Covalent organic frameworks (COFs) are promising for catalysis, sensing, gas storage, adsorption, optoelectricity, etc. owning to the unprecedented combination of large surface area, high crystallinity, tunable pore size, and unique molecular architecture. Although COFs are in their initial research stage, progress has been made in the design and synthesis of COF‐based electrocatalysis for the oxygen reduction reaction, oxygen evolution reaction, hydrogen evolution reaction, and CO2reduction in energy conversion and fuel generation. Design principles are also established for some of the COF materials toward rational design and rapid screening of the best electrocatalysts for a specific application. Herein, the recent advances in the design and synthesis of COF‐based catalysts for clean energy conversion and storage are presented. Future research directions and perspectives are also being discussed for the development of efficient COF‐based electrocatalysts.
- PAR ID:
- 10410114
- Date Published:
- Journal Name:
- Materials Chemistry Frontiers
- ISSN:
- 2052-1537
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Covalent organic frameworks (COFs) have received broad interest owing to their permanent porosity, high stability, and tunable functionalities. COFs with long‐range π‐conjugation and photosensitizing building blocks have been explored for sustainable photocatalysis. Herein, we report the first example of COF‐based energy transfer Ni catalysis. A pyrene‐based COF with sp2carbon‐conjugation was synthesized and used to coordinate NiIIcenters through bipyridine moieties. Under light irradiation, enhanced energy transfer in the COF facilitated the excitation of Ni centers to catalyze borylation and trifluoromethylation reactions of aryl halides. The COF showed two orders of magnitude higher efficiency in these reactions than its homogeneous control and could be recovered and reused without significant loss of catalytic activity.
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more » « less
Abstract Covalent organic frameworks (COFs) have received broad interest owing to their permanent porosity, high stability, and tunable functionalities. COFs with long‐range π‐conjugation and photosensitizing building blocks have been explored for sustainable photocatalysis. Herein, we report the first example of COF‐based energy transfer Ni catalysis. A pyrene‐based COF with sp2carbon‐conjugation was synthesized and used to coordinate NiIIcenters through bipyridine moieties. Under light irradiation, enhanced energy transfer in the COF facilitated the excitation of Ni centers to catalyze borylation and trifluoromethylation reactions of aryl halides. The COF showed two orders of magnitude higher efficiency in these reactions than its homogeneous control and could be recovered and reused without significant loss of catalytic activity.
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Abstract The first synthesis and comprehensive characterization of two vinyl tetrazine‐linked covalent organic frameworks (COF), TA‐COF‐1 and TA‐COF‐2, are reported. These materials exhibit high crystallinity and high specific surface areas of 1323 and 1114 m2g−1. The COFs demonstrate favorable band positions and narrow band gaps suitable for light‐driven applications. These advantages enable TA‐COFs to act as reusable metal‐free photocatalysts in the arylboronic acids oxidation and light‐induced coupling of benzylamines. In addition, these TA‐COFs show acid sensing capabilities, exhibiting visible and reversible color changes upon exposure to HCl solution, HCl vapor, and NH3vapor. Further, the TA‐COFs outperform a wide range of previously reported COF photocathodes. The tetrazine linker in the COF skeleton represents a significant advancement in the field of COF synthesis, enhancing the separation efficiency of charge carriers during the photoreaction and contributing to their photocathodic properties. TA‐COFs can also degrade 5‐nitro‐1,2,4‐triazol‐3‐one (NTO), an insensitive explosive present in industrial wastewater, in 20 min in a sunlight‐driven photocatalytic process; thus, revealing dual functionality of the protonated TA‐COFs as both photodegradation and Brønsted acid catalysts. This pioneering work opens new avenues for harnessing the potential of the tetrazine linker in COF‐based materials, facilitating advances in catalysis, sensing, and other related fields.
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Covalent organic framework (COF)-supported palladium catalysts have garnered enormous attention for cross-coupling reactions. However, the limited linkage types in COF hosts and their suboptimal catalytic performance have hindered their widespread implementation. Herein, we present the first study immobilizing palladium acetate onto a dioxin-linked COF (Pd/COF-318) through a facile solution impregnation approach. By virtue of its permanent porosity, accessible Pd sites arranged in periodic skeletons, and framework robustness, the resultant Pd/COF-318 exhibits exceptionally high activity and broad substrate scope for the Suzuki–Miyaura coupling reaction between aryl bromides and arylboronic acids at room temperature within an hour, rendering it among the most effective Pd/COF catalysts for Suzuki–Miyaura coupling reactions to date. Moreover, Pd/COF-318 demonstrates excellent recyclability, retaining high activity over five cycles without significant deactivation. The leaching test confirms the heterogeneity of the catalyst. This work uncovers the vast potential of dioxin-linked COFs as catalyst supports for highly active, selective, and durable organometallic catalysis.
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D3QM00188A
