous melamine-formaldehyde resins for hexavalent chromium removal , 2015 .

[37]  Xinhong Song,et al.  A facile synthesis of highly luminescent nitrogen-doped graphene quantum dots for the detection of 2,4,6-trinitrophenol in aqueous solution. , 2015, Nanoscale.

[38]  Jian Zhang,et al.  Water-Stable Metal–Organic Frameworks for Fast and High Dichromate Trapping via Single-Crystal-to-Single-Crystal Ion Exchange , 2015 .

[39]  Zu-Jin Lin,et al.  Metal-organic frameworks based on flexible ligands (FL-MOFs): structures and applications. , 2014, Chemical Society reviews.

[40]  Rochus Schmid,et al.  Structural complexity in metal-organic frameworks: simultaneous modification of open metal sites and hierarchical porosity by systematic doping with defective linkers. , 2014, Journal of the American Chemical Society.

[41]  Xin-Xiong Li,et al.  A cationic metal-organic framework consisting of nanoscale cages: capture, separation, and luminescent probing of Cr(2)O7(2-) through a single-crystal to single-crystal process. , 2013, Angewandte Chemie.

[42]  Michael J. Katz,et al.  A facile synthesis of UiO-66, UiO-67 and their derivatives. , 2013, Chemical communications.

[43]  David Fairen-Jimenez,et al.  Vapor-phase metalation by atomic layer deposition in a metal-organic framework. , 2013, Journal of the American Chemical Society.

[44]  J. Lee,et al.  N/S-heterocyclic contaminant removal from fuels by the mesoporous metal-organic framework MIL-100: the role of the metal ion. , 2013, Journal of the American Chemical Society.

[45]  B. D. Pandey,et al.  Chemical and microbial remediation of hexavalent chromium from contaminated soil and mining/metallurgical solid waste: a review. , 2013, Journal of hazardous materials.

[46]  Chao Zhou,et al.  Calcined graphene/MgAl-layered double hydroxides for enhanced Cr(VI) removal , 2013 .

[47]  Jeill Oh,et al.  Hexavalent chromium removal by various adsorbents: Powdered activated carbon, chitosan, and single/multi-walled carbon nanotubes , 2013 .

[48]  G. Qian,et al.  Chromium (VI) and zinc (II) waste water co-treatment by forming layered double hydroxides: mechanism discussion via two different processes and application in real plating water. , 2012, Journal of hazardous materials.

[49]  Y. A. Abou El-Reash,et al.  Adsorption of Cr(VI) and As(V) ions by modified magnetic chitosan chelating resin. , 2011, International journal of biological macromolecules.

[50]  Honghan Fei,et al.  A new paradigm for anion trapping in high capacity and selectivity: crystal-to-crystal transformation of cationic materials. , 2011, Journal of the American Chemical Society.

[51]  Peter Behrens,et al.  Modulated synthesis of Zr-based metal-organic frameworks: from nano to single crystals. , 2011, Chemistry.

[52]  Klaus Huber,et al.  Controlling Zeolitic Imidazolate Framework Nano- and Microcrystal Formation: Insight into Crystal Growth by Time-Resolved In Situ Static Light Scattering , 2011 .

[53]  Wenmin Wang,et al.  A novel method for amino starch preparation and its adsorption for Cu(II) and Cr(VI). , 2010, Journal of hazardous materials.

[54]  M. D. da Silva,et al.  Adsorption of Cr(VI) from aqueous solution by hydrous zirconium oxide. , 2010, Journal of hazardous materials.

[55]  W. Daud,et al.  Removal of Hexavalent Chromium-Contaminated Water and Wastewater: A Review , 2009 .

[56]  Carlo Lamberti,et al.  A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. , 2008, Journal of the American Chemical Society.

[57]  Z. Dong,et al.  Application of layered double hydroxides for removal of oxyanions: a review. , 2008, Water research.

[58]  C. Serre,et al.  Synthesis and catalytic properties of MIL-100(Fe), an iron(III) carboxylate with large pores. , 2007, Chemical communications.

[59]  Xiao-Ming Chen,et al.  Ligand-directed strategy for zeolite-type metal-organic frameworks: zinc(II) imidazolates with unusual zeolitic topologies. , 2006, Angewandte Chemie.

[60]  Max Costa,et al.  Toxicity and Carcinogenicity of Chromium Compounds in Humans , 2006 .

[61]  Gérard Férey,et al.  A hybrid solid with giant pores prepared by a combination of targeted chemistry, simulation, and powder diffraction. , 2004, Angewandte Chemie.

[62]  Ian D. Williams,et al.  A chemically functionalizable nanoporous material (Cu3(TMA)2(H2O)3)n , 1999 .

[63]  William A. Telliard,et al.  PRIORITY POLLUTANTS I-A PERSPECTIVES VIEW , 1979 .

[64]  Linhua Jiang,et al.  Resin oxidization phenomenon and its influence factor during chromium(VI) removal from wastewater using gel-type anion exchangers , 2016 .