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      Benzothiadiazole functionalized D–A type covalent organic frameworks for effective photocatalytic reduction of aqueous chromium(vi)

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          Abstract

          Photocatalytic covalent organic frameworks were facilely constructed via the integration of alternative donor–acceptor units into the 2D extended and crystalline scaffolds, which exhibit excellent photodegradation efficiency toward aqueous Cr( vi).

          Abstract

          Covalent organic frameworks (COFs) have received increasing research interest as an emerging class of crystalline and porous polymers. Herein, we prepared two new benzothiadiazole (BT) functionalized COFs ( i.e. TPB-BT-COF and TAPT-BT-COF), which exhibit good crystallinity, high porosity, and excellent stability in harsh conditions. Their applications for photoreduction of Cr( vi) species under visible light irradiation were investigated. Over 99% Cr( vi) was reduced by utilizing TPB-BT-COF as catalyst without any sacrificial agents or additional pH adjustment. The photocatalytic rate of TPB-BT-COF is faster than that of TAPT-BT-COF, which can be attributed to more negative conduction band and narrower bandgap. Our results indicate that co-condensation of electron deficient units into the COF skeleton is conducive to efficient separation of photoexcited electrons and holes, which in turn leads to superior photocatalytic activities.

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          Most cited references65

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          A metal-free polymeric photocatalyst for hydrogen production from water under visible light.

          The production of hydrogen from water using a catalyst and solar energy is an ideal future energy source, independent of fossil reserves. For an economical use of water and solar energy, catalysts that are sufficiently efficient, stable, inexpensive and capable of harvesting light are required. Here, we show that an abundant material, polymeric carbon nitride, can produce hydrogen from water under visible-light irradiation in the presence of a sacrificial donor. Contrary to other conducting polymer semiconductors, carbon nitride is chemically and thermally stable and does not rely on complicated device manufacturing. The results represent an important first step towards photosynthesis in general where artificial conjugated polymer semiconductors can be used as energy transducers.
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            Porous, crystalline, covalent organic frameworks.

            Covalent organic frameworks (COFs) have been designed and successfully synthesized by condensation reactions of phenyl diboronic acid {C6H4[B(OH)2]2} and hexahydroxytriphenylene [C18H6(OH)6]. Powder x-ray diffraction studies of the highly crystalline products (C3H2BO)6.(C9H12)1 (COF-1) and C9H4BO2 (COF-5) revealed expanded porous graphitic layers that are either staggered (COF-1, P6(3)/mmc) or eclipsed (COF-5, P6/mmm). Their crystal structures are entirely held by strong bonds between B, C, and O atoms to form rigid porous architectures with pore sizes ranging from 7 to 27 angstroms. COF-1 and COF-5 exhibit high thermal stability (to temperatures up to 500 degrees to 600 degrees C), permanent porosity, and high surface areas (711 and 1590 square meters per gram, respectively).
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              Construction of crystalline 2D covalent organic frameworks with remarkable chemical (acid/base) stability via a combined reversible and irreversible route.

              Two new chemically stable [acid and base] 2D crystalline covalent organic frameworks (COFs) (TpPa-1 and TpPa-2) were synthesized using combined reversible and irreversible organic reactions. Syntheses of these COFs were done by the Schiff base reactions of 1,3,5-triformylphloroglucinol (Tp) with p-phenylenediamine (Pa-1) and 2,5-dimethyl-p-phenylenediamine (Pa-2), respectively, in 1:1 mesitylene/dioxane. The expected enol-imine (OH) form underwent irreversible proton tautomerism, and only the keto-enamine form was observed. Because of the irreversible nature of the total reaction and the absence of an imine bond in the system, TpPa-1 and TpPa-2 showed strong resistance toward acid (9 N HCl) and boiling water. Moreover, TpPa-2 showed exceptional stability in base (9 N NaOH) as well.
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                Author and article information

                Contributors
                Journal
                JMCAET
                Journal of Materials Chemistry A
                J. Mater. Chem. A
                Royal Society of Chemistry (RSC)
                2050-7488
                2050-7496
                January 15 2019
                2019
                : 7
                : 3
                : 998-1004
                Affiliations
                [1 ]Department of Chemistry
                [2 ]Tianjin Key Laboratory of Molecular Optoelectronic Science
                [3 ]Tianjin University
                [4 ]Tianjin 300072
                [5 ]China
                [6 ]Analytical and Testing Center
                [7 ]Jinan University
                [8 ]Guangzhou 510632
                Article
                10.1039/C8TA10046B
                0b61ce96-7475-45c8-ba04-e756d44f8949
                © 2019

                http://rsc.li/journals-terms-of-use

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