Dr. Shuailei Xie, Dr. Ruoyang Liu, Nengyi Liu, Hetao Xu, Prof. Dr. Xiong Chen, Prof. Dr. Xinchen Wang, Prof. Dr. Donglin Jiang
{"title":"用于光催化水氧化成氧的垂直扩展共价有机框架。","authors":"Dr. Shuailei Xie, Dr. Ruoyang Liu, Nengyi Liu, Hetao Xu, Prof. Dr. Xiong Chen, Prof. Dr. Xinchen Wang, Prof. Dr. Donglin Jiang","doi":"10.1002/anie.202416771","DOIUrl":null,"url":null,"abstract":"<p>Covalent organic frameworks with unique π architectures and pores could be developed as photocatalysts for transformations. However, they usually form π-stacking layers, so that only surface layers function in photocatalysis. Here we report a strategy for developing vertically expanded frameworks to expose originally inaccessible active sites hidden in layers to catalysis. We designed covalently linked two-dimensional cobalt(II) porphyrin layers and explored coordination bonds to connect the cobalt(II) porphyrin layers with bidentate ligands via a three-component one-pot polymerization. The resultant frameworks expand the interlayer space greatly, where both the up and down faces of each cobalt(II) porphyrin layer are exposed to reactants. Unexpectedly, the vertically expanded frameworks increase skeleton oxidation potentials, decrease exciton dissociation energy, improve pore hydrophilicity and affinity to water, and facilitate water delivery. Remarkably, these positive effects work collectively in the photocatalysis of water oxidation into oxygen, with an oxygen production rate of 1155 μmol g<sup>−1</sup> h<sup>−1</sup>, a quantum efficiency of 1.24 % at 450 nm, and a turnover frequency of 1.39 h<sup>−1</sup>, which is even 5.1-fold as high as that of the π-stacked frameworks and ranks them the most effective photocatalysts. This strategy offers a new platform for designing layer frameworks to build various catalytic systems for chemical transformations.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"64 4","pages":""},"PeriodicalIF":16.1000,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Vertically Expanded Covalent Organic Frameworks for Photocatalytic Water Oxidation into Oxygen\",\"authors\":\"Dr. Shuailei Xie, Dr. Ruoyang Liu, Nengyi Liu, Hetao Xu, Prof. Dr. Xiong Chen, Prof. Dr. Xinchen Wang, Prof. Dr. Donglin Jiang\",\"doi\":\"10.1002/anie.202416771\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Covalent organic frameworks with unique π architectures and pores could be developed as photocatalysts for transformations. However, they usually form π-stacking layers, so that only surface layers function in photocatalysis. Here we report a strategy for developing vertically expanded frameworks to expose originally inaccessible active sites hidden in layers to catalysis. We designed covalently linked two-dimensional cobalt(II) porphyrin layers and explored coordination bonds to connect the cobalt(II) porphyrin layers with bidentate ligands via a three-component one-pot polymerization. The resultant frameworks expand the interlayer space greatly, where both the up and down faces of each cobalt(II) porphyrin layer are exposed to reactants. Unexpectedly, the vertically expanded frameworks increase skeleton oxidation potentials, decrease exciton dissociation energy, improve pore hydrophilicity and affinity to water, and facilitate water delivery. Remarkably, these positive effects work collectively in the photocatalysis of water oxidation into oxygen, with an oxygen production rate of 1155 μmol g<sup>−1</sup> h<sup>−1</sup>, a quantum efficiency of 1.24 % at 450 nm, and a turnover frequency of 1.39 h<sup>−1</sup>, which is even 5.1-fold as high as that of the π-stacked frameworks and ranks them the most effective photocatalysts. 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Vertically Expanded Covalent Organic Frameworks for Photocatalytic Water Oxidation into Oxygen
Covalent organic frameworks with unique π architectures and pores could be developed as photocatalysts for transformations. However, they usually form π-stacking layers, so that only surface layers function in photocatalysis. Here we report a strategy for developing vertically expanded frameworks to expose originally inaccessible active sites hidden in layers to catalysis. We designed covalently linked two-dimensional cobalt(II) porphyrin layers and explored coordination bonds to connect the cobalt(II) porphyrin layers with bidentate ligands via a three-component one-pot polymerization. The resultant frameworks expand the interlayer space greatly, where both the up and down faces of each cobalt(II) porphyrin layer are exposed to reactants. Unexpectedly, the vertically expanded frameworks increase skeleton oxidation potentials, decrease exciton dissociation energy, improve pore hydrophilicity and affinity to water, and facilitate water delivery. Remarkably, these positive effects work collectively in the photocatalysis of water oxidation into oxygen, with an oxygen production rate of 1155 μmol g−1 h−1, a quantum efficiency of 1.24 % at 450 nm, and a turnover frequency of 1.39 h−1, which is even 5.1-fold as high as that of the π-stacked frameworks and ranks them the most effective photocatalysts. This strategy offers a new platform for designing layer frameworks to build various catalytic systems for chemical transformations.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.