Reactive Chlorine Capture by Dichlorination of Alkene Linkers in Metal-Organic Frameworks.

Chlorine (Cl2) is a toxic and corrosive gas that is both an essential reagent in industry and a potent chemical warfare agent. Materials that can strongly bind Cl2 at low pressures are essential for industrial and civilian personal protective equipment (PPE). Herein, we report the first examples of irreversible Cl2 capture via the dichlorination of alkene linkages in Zr-based metal-organic frameworks. Frameworks constructed from fumarate (Zr-fum) and stilbene (Zr-stilbene) linkers retain long-range order and accessible porosity after alkene dichlorination. In addition, energy-dispersive X-ray spectroscopy reveals an even distribution of Cl throughout both materials after Cl2 capture. Cl2 uptake experiments reveal high irreversible uptake of Cl2 (>10 wt %) at low partial pressures (<100 mbar), particularly in Zr-fum. In contrast, traditional porous carbons mostly display reversible Cl2 capture, representing a continued risk to users after exposure. Overall, our results support that alkene dichlorination represents a new pathway for reactive Cl2 capture, opening new opportunities for binding this gas irreversibly in PPE.

[1]  Sanliang Ling,et al.  Controlling the Flexibility of MIL‐88A(Sc) Through Synthetic Optimisation and Postsynthetic Halogenation , 2022, Chemistry.

[2]  M. Manos,et al.  Fabric phase sorpitive extraction and passive sampling of ultraviolet filters from natural waters using a zirconium metal organic framework-cotton composite. , 2022, Journal of chromatography. A.

[3]  H. V. van Leeuwen,et al.  Immobilized Regenerable Active Chlorine within a Zirconium-Based MOF Textile Composite to Eliminate Biological and Chemical Threats. , 2021, Journal of the American Chemical Society.

[4]  M. Montazer,et al.  Biomedical Applicable Cellulose Fabric Modified with Zirconium‐Based Metal‐Organic Frameworks (Zr‐MOFs) , 2021, Starch - Stärke.

[5]  Phillip J. Milner,et al.  Evaluating the Robustness of Metal-Organic Frameworks for Synthetic Chemistry. , 2021, ACS applied materials & interfaces.

[6]  M. Javed,et al.  Engineering of Zirconium based metal-organic frameworks (Zr-MOFs) as efficient adsorbents , 2020 .

[7]  R. Schmid,et al.  Frustrated flexibility in metal-organic frameworks , 2020, Nature Communications.

[8]  K. Lillerud,et al.  Twinning in Zr-Based Metal-Organic Framework Crystals , 2020, Chemistry.

[9]  Yu-xu Zhong,et al.  Combining Two into One: A Dual-Function H5PV2Mo10O40@MOF-808 Composite as a Versatile Decontaminant for Sulfur Mustard and Soman. , 2020, Inorganic chemistry.

[10]  S. Dhomse,et al.  Delay in recovery of the Antarctic ozone hole from unexpected CFC-11 emissions , 2019, Nature Communications.

[11]  C. Janiak,et al.  Facile in Situ Halogen Functionalization via Triple-Bond Hydrohalogenation: Enhancing Sorption Capacities through Halogenation to Halofumarate-Based Zr(IV)-Metal-Organic Frameworks , 2019, Chemistry of Materials.

[12]  C. Serre,et al.  Engineering Structural Dynamics of Zirconium Metal-Organic Frameworks Based on Natural C4-linkers. , 2019, Journal of the American Chemical Society.

[13]  O. Farha,et al.  Zirconium-Based Metal–Organic Framework with 9-Connected Nodes for Ammonia Capture , 2019, ACS Applied Nano Materials.

[14]  Alexander C. Forse,et al.  Runaway Carbon Dioxide Conversion Leads to Enhanced Uptake in a Nanohybrid Form of Porous Magnesium Borohydride , 2019, Advanced materials.

[15]  Adam J. Rieth,et al.  Kinetic stability of metal–organic frameworks for corrosive and coordinating gas capture , 2019, Nature Reviews Materials.

[16]  Wei Zhou,et al.  Porous metal-organic frameworks for gas storage and separation: Status and challenges. , 2019, EnergyChem.

[17]  Omar K Farha,et al.  Optimizing Toxic Chemical Removal through Defect-Induced UiO-66-NH2 Metal-Organic Framework. , 2017, Chemistry.

[18]  Thomas H. Epps,et al.  Tuning the Morphology and Activity of Electrospun Polystyrene/UiO-66-NH2 Metal-Organic Framework Composites to Enhance Chemical Warfare Agent Removal. , 2017, ACS applied materials & interfaces.

[19]  Jared B. DeCoste,et al.  Filtration of chlorine and hydrogen chloride gas by engineered UiO-66-NH2 metal-organic framework. , 2017, Journal of hazardous materials.

[20]  Christopher H. Hendon,et al.  Reversible Capture and Release of Cl2 and Br2 with a Redox-Active Metal-Organic Framework. , 2017, Journal of the American Chemical Society.

[21]  Jared B. DeCoste,et al.  MOFabric: Electrospun Nanofiber Mats from PVDF/UiO-66-NH2 for Chemical Protection and Decontamination. , 2017, ACS applied materials & interfaces.

[22]  Sachin Chavan,et al.  A Facile “Green” Route for Scalable Batch Production and Continuous Synthesis of Zirconium MOFs , 2016 .

[23]  R. Marshall,et al.  Stereoselective Halogenation of Integral Unsaturated C‐C Bonds in Chemically and Mechanically Robust Zr and Hf MOFs , 2016, Chemistry.

[24]  R. Marshall,et al.  Single-Crystal to Single-Crystal Mechanical Contraction of Metal-Organic Frameworks through Stereoselective Postsynthetic Bromination. , 2015, Journal of the American Chemical Society.

[25]  Gregory W. Peterson,et al.  Evaluation of MOFs for air purification and air quality control applications: Ammonia removal from air , 2015 .

[26]  S. Denmark,et al.  Catalytic, stereospecific syn-dichlorination of alkenes , 2015, Nature Chemistry.

[27]  Omar M Yaghi,et al.  Water adsorption in porous metal-organic frameworks and related materials. , 2014, Journal of the American Chemical Society.

[28]  Michael O’Keeffe,et al.  The Chemistry and Applications of Metal-Organic Frameworks , 2013, Science.

[29]  Hongwei Wu,et al.  Release of Chlorine during Mallee Bark Pyrolysis , 2013 .

[30]  S. Richardson,et al.  Comparison of byproduct formation in waters treated with chlorine and iodine: relevance to point-of-use treatment. , 2010, Environmental science & technology.

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

[32]  O. Yaghi,et al.  Metal-organic frameworks with high capacity and selectivity for harmful gases , 2008, Proceedings of the National Academy of Sciences.

[33]  Anil K. Saroha,et al.  Safe handling of chlorine , 2006 .

[34]  J. Fauvarque.  The Chlorine Industry , 1996 .

[35]  M. Zahniser,et al.  Reactive Uptake of Cl2(g) and Br2(g) by Aqueous Surfaces as a Function of Br- and I- Ion Concentration: The Effect of Chemical Reaction at the Interface , 1995 .

[36]  S. Hahn,et al.  Novel polymeric structures via the chlorination of cis-1,4-polybutadiene in the presence of aryl nucleophiles , 1993 .

[37]  M. Ruasse.  Bromonium ions or .beta.-bromocarbocations in olefin bromination. A kinetic approach to product selectivities , 1990 .

[38]  P. Mare.  Pathways in electrophilic aromatic substitutions. Cyclohexadienes and related compounds as intermediates in halogenation , 1974 .