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Ultrahigh adsorption and singlet-oxygen mediated degradation for efficient synergetic removal of bisphenol A by a stable zirconium-porphyrin metal-organic framework

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Scientific Reports

Nature Publishing Group UK

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      Abstract

      Bisphenol A (BPA), one of 23 most important endocrine disrupting chemicals, was efficiently removed and sequentially photodegraded by a zirconium-porphyrin metal–organic framework (MOF) catalyst under visible light for water treatment. Well control of photodegradation allows the kinetic separation of adsorption step and photodegradation step. Ultrahigh adsorption uptake of 487.69 ± 8.37 mg g−1 is observed, while efficient photodegradation could be observed within 20 min at the rate of 0.004 mg min−1. The synergetic effect boosts the photocatalytic efficiency and confirms that the catalysis happens inside the MOF pores other than in the solution phase. Furthermore, the mechanism was elucidated by diverse control experiments, such as in the conditions of 1O2 scavenger, in darkness and with the changes of light sensitizing ligands. It confirmed that BPA was oxidized by the 1O2 which was generated from porphyrin ligand within MOFs under visible-light. The excellent reusability and wide range of suitable pH range make the Zr-porphyrin MOFs practical for the photocatalytic water treatment processes.

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        Selective gas adsorption and separation in metal-organic frameworks.

        Adsorptive separation is very important in industry. Generally, the process uses porous solid materials such as zeolites, activated carbons, or silica gels as adsorbents. With an ever increasing need for a more efficient, energy-saving, and environmentally benign procedure for gas separation, adsorbents with tailored structures and tunable surface properties must be found. Metal-organic frameworks (MOFs), constructed by metal-containing nodes connected by organic bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas separations due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. This critical review starts with a brief introduction to gas separation and purification based on selective adsorption, followed by a review of gas selective adsorption in rigid and flexible MOFs. Based on possible mechanisms, selective adsorptions observed in MOFs are classified, and primary relationships between adsorption properties and framework features are analyzed. As a specific example of tailor-made MOFs, mesh-adjustable molecular sieves are emphasized and the underlying working mechanism elucidated. In addition to the experimental aspect, theoretical investigations from adsorption equilibrium to diffusion dynamics via molecular simulations are also briefly reviewed. Furthermore, gas separations in MOFs, including the molecular sieving effect, kinetic separation, the quantum sieving effect for H2/D2 separation, and MOF-based membranes are also summarized (227 references).
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          Enantioselective catalysis with homochiral metal-organic frameworks.

          This tutorial review presents recent developments of homochiral metal-organic frameworks (MOFs) in enantioselective catalysis. Following a brief introduction of the basic concepts and potential virtues of MOFs in catalysis, we summarize three distinct strategies that have been utilized to synthesize homochiral MOFs. Framework stability and accessibility of the open channels to reagents are then addressed. We finally survey recent successful examples of catalytically active homochiral MOFs based on three approaches, namely, homochiral MOFs with achiral catalytic sites, incorporation of asymmetric catalysts directly into the framework, and post-synthetic modification of homochiral MOFs. Although still in their infancy, homochiral MOFs have clearly demonstrated their utility in heterogeneous asymmetric catalysis, and a bright future is foreseen for the development of practically useful homochiral MOFs in the production of optically pure organic molecules.
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            Author and article information

            Affiliations
            ISNI 0000 0001 0089 5711, GRID grid.260474.3, Jiangsu Key Laboratory of Biofunctional Materials, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, , School of Chemistry and Materials Science, Nanjing Normal University, ; Nanjing, 210023 P. R. China
            Contributors
            ORCID: http://orcid.org/0000-0002-6245-4759, guzhiyuan@njnu.edu.cn
            Journal
            Sci Rep
            Sci Rep
            Scientific Reports
            Nature Publishing Group UK (London )
            2045-2322
            24 July 2017
            24 July 2017
            2017
            : 7
            5524690
            6194
            10.1038/s41598-017-06194-z
            © The Author(s) 2017

            Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

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