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      Photocatalytic overall water splitting by conjugated semiconductors with crystalline poly(triazine imide) frameworks†

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          Abstract

          In this work, we apply a carbon nitride semiconductor with a crystalline poly(triazine imide) (PTI) frameworks to photocatalytic overall water splitting.

          Abstract

          Photocatalytic water splitting is an ideal pathway to produce hydrogen for the future energy supply due to the sustainability of solar energy and the mild reaction conditions. In the past four decades, many inorganic semiconductor photocatalysts have been studied for this purpose. In recent years, conjugated polymers, in particular covalent carbon nitride frameworks, have rapidly emerged as a new family of photocatalysts. However, the use of conjugated photocatalysts in overall water splitting in the absence of sacrificial agents has been much less reported. Herein, we used surface kinetic control to photocatalyze overall water splitting by a covalent carbon nitride semiconductor with a crystalline poly(triazine imide) (PTI) frameworks. Our study demonstrates that the loading of a Pt co-catalyst on the PTI surface plays the key role in inducing overall water splitting. The co-deposition of a cobalt species can effectively increase the photocatalytic activity and adjust the ratio of H 2 and O 2 produced, as well as enhancing the stability of the photocatalyst. The optimal sample with the dual co-catalysts shows an apparent quantum yield of 2.1% for the overall water splitting reaction.

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          Roles of cocatalysts in photocatalysis and photoelectrocatalysis.

          Since the 1970s, splitting water using solar energy has been a focus of great attention as a possible means for converting solar energy to chemical energy in the form of clean and renewable hydrogen fuel. Approaches to solar water splitting include photocatalytic water splitting with homogeneous or heterogeneous photocatalysts, photoelectrochemical or photoelectrocatalytic (PEC) water splitting with a PEC cell, and electrolysis of water with photovoltaic cells coupled to electrocatalysts. Though many materials are capable of photocatalytically producing hydrogen and/or oxygen, the overall energy conversion efficiency is still low and far from practical application. This is mainly due to the fact that the three crucial steps for the water splitting reaction: solar light harvesting, charge separation and transportation, and the catalytic reduction and oxidation reactions, are not efficient enough or simultaneously. Water splitting is a thermodynamically uphill reaction, requiring transfer of multiple electrons, making it one of the most challenging reactions in chemistry. This Account describes the important roles of cocatalysts in photocatalytic and PEC water splitting reactions. For semiconductor-based photocatalytic and PEC systems, we show that loading proper cocatalysts, especially dual cocatalysts for reduction and oxidation, on semiconductors (as light harvesters) can significantly enhance the activities of photocatalytic and PEC water splitting reactions. Loading oxidation and/or reduction cocatalysts on semiconductors can facilitate oxidation and reduction reactions by providing the active sites/reaction sites while suppressing the charge recombination and reverse reactions. In a PEC water splitting system, the water oxidation and reduction reactions occur at opposite electrodes, so cocatalysts loaded on the electrode materials mainly act as active sites/reaction sites spatially separated as natural photosynthesis does. In both cases, the nature of the loaded cocatalysts and their interaction with the semiconductor through the interface/junction are important. The cocatalyst can provide trapping sites for the photogenerated charges and promote the charge separation, thus enhancing the quantum efficiency; the cocatalysts could improve the photostability of the catalysts by timely consuming of the photogenerated charges, particularly the holes; most importantly, the cocatalysts catalyze the reactions by lowering the activation energy. Our research shows that loading suitable dual cocatalysts on semiconductors can significantly increase the photocatalytic activities of hydrogen and oxygen evolution reactions, and even make the overall water splitting reaction possible. All of these findings suggest that dual cocatalysts are necessary for developing highly efficient photocatalysts for water splitting reactions.
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            Iodine modified carbon nitride semiconductors as visible light photocatalysts for hydrogen evolution.

            An optimized and general synthetic strategy based on in-situ iodine modifying of polymeric graphitic carbon nitride is discussed. The as-prepared iodine functionalized g-CN shows enhanced electronic and optical properties, as well as increased photocatalytic activities in an assay of hydrogen evolution.
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              Ionothermal synthesis of crystalline, condensed, graphitic carbon nitride.

              Herein we report the synthesis of a crystalline graphitic carbon nitride, or g-C(3)N(4), obtained from the temperature-induced condensation of dicyandiamide (NH(2)C(=NH)NHCN) by using a salt melt of lithium chloride and potassium chloride as the solvent. The proposed crystal structure of this g-C(3)N(4) species is based on sheets of hexagonally arranged s-heptazine (C(6)N(7)) units that are held together by covalent bonds between C and N atoms which are stacked in a graphitic, staggered fashion, as corroborated by powder X-ray diffractometry and high-resolution transmission electron microscopy.
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                Author and article information

                Journal
                Chem Sci
                Chem Sci
                Chemical Science
                Royal Society of Chemistry
                2041-6520
                2041-6539
                1 August 2017
                30 May 2017
                : 8
                : 8
                : 5506-5511
                Affiliations
                [a ] State Key Laboratory of Photocatalysis on Energy and Environment , College of Chemistry , Fuzhou University , Fuzhou , Fujian 350002 , P. R. China . Email: xcwang@ 123456fzu.edu.cn ; http://wanglab.fzu.edu.cn
                Author information
                http://orcid.org/0000-0002-2490-3568
                Article
                c7sc00900c
                10.1039/c7sc00900c
                5613792
                28970930
                914c973e-49b2-494e-a09b-2d999a1fb928
                This journal is © The Royal Society of Chemistry 2017

                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
                : 26 February 2017
                : 30 May 2017
                Categories
                Chemistry

                Notes

                †Electronic supplementary information (ESI) available: Characterization and experimental details. See DOI: 10.1039/c7sc00900c


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