Journal of Molecular Structure, Год журнала: 2025, Номер unknown, С. 142061 - 142061
Опубликована: Март 1, 2025
Язык: Английский
Advanced Functional Materials, Год журнала: 2024, Номер unknown
Опубликована: Март 10, 2024
Abstract Covalent organic frameworks (COFs) attract significant attention due to their ordered, crystalline, porous, metal‐free, and predictable structures. These unique characteristics offer great opportunities for the diffusion transmission of photogenerated charges during photocatalysis. Currently, a considerable number COFs are used as metal‐free semiconductor photocatalysts. This review aims understand relationships between structure photocatalysis performance provides in‐depth insight into synthetic strategy improve performance. Subsequently, focuses on structural motif in sustainable photocatalytic hydrogen evolution, carbon dioxide reduction, peroxide generation, compound transformations. Last, conjunction with progress achieved challenges yet be overcome, candid discussion is undertaken regarding field COF photocatalysis, accompanied by presentation potential research avenues future directions. seeks provide readers comprehensive understanding pivotal role robust guidance innovative utilization
Язык: Английский
Процитировано
66
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
Процитировано
34
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(36)
Опубликована: Июнь 21, 2024
Abstract Hydrogen‐bonded organic frameworks (HOFs) are outstanding candidates for photocatalytic hydrogen evolution. However, most of reported HOFs suffer from poor stability and activity in the absence Pt cocatalyst. Herein, a series metal (Co 2 ‐HOF‐X, X=COOMe, Br, tBu OMe) have been rationally constructed based on dinuclear cobalt complexes, which exhibit exceptional presence strong acid (12 M HCl) base (5 NaOH) at least 10 days. More impressively, by varying ‐X groups microenvironment Co ‐HOF‐X can be modulated, giving rise to obviously different H production rates, following −X group sequence −COOMe>−Br>−tBu>−OMe. The optimized ‐HOF‐COOMe shows generation rate up 12.8 mmol g −1 h any additional noble‐metal photosensitizers cocatalysts, is superior Pt‐assisted systems. Experiments theoretical calculations reveal that grafted possess electron‐withdrawing ability, thus regulating electronic structures catalytic centres proton activation barrier production, leading distinctly activity.
Язык: Английский
Процитировано
20
Accounts of Chemical Research, Год журнала: 2025, Номер unknown
Опубликована: Фев. 21, 2025
ConspectusMetal-organic frameworks (MOFs) and covalent organic (COFs), as emerging porous crystalline materials, have attracted remarkable attention in chemistry, physics, materials science. MOFs are constructed by metal clusters (or ions) linkers through coordination bonds, while COFs prepared pure building blocks via bonds. Because of the nature linkages, their own shortcomings. Typically, relatively weak bond strengths bonds lead to poor chemical stability MOFs, which limits practical implementations. On other hand, due strong exhibit rather higher under harsh conditions, compared MOFs. However, lack open sites restricts functionalization application. Therefore, it is hypothesized that "cream-skimming" would address these drawbacks produce a new class material, namely, metal-organic (CMOFs), with unprecedented structural complexity advanced functionality. The CMOFs reveal synthetic approach for preparation reticular materials. Specifically, ions reacted chelating ligands assemble complexes or functional reactive (e.g., -CHO, -NH2), can be further connected form networked structures dynamic chemistry (DCC). isolated complex cluster precursors show enhanced prevents decomposition rearrangements during self-assembly process CMOFs. Since topology preassembled nodes well-defined, structure readily predicted upon directed networking Unaccessible from unstable highly ion/clusters traditional conditions DCC approach. Moreover, synergize advantages COFs, containing active ensuring various interesting properties, linkages allow high even conditions. In past few years, our group has specifically focused on development general strategies coinage (Cu, Ag, Au)-based cyclic trinuclear units (CTUs) DCC. CTUs trigonal planar functionalized sites, such -NH2 react afford Notably, also features properties including metallophilic attraction, π-acidity/basicity, luminescence, redox activity catalytic activity, incorporated into we envision promising platforms not only novel but potential applications many research fields gas absorption/separation, sensing, full-color display, catalysis, energy, biological applications. this Account, summarize recent studies CMOFs, starting linkage topological design, transformation, morphological control, fields. We discuss future opportunities challenges rapidly developed field hope Account may promote scientific discoveries CMOF-based technologies future.
Язык: Английский
Процитировано
5
Coordination Chemistry Reviews, Год журнала: 2025, Номер 533, С. 216507 - 216507
Опубликована: Фев. 21, 2025
Язык: Английский
Процитировано
3
Chemistry of Materials, Год журнала: 2024, Номер 36(15), С. 7362 - 7369
Опубликована: Июль 26, 2024
Covalent organic frameworks (COFs) linked by imine bonds have attracted significant attention, primarily due to the accessibility of monomers and facile synthesis highly crystalline materials. However, reversible nature raises stability concerns for these materials in practical applications. Therefore, there is a pressing need development imine-linked COFs that can combine high crystallinity, good stability, functionality. Here, adopting two-in-one molecular design strategy, we designed an building block containing both acetal amino connecting groups, featuring pyridine functional site, with side chains consisting alkoxyl groups. Following synthesis, elements were combined confined channel (0.85 nm), leading two-dimensional (2D) (COF-LIFM4 COF-LIFM5) crystallinity strong acid base conditions. Moreover, COF-LIFM5 exhibited favorable CO2 affinity appropriate hydrophobicity, making it promising modifier improving mass transfer reduction reaction (CO2RR). As result, Cu/COF-LIFM5 showcased enhanced C2+ product selectivity CO2RR, Faradaic efficiency exceeding 80% at current density 500 mA cm–2 flow cell.
Язык: Английский
Процитировано
10
Small, Год журнала: 2025, Номер unknown
Опубликована: Март 5, 2025
The recovery of radioactive iodine from nuclear waste and contaminated water sources is a critical environmental concern, which poses significant technical challenges. Herein, the study has demonstrated that tuning electronic properties diketopyrrolopyrrole-based donor-acceptor covalent organic frameworks (COFs) enhances trapping, improves charge transport, strengthens interactions - establishing structure-property relationship. This achieved by synthesizing COFs with linker 3,6-bis(4-(1,3-dioxolan-2-yl)phenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (DKP) in combination either electron acceptor 4,4',4″-(1,3,5-triazine-2,4,6-triyl)trianiline (TTT-DKP) or donor N1,N1-bis(4-aminophenyl)benzene-1,4-diamine (TAPA-DKP) linkers. These COFs, abundant sorption sites, thermal chemical stability, optimized pore environments, efficiently bind vapor solution phases. TAPA-DKP COF, containing electron-donating moieties, showed high uptake 3.52 g/g, exceeding 2.81 g/g electron-deficient TTT-DKP phase, both following pseudo-second-order kinetics. Density functional theory (DFT) calculations reveal adsorption sites showing COF binds I2 more effectively via its electron-rich highlighting role property modulation adsorption.
Язык: Английский
Процитировано
2
Science China Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Янв. 3, 2025
Язык: Английский
Процитировано
1
Advances in Colloid and Interface Science, Год журнала: 2025, Номер unknown, С. 103507 - 103507
Опубликована: Апрель 1, 2025
Язык: Английский
Процитировано
1
Nature Communications, Год журнала: 2024, Номер 15(1)
Опубликована: Авг. 9, 2024
Membrane reactors are known for their efficiency and superior operability compared to traditional batch processes, but limited diversity poses challenges in meeting various reaction requirements. Herein, we leverage the molecular tunability of covalent organic frameworks (COFs) broaden applicability membrane reactors. Our COF demonstrates an exceptional ability achieve complete conversion just 0.63 s at room temperature-a benchmark Knoevenagel condensation. This performance significantly surpasses that corresponding homogeneous catalyst powder by factors 176 375 turnover frequency, respectively. The enhanced concentration reactants rapid removal generated water within greatly accelerate reaction, reducing apparent activation energy. Consequently, this reactor enables reactions unattainable using both powders catalysts. Considering versatility, our findings highlight substantial promise COF-based transformations.
Язык: Английский
Процитировано
8