☆ 4.8 Review

Porphyrin and phthalocyanine based covalent organic frameworks for electrocatalysis

COORDINATION CHEMISTRY REVIEWS (2022)

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A Nitrogen, Sulfur co-Doped Porphyrin-based Covalent Organic Framework as an Efficient Catalyst for Oxygen Reduction

Yu Xiaoming et al.

Summary: ORR is crucial for energy conversion systems, and the development of cheap, durable and highly-active catalysts is urgently needed. This study introduces a metal-free nitrogen and sulfur co-doped porphyrin-based COF as an efficient ORR catalyst, showcasing improved activity and synergistic effects compared to single-atom doping. Reasonable design of stable metal-free COFs with high electrochemical activity can promote their wide applications.

CHEMICAL RESEARCH IN CHINESE UNIVERSITIES (2022)

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Review Chemistry, Multidisciplinary

Conductive metal and covalent organic frameworks for electrocatalysis: design principles, recent progress and perspective

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Summary: Metal and covalent organic frameworks (MOFs/COFs) are promising catalyst candidates due to their porous nature, chemically defined active sites, and structural diversity. However, they often lack sufficient electrical conductivity to be effective electrocatalysts. This review highlights the design principles of conductive MOFs/COFs and their recent applications in electrocatalytic reactions, such as CO2RR, water splitting, and ORR. Future challenges and prospects for using conductive MOFs/COFs as electrocatalysts are also discussed.

NANOSCALE (2022)

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Article Chemistry, Physical

Three-dimensional porphyrinic covalent organic frameworks for highly efficient electroreduction of carbon dioxide

Shao-Yi Chi et al.

Summary: Covalent organic frameworks (COFs), a class of promising materials, have been used to electrochemically convert CO2 into valuable chemicals. Researchers synthesized a porous three-dimensional (3D) cobalt porphyrinic COF, 3D-Por(Co/H)-COF, and found that it exhibited high activity and efficiency for the CO2 reduction reaction. This work provides a new approach to improve electrocatalytic activity by changing the dimensions of the catalyst.

JOURNAL OF MATERIALS CHEMISTRY A (2022)

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Article Chemistry, Physical

Covalently anchoring covalent organic framework on carbon nanotubes for highly efficient electrocatalytic CO2 reduction

Hong Dong et al.

Summary: By covalently anchoring porphyrin-based COFs nanosheets on carbon nanotubes, efficient electrocatalytic CO2 reduction reactions can be achieved with enhanced activity and selectivity, especially with the formation of copper-based nanoclusters playing a crucial role in improving performance.

APPLIED CATALYSIS B-ENVIRONMENTAL (2022)

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Review Materials Science, Multidisciplinary

Recent progress in structural modulation of metal nanomaterials for electrocatalytic CO2 reduction

Chen-Huai Yang et al.

Summary: Metal nanomaterials have been widely used as electrocatalysts for ECR, and structural modulation including size, facet, grain boundary, composition, interface, ligand modification, and crystal phase can effectively improve catalytic performance. Designing stable and efficient catalysts is crucial for the electrochemical reduction of CO2 into high value-added products.

RARE METALS (2021)

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Stable Dioxin-Linked Metallophthalocyanine Covalent Organic Frameworks (COFs) as Photo-Coupled Electrocatalysts for CO2 Reduction

Meng Lu et al.

Summary: This study designed a series of stable metallophthalocyanine COFs as novel single-site catalysts with outstanding activity and selectivity for electrocatalytic CO2 reduction. Coupled with light, these COFs showed improved efficiency and potential for applications in the field of electrocatalysis.

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Controlling Solar Hydrogen Production by Organizing Porphyrins

Vasilis Nikolaou et al.

Summary: In this study, a highly efficient photocatalytic system for H-2 production is developed using porphyrins as photocatalysts. Self-organization of PdTCP and PtTCP into H- and J-aggregates on TiO2 NPs is crucial for H-2 evolution, with J-aggregated PtTCPs showing higher efficiency than H-aggregated PdTCPs. The simultaneous adsorption of PdTCP and PtTCP onto TiO2 NPs results in the most efficient catalytic system, achieving high turnover numbers.

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Stable Bimetallic Polyphthalocyanine Covalent Organic Frameworks as Superior Electrocatalysts

Yan Yue et al.

Summary: The study focuses on the development of highly stable bimetallic COFs for electrocatalytic CO2 reduction. The resulting CuPcF8-CoNPc-COF exhibits exceptional stability and electrocatalytic performance, with a faradaic efficiency of 97% and a turnover frequency of 2.87 s(-1).

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Rational design of isostructural 2D porphyrin-based covalent organic frameworks for tunable photocatalytic hydrogen evolution

Rufan Chen et al.

Summary: Covalent organic frameworks show promise in photocatalytic hydrogen generation from water, with the incorporation of different transition metals allowing for tuning of the hydrogen evolution rate.

NATURE COMMUNICATIONS (2021)

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Highly stable dioxin-linked metallophthalocyanine covalent organic frameworks

Zepeng Lei et al.

Summary: Highly stable metallophthalocyanine-based covalent organic frameworks (MPc-dxCOFs) with robust 1,4-dioxin bonds show excellent structural stability even under harsh conditions, and can be used as efficient electrocatalysts for the oxygen reduction reaction without the need for pyrolysis treatment.

CHINESE CHEMICAL LETTERS (2021)

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Review Chemistry, Inorganic & Nuclear

Porphyrin- and porphyrinoid-based covalent organic frameworks (COFs): From design, synthesis to applications

Minghui Chen et al.

Summary: COFs are a type of structurally ordered porous materials constructed with light atoms through covalent bonds, with recent interest in tetrapyrrolic macrocycle-based COFs using porphyrin and its analogs as building blocks, showing potential applications in diverse fields.

COORDINATION CHEMISTRY REVIEWS (2021)

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Article Chemistry, Multidisciplinary

Two-Dimensional Covalent Organic Frameworks with Cobalt(II)-Phthalocyanine Sites for Efficient Electrocatalytic Carbon Dioxide Reduction

Bin Han et al.

Summary: The study presents the design and synthesis of two-dimensional polyimide-linked phthalocyanine COFs with stable properties, showing potential applications in electrocatalysis.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Fine tuning of supported covalent organic framework with molecular active sites loaded as efficient electrocatalyst for water oxidation

Zhijian Gan et al.

Summary: This paper reports an ideal platform constructed by COFs and MWCNTs to illustrate key factors in COF-based electrocatalysts for oxygen evolution. Fine tuning of COF layers reveals that optimized catalytic performance relies on proper loading of molecular catalysts and a novel strategy of diluting active sites is proposed to enhance intrinsic activity. The generality of fine regulation is fully demonstrated with different COFs, shedding light on the broad applications of molecular catalysts.

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Review Chemistry, Multidisciplinary

Metal-Organic Frameworks-Derived Self-Supported Carbon-Based Composites for Electrocatalytic Water Splitting

Yikang Cong et al.

Summary: Electrocatalytic water splitting is a promising strategy for sustainable hydrogen energy development, and self-supported metal-organic frameworks (MOFs) can be suitable templates/precursors to construct free-standing carbon-based composites with well-aligned array architecture and evenly distributed active sites, serving as alternative options to non-noble metal-included electrocatalysts.

CHEMISTRY-A EUROPEAN JOURNAL (2021)

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Porphyrin- and phthalocyanine-based porous organic polymers: From synthesis to application

Wenyan Ji et al.

Summary: This article summarizes the characteristics of porphyrins and phthalocyanines and their important role in constructing porous organic polymers, introduces different preparation methods and application areas, and emphasizes the importance of structural design on performance.

COORDINATION CHEMISTRY REVIEWS (2021)

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Article Chemistry, Multidisciplinary

A Cubic 3D Covalent Organic Framework with nbo Topology

Xue Wang et al.

Summary: By using tetrahedral spiroborate linkages, square-planar cobalt(II) phthalocyanine units are assembled into a 3D COF with noninterpenetrated nbo topology, exhibiting high crystallinity and long-range order. The COF has cubic pores and permanent porosity, with a BET surface area of 1726 m(2) g(-1).

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Covalent Organic Frameworks as Emerging Platforms for CO2 Photoreduction

Ha L. Nguyen et al.

Summary: Covalent organic frameworks (COFs) are a new class of porous crystalline materials with semiconductor properties, showing promising performance in CO2 photoreduction catalysis. Principles of design and recent advancements in using COFs for CO2 photoreduction can serve as a reference for developing CO2 reduction catalysts.

ACS CATALYSIS (2021)

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Constructing Catalytic Crown Ether-Based Covalent Organic Frameworks for Electroreduction of CO2

Shuhao An et al.

Summary: A crown ether and cobalt-porphyrin-based COF was developed for catalytic reduction of carbon dioxide, showing remarkable performance with high Faradaic efficiencies and maximum turnover frequency. The crown ether units enhanced the hydrophilicity, electron transfer ability, and binding capacity of the COF, leading to its excellent catalytic performance.

ACS ENERGY LETTERS (2021)

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Review Chemistry, Physical

Atomically Structural Regulations of Carbon-Based Single-Atom Catalysts for Electrochemical CO2 Reduction

Shu-Guo Han et al.

Summary: Carbon-based single-atom catalysts (SACs) have shown significant potential for electrochemical carbon dioxide reduction reaction (CO2RR) by regulating the coordination structures of metal centers and the microenvironments of substrates. This review summarizes recent advances in synthetic strategies and the structure-performance relationship of SACs towards CO2RR, highlighting the challenges and research directions for SACs in the future.

SMALL METHODS (2021)

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Article Chemistry, Multidisciplinary

Two-dimensional porphyrin covalent organic frameworks with tunable catalytic active sites for the oxygen reduction reaction

Jie-Yu Yue et al.

Summary: The ORR catalytic activity of four novel two-dimensional porphyrin COFs was tuned by changing the M atom in the center of the porphyrin backbone. The experimental structure-function relationship was consistent with density functional theory calculations based on the O-2-O-2*-OOH*-O*-OH*-OH- route.

CHEMICAL COMMUNICATIONS (2021)

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Review Chemistry, Multidisciplinary

Recent advances in electrocatalysis with phthalocyanines

Shaoxuan Yang et al.

Summary: The applications of phthalocyanines (Pcs) in electrocatalysis have attracted attention due to their advantages of low cost, facile synthesis, and good chemical stability. Pcs offer high tailorability and structural diversity, making them promising for optimization in electrochemical devices and for various electrochemical reactions. Further research is needed to explore the structure-composition catalytic activity relationships of different Pc materials for future practical applications.

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Review Chemistry, Physical

Pyrolysis-free covalent organic framework-based materials for efficient oxygen electrocatalysis

Xun Cui et al.

Summary: Pyrolysis-free covalent organic frameworks (COFs) serve as a promising platform for oxygen electrocatalysis research, enabling the preservation of active sites and facilitating a deeper understanding of electrocatalytic mechanisms. Their tunable porosity, atomically precise structures, and programmable topological architectures make them ideal candidates for high-performance electrocatalysts.

JOURNAL OF MATERIALS CHEMISTRY A (2021)

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Construction of a polymeric cobalt phthalocyanine@mesoporous graphitic carbon nitride composite for efficient photocatalytic CO2 reduction

Hongwei Li et al.

Summary: By polymerizing cobalt phthalocyanine on mesoporous g-C3N4, a hybrid organic/inorganic photocatalyst was prepared for efficient CO2 reduction to CO under visible light irradiation in organic solvents. The photocatalyst exhibited high activity and long-term stability, offering a versatile strategy for synthesizing active composite materials for photocatalysis.

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A 2D porphyrin-based covalent organic framework with TEMPO for cooperative photocatalysis in selective aerobic oxidation of sulfides

Keyu Feng et al.

Summary: 2D covalent organic frameworks (2D COFs) have attracted increasing attention in photocatalysis, and combining them with redox mediators can significantly enhance the catalytic efficiency, leading to a cooperative photocatalysis process. This study highlights the potential of 2D COFs as a unique platform for constructing cooperative photocatalysts with redox mediators.

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Porphyrin-based frameworks for oxygen electrocatalysis and catalytic reduction of carbon dioxide

Zuozhong Liang et al.

Summary: This review discusses the wide application of porphyrin-based frameworks in energy-related conversion and storage technologies, performance comparison, and structure-activity relationship. Regulating the porous structures of frameworks and growing them on conductive supports enhance electrocatalytic performance.

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Photocatalytic hydrogen production of porphyrin nanostructures: spheres vs. fibrils, a case study

Vasilis Nikolaou et al.

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Qiao Wu et al.

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