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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 1O 2 scavenger, in darkness and with the changes of light sensitizing ligands. It confirmed that BPA was oxidized by the 1O 2 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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          Luminescent metal-organic frameworks for chemical sensing and explosive detection.

          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.
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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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              Metal-organic frameworks for artificial photosynthesis and photocatalysis.

              Solar energy is an alternative, sustainable energy source for mankind. Finding a convenient way to convert sunlight energy into chemical energy is a key step towards realizing large-scale solar energy utilization. Owing to their structural regularity and synthetic tunability, metal-organic frameworks (MOFs) provide an interesting platform to hierarchically organize light-harvesting antennae and catalytic centers to achieve solar energy conversion. Such photo-driven catalytic processes not only play a critical role in the solar to chemical energy conversion scheme, but also provide a novel methodology for the synthesis of fine chemicals. In this review, we summarize the fundamental principles of energy transfer and photocatalysis and provide an overview of the latest progress in energy transfer, light-harvesting, photocatalytic proton and CO2 reduction, and water oxidation using MOFs. The applications of MOFs in organic photocatalysis and degradation of model organic pollutants are also discussed.
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                Author and article information

                Contributors
                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
                : 6297
                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
                Author information
                http://orcid.org/0000-0002-6245-4759
                Article
                6194
                10.1038/s41598-017-06194-z
                5524690
                62c69028-eba6-4f6a-9ef9-9a8e8f16d01a
                © 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/.

                History
                : 10 March 2017
                : 7 June 2017
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