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      Stepwise observation and quantification and mixed matrix membrane separation of CO 2 within a hydroxy-decorated porous host†

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          Abstract

          CO 2 binding and separation using porous MFM-300(V III) has been fully studied.

          Abstract

          The identification of preferred binding domains within a host structure provides important insights into the function of materials. State-of-the-art reports mostly focus on crystallographic studies of empty and single component guest-loaded host structures to determine the location of guests. However, measurements of material properties ( e.g., adsorption and breakthrough of substrates) are usually performed for a wide range of pressure (guest coverage) and/or using multi-component gas mixtures. Here we report the development of a multifunctional gas dosing system for use in X-ray powder diffraction studies on Beamline I11 at Diamond Light Source. This facility is fully automated and enables in situ crystallographic studies of host structures under (i) unlimited target gas loadings and (ii) loading of multi-component gas mixtures. A proof-of-concept study was conducted on a hydroxyl-decorated porous material MFM-300(V III) under (i) five different CO 2 pressures covering the isotherm range and (ii) the loading of equimolar mixtures of CO 2/N 2. The study has successfully captured the structural dynamics underpinning CO 2 uptake as a function of surface coverage. Moreover, MFM-300(V III) was incorporated in a mixed matrix membrane (MMM) with PIM-1 in order to evaluate the CO 2/N 2 separation potential of this material. Gas permeation measurements on the MMM show a great improvement over the bare PIM-1 polymer for CO 2/N 2 separation based on the ideal selectivity.

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          Luminescent metal-organic frameworks for chemical sensing and explosive detection.

          Zhichao Hu, Benjamin J Deibert, Jing Li (2014)
          Metal-organic frameworks (MOFs) are a unique class of crystalline solids comprised of metal cations (or metal clusters) and organic ligands that have shown promise for a wide variety of applications. Over the past 15 years, research and development of these materials have become one of the most intensely and extensively pursued areas. A very interesting and well-investigated topic is their optical emission properties and related applications. Several reviews have provided a comprehensive overview covering many aspects of the subject up to 2011. This review intends to provide an update of work published since then and focuses on the photoluminescence (PL) properties of MOFs and their possible utility in chemical and biological sensing and detection. The spectrum of this review includes the origin of luminescence in MOFs, the advantages of luminescent MOF (LMOF) based sensors, general strategies in designing sensory materials, and examples of various applications in sensing and detection.
          Article 0 comments Cited 915 times – based on 0 reviews     Review now
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            Highly efficient separation of carbon dioxide by a metal-organic framework replete with open metal sites.

            David Britt, Hiroyasu Furukawa, Bo Wang … (2009)
            Selective capture of CO(2), which is essential for natural gas purification and CO(2) sequestration, has been reported in zeolites, porous membranes, and amine solutions. However, all such systems require substantial energy input for release of captured CO(2), leading to low energy efficiency and high cost. A new class of materials named metal-organic frameworks (MOFs) has also been demonstrated to take up voluminous amounts of CO(2). However, these studies have been largely limited to equilibrium uptake measurements, which are a poor predictor of separation ability, rather than the more industrially relevant kinetic (dynamic) capacity. Here, we report that a known MOF, Mg-MOF-74, with open magnesium sites, rivals competitive materials in CO(2) capture, with 8.9 wt. % dynamic capacity, and undergoes facile CO(2) release at significantly lower temperature, 80 degrees C. Mg-MOF-74 offers an excellent balance between dynamic capacity and regeneration. These results demonstrate the potential of MOFs with open metal sites as efficient CO(2) capture media.
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              Selectivity and direct visualization of carbon dioxide and sulfur dioxide in a decorated porous host.

              Sihai Yang, Junliang Sun, Anibal J Ramirez-Cuesta … (2012)
              Understanding the mechanism by which porous solids trap harmful gases such as CO(2) and SO(2) is essential for the design of new materials for their selective removal. Materials functionalized with amine groups dominate this field, largely because of their potential to form carbamates through H(2)N(δ(-))···C(δ(+))O(2) interactions, thereby trapping CO(2) covalently. However, the use of these materials is energy-intensive, with significant environmental impact. Here, we report a non-amine-containing porous solid (NOTT-300) in which hydroxyl groups within pores bind CO(2) and SO(2) selectively. In situ powder X-ray diffraction and inelastic neutron scattering studies, combined with modelling, reveal that hydroxyl groups bind CO(2) and SO(2) through the formation of O=C(S)=O(δ(-))···H(δ(+))-O hydrogen bonds, which are reinforced by weak supramolecular interactions with C-H atoms on the aromatic rings of the framework. This offers the potential for the application of new 'easy-on/easy-off' capture systems for CO(2) and SO(2) that carry fewer economic and environmental penalties.
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                Author and article information

                Journal
                Journal ID (nlm-ta): Chem Sci
                Journal ID (iso-abbrev): Chem Sci
                Title: Chemical Science
                Publisher: Royal Society of Chemistry
                ISSN (Print): 2041-6520
                ISSN (Electronic): 2041-6539
                Publication date (Print): 1 April 2017
                Publication date (Electronic): 27 February 2017
                Volume: 8
                Issue: 4
                Pages: 3239-3248
                Affiliations
                [a ] School of Chemistry , University of Manchester , Oxford Road , Manchester , M13 9PL , UK . Email: Sihai.Yang@ 123456manchester.ac.uk ; Email: M.Schroder@ 123456manchester.ac.uk
                [b ] Diamond Light Source , Harwell Science and Innovation Campus , Didcot , Oxfordshire , OX11 0DE , UK . Email: chiu.tang@ 123456diamond.ac.uk
                [c ] Department of Chemistry , University of Liverpool , Liverpool , L69 7ZD , UK
                [d ] Fraunhofer IAP , FB3, Geiselbergstrasse 69 , Potsdam-Golm , 14476 , Germany
                Author information
                http://orcid.org/0000-0001-6992-0700
                Article
                Publisher ID: c6sc04343g
                DOI: 10.1039/c6sc04343g
                PMC ID: 5414597
                PubMed ID: 28507700
                SO-VID: 17ddf9d2-8ee5-4488-8301-b85b0bc71a09
                Copyright © This journal is © The Royal Society of Chemistry 2017
                License:

                This is an Open Access article distributed under the terms of the Creative Commons Attribution 3.0 Unported License ( http://creativecommons.org/licenses/by/3.0/) which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

                History
                Date received : 29 September 2016
                Date accepted : 3 February 2017
                Categories
                Subject: Chemistry

                Notes

                †Electronic supplementary information (ESI) available. CCDC 1504685–1504693. See DOI: 10.1039/c6sc04343g


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