Covalent Organic Frameworks for Photocatalytic Reduction of Carbon Dioxide: A Review

ACS Nano, Год журнала: 2024, Номер 18(33), С. 21804 - 21835

Опубликована: Авг. 8, 2024

Covalent organic frameworks (COFs) are crystalline networks with extended backbones cross-linked by covalent bonds. Due to the semiconductive properties and variable metal coordinating sites, along rapid development in linkage chemistry, utilization of COFs photocatalytic CO2RR has attracted many scientists' interests. In this Review, we summarize latest research progress on for CO2 reduction. first part, present COF linkages that have been used CO2RR, discuss four mechanisms including as intrinsic photocatalysts, photosensitive motifs metalated semiconductors heterojunction photocatalysts. Then, principles structural designs functional building units stacking mode exchange. Finally, outlook challenges provided. This Review is intended give some guidance design synthesis diverse different linkages, various structures, divergent modes efficient photoreduction CO2.

Язык: Английский

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Three‐dimensional Covalent Organic Framework with Dense Lithiophilic Sites as Protective Layer to Enable High‐Performance Lithium Metal Battery

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 5, 2024

Lithium (Li) metal batteries with remarkable energy densities are restrained by short lifetime and low Coulombic efficiency (CE), resulting from the accumulative Li dendrites dead during cycling. Here, we prepared a new three-dimensional (3D) covalent organic framework (COF) dense lithiophilic sites (heteoatom weight contents of 32.32 wt %) as an anodic protective layer batteries. The 3D COF was synthesized using [6+4] synthesis strategy inducing flexible 6-connected cyclotriphosphazene derivative aldehyde 4-connected porphyrin-based tetraphenylamines. Both phosphazene porphyrin rings in served electron-rich sites, enhancing homogeneous

Язык: Английский

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sp² Carbon‐Conjugated Covalent Organic Frameworks (sp²c‐COFs): Synthesis and Application in Photocatalytic Water Splitting

Macromolecular Rapid Communications, Год журнала: 2025, Номер unknown

Опубликована: Фев. 9, 2025

Abstract Preparation of irreversible sp 2 carbon‐conjugated covalent organic frameworks (sp c‐COFs) with specific porosity, easy structural functionalization, high chemical stability, and unique π‐electron conjugation structure (especially the combination π–π stacking interactions system), can remove barrier electron transfer provide a advantage for photocatalytic water splitting. Herein, based on three kinds reactions (Aldol condensation reaction, Knoevenagel Horner‐Wadsworth‐Emmons reaction) guided by precise modulation ligand topology, this review summarizes synthesis c‐COFs their applications in photoelectrocatalytic splitting (hydrogen evolution oxygen reactions). Furthermore, challenges possible research directions are also provided.

Язык: Английский

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Templated Freeze‐Casting for Porous Organic Battery Electrodes with High‐Rate Capabilities

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 12, 2025

Abstract Redox‐active polymer (RAP)‐based organic electrodes offer versatile energy storage solutions across various battery systems. However, effective dispersion of active materials with conductive additives remains challenging, limiting site accessibility and material utilization. This study introduces camphene (CAMP), a bio‐derived solvent, to fabricate porous through templated freeze casting. Compared conventional N‐methyl‐2‐pyrrolidone (NMP)‐cast electrodes, CAMP‐cast exhibit superior ion diffusion, lower charge transfer resistance, enhanced reaction kinetics three different RAPs. results in excellent rate capabilities significant capacity retention even at 20 A g −1 current density. At higher mass loadings (>1.0 mg cm − 2 ), achieve areal capacities ≈0.15 mAh 0.5 over 1000 cycles maintain more than 80% after 500 . These findings demonstrate CAMP's potential as an eco‐friendly alternative NMP for producing high‐performance offering sustainable approach advanced solutions.

Язык: Английский

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Modulating N‐Heterocyclic Microenvironment in β‐Ketoenamine Covalent Organic Frameworks to Boost Overall Photosynthesis of H₂O₂

Small, Год журнала: 2025, Номер unknown

Опубликована: Фев. 28, 2025

Abstract Covalent Organic Frameworks (COFs) have emerged as promising platforms for photocatalytic synthesis of hydrogen peroxide (H 2 O ) due to their tunable chemical compositions and efficient catalytic functionalities. Inspired by the role microenvironment in enzyme catalysis, this study introduces various N‐heterocyclic species into β ‐ketoenamine COFs (N x ‐COFs, where N represents number nitrogen atoms N‐heterocycle) regulate around sites on acceptor‐donor‐acceptor (A‐D‐A) foroverall H photosynthesis pure water. The ‐COFs exhibit distinct photosynthetic rates following sequence 3 ‐COF > 1 0 ‐COF, with triazine structure showing highest generation rate (4881 µmol h −1 g decent solar‐to‐chemical conversion (SCC) efficiency (0.413%), surpassing many existing COF‐based catalysts. In situ characterization theoretical calculations support experimental results, revealing that promote through both an indirect stepwise single‐electron oxygen reduction reaction (1e − ORR) mechanism a direct two‐electron water oxidation (2e WOR) pathway. This advances design paradigm photocatalysts modulating within A‐D‐A COFs, paving way development more robust systems overall .

Язык: Английский

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Tailoring lithium-friendly Cu current collectors for ultra-smooth lithium anodes with an innovative surface reconstruction strategy

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 161583 - 161583

Опубликована: Март 1, 2025

Язык: Английский

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An Electrochemically‐Driven Reconstruction Strategy to Realize Highly Crystalline Covalent Organic Frameworks for Enhanced Hydrogen Evolution Reaction

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Март 19, 2025

Abstract Developing diverse methods to approach highly crystalline covalent organic frameworks (COFs) for improvement of their electrocatalytic hydrogen evolution reaction (HER) activity is important but very challenging. Herein, the first time, an electrochemically‐driven reconstruction strategy demonstrated convert semi‐polymerized low‐crystalline COFs into crystalline, structurally ordered with enhanced HER activity. In situ and ex characterizations reveal that cyclic voltammetry (CV) cycles can promote crystallinity, thereby leading improved conductivity, increased active site density, superior stability. As a result, COF achieves low overpotentials 103.6 219.4 mV at 10 50 mA cm −2 , respectively, excellent stability (1200 h ). More importantly, this generalizable effective various imine‐linked different bonding types, significantly improving crystallinity This work not only establishes novel method constructing also demonstrates versatility electrochemically driven structural modulation in enhancing catalytic performance COFs.

Язык: Английский

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Interface preassembly oriented growth strategy towards flexible crystalline covalent organic framework films for OLEDs

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Апрель 8, 2025

Abstract The synthesis of flexible crystalline films for optoelectronic applications remains a significant chemical challenge due to the inherent contradiction between flexibility and crystallinity. delicate balance crystallinity has long constituted barrier development high-performance materials. Herein, an interface preassembly oriented growth (IPOG) strategy been explored fabricate covalent organic framework (COF) with controllable thickness. By synergistically modulating hydrophilic hydrophobic interactions along interfacial confinement, set uniform COF were successfully synthesized. This achievement unlocks potential COFs device in light-emitting diodes, leading unprecedented high-efficiency electroluminescence from COFs. groundbreaking advancement not only lays foundation progress COF-based OLEDs but also signifies advent era materials, wherein exceptional mechanical properties are seamlessly integrated superior electronic performance, thus heralding transformative impact on landscape electronics.

Язык: Английский

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High-rate yet dendrite-free lithium-metal batteries enabled by epitaxial growth of lithiophilic Cu particles on Cu foils with a double reducing agent strategy

Applied Surface Science, Год журнала: 2025, Номер unknown, С. 163218 - 163218

Опубликована: Апрель 1, 2025

Язык: Английский

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Cathodic dehalogenation polymerization of 2′,3′,5′,6′-tetrafluoro-4,4″-diiodo-1,1′:4′,1″-terphenyl on zinc metal surface for anode protection

Microstructures, Год журнала: 2025, Номер 5(3)

Опубликована: Апрель 17, 2025

Fluorine-containing poly(p-phenylene) (CityU-42) films on zinc surfaces were directly synthesized using a cathodic dehalogenation C-C coupling strategy. The as-prepared polymers can effectively protect the substrate in aqueous zinc-ion batteries. Because CityU-42 is rich electronegative fluorine group, it attract uniform deposition and rapid diffusion of Zn2+ surface anode. Moreover, large number benzene rings provide certain mechanical strength, enabling protective layer to inhibit growth dendrites. As result, symmetric Zn cell used CityU-42@Zn stably cycle for over 1,900 h under 5 mA cm-2 1 mAh cm-2, while V2O5 full cells maintain high capacity retention after 800 cycles at A g-1. results highlight potential synthesizing conjugated technology, paving way further advancement field energy storage technology.

Язык: Английский

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