The Importance and Discovery of Highly Connected Covalent Organic Framework Net Topologies DOI
Tsukasa Irie, Saikat Das, Qianrong Fang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Furthering the field of synthetic organic chemistry from discrete molecules regime to extended structure regime, covalent frameworks (COFs) represent a new genre crystalline porous materials featuring designability with molecular-level precision, well-defined porosity, and exceptional stability imparted by robust linkages reticulating molecules. The topology COFs is principal feature that regulates their functionality usability for emerging technologies. Profound comprehension network topologies maneuvering them toward targeted applications are crucial advancing realm COF research developing novel functional exciting breakthroughs. In this Perspective, we discuss recent pursuits contributing discovery highly connected nets having topologies, assess key challenges achieving such offer insights into current scenario future directions.

Language: Английский

Highly Connected Three-Dimensional Covalent Organic Framework with Flu Topology for High-Performance Li-S Batteries DOI
Wenbo Liu, Kang Wang,

Xiaoning Zhan

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(14), P. 8141 - 8149

Published: March 29, 2023

Lithium-sulfur batteries (LSBs) have been considered as a promising candidate for next-generation energy storage devices, which however still suffer from the shuttle effect of intermediate lithium polysulfides (LiPSs). Covalent-organic frameworks (COFs) exhibited great potential sulfur hosts LSBs to solve such problem. Herein, pentiptycene-based D2h symmetrical octatopic polyaldehyde, 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-formylphenyl)pentiptycene (DMOPTP), was prepared and utilized building block toward preparing COFs. Condensation DMOPTP with 4-connected tetrakis(4-aminophenyl)methane affords an expanded [8 + 4] connected network 3D-flu-COF, flu topology. The non-interpenetrated nature topology endows 3D-flu-COF high Brunauer-Emmett-Teller surface area 2860 m2 g-1, large octahedral cavities, cross-linked tunnels in framework, enabling loading capacity (∼70 wt %), strong LiPS adsorption capability, facile ion diffusion. Remarkably, when used host LSBs, delivers 1249 mA h g-1 at 0.2 C (1.0 = 1675 g-1), outstanding rate capability (764 5.0 C), excellent stability, representing one best results among thus far reported COF-based materials being competitive state-of-the-art inorganic materials.

Language: Английский

Citations

102
Integrating Enrichment, Reduction, and Oxidation Sites in One System for Artificial Photosynthetic Diluted CO2 Reduction DOI
Yan Yang,

Hong‐Yu Zhang,

Ya Wang

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(40)

Published: June 26, 2023

Artificial photosynthetic diluted CO2 reduction directly driven by natural sunlight is a challenging, but promising way to realize carbon-resources recycling utilization. Herein, three-in-one photocatalytic system of enrichment, and H2 O oxidation sites designed for reduction. A Zn-Salen-based covalent organic framework (Zn-S-COF) with reductive synthesized; then, ionic liquids (ILs) are loaded into the pores. As result, [Emim]BF4 @Zn-S-COF shows visible-light-driven -to-CO conversion rate 105.88 µmol g-1 h-1 under (15%) atmosphere, even superior than most photocatalysts in high concentrations . Moreover, also reaches 126.51 5 h. Further experiments theoretical calculations reveal that triazine ring Zn-S-COF promotes activity sites, ILs provide an enriched realizing efficient

Language: Английский

Citations

81
Covalent organic frameworks in heterogeneous catalysis: recent advances and future perspective DOI
Ziad Alsudairy,

Normanda Brown,

Allea Campbell

et al.

Materials Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 7(16), P. 3298 - 3331

Published: Jan. 1, 2023

This review provides an overview of the recent advances in heterogeneous catalysis using COFs, primarily from 2020 to 2023, covering fundamentals, advantages, current challenges, and future perspectives.

Language: Английский

Citations

68
Dual Photosensitizer Coupled Three‐Dimensional Metal‐Covalent Organic Frameworks for Efficient Photocatalytic Reactions DOI
Meng Lu, Shuai‐Bing Zhang, Mingyi Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: June 7, 2023

In this work, we innovatively assembled two types of traditional photosensitizers, that is pyridine ruthenium/ferrum (Ru(bpy)32+ /Fe(bpy)32+ ) and porphyrin/metalloporphyrin complex (2HPor/ZnPor) by covalent linkage to get a series dual photosensitizer-based three-dimensional metal-covalent organic frameworks (3D MCOFs), which behaved strong visible light-absorbing ability, efficient electron transfer suitable band gap for highly photocatalytic hydrogen (H2 evolution. Rubpy-ZnPor COF achieved the highest H2 yield (30 338 μmol g-1 h-1 with apparent quantum efficiency (AQE) 9.68 %@420 nm, showed one best performances among all reported based photocatalysts. Furthermore, in situ produced was successfully tandem used alkyne hydrogenation ≈99.9 % conversion efficiency. Theoretical calculations reveal both photosensitizer units MCOFs can be photoexcited thus contribute optimal activity. This work develops general strategy shows great potential using multiple photosensitive materials field photocatalysis.

Language: Английский

Citations

67
Structural Motifs in Covalent Organic Frameworks for Photocatalysis DOI

Liyang Qin,

Chengdi Ma,

Jian Zhang

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: March 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

Language: Английский

Citations

67
3D covalent organic framework membrane with fast and selective ion transport DOI Creative Commons

Tianhao Zhu,

Yan Kong, Bohui Lyu

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Sept. 22, 2023

3D ionic covalent organic framework (COF) membranes, which are envisioned to be able break the trade-off between ion conductivity and selectivity, waiting for exploitation. Herein, we report fabrication of a sulfonic acid-functionalized COF membrane (3D SCOF) efficient selective transport, using dual acid-mediated interfacial polymerization strategy. The SCOF membranes possess highly interconnected transport channels, ultramicroporous pore sizes (0.97 nm), abundant sulfonate groups (with high exchange capacity 4.1 mmol g-1), leading proton 843 mS cm-1 at 90 °C. When utilized in osmotic energy conversion, power density 21.2 W m-2, remarkable selectivity 0.976 thus an exceptional conversion efficiency 45.3% simultaneously achieved. This work provides alternative approach promotes applications COFs separation.

Language: Английский

Citations

66
Optimization Strategies of Covalent Organic Frameworks and Their Derivatives for Electrocatalytic Applications DOI
Liyuan Xiao, Zhenlü Wang, Jingqi Guan

et al.

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(11)

Published: Nov. 27, 2023

Abstract Covalent organic frameworks (COFs) are crystalline porous polymers that can be precisely integrated by building blocks to achieve pre‐designed composition, components, and functions, making them a powerful platform for the development of molecular devices in field electrocatalysis. The precise control channel/dopant positions highly ordered network structures COFs provide an ideal material system applications advanced In this paper, topological structure design synthesis methods reviewed detail, their principles deeply analyzed. addition, derivatives electrocatalysis systematically summarized optimization strategies proposed. Finally, application prospects challenges may encountered future prospected, providing helpful guidance research.

Language: Английский

Citations

58
Three-dimensional covalent organic frameworks with pto and mhq-z topologies based on Tri- and tetratopic linkers DOI Creative Commons
Dongyang Zhu, Yifan Zhu, Yu Chen

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 19, 2023

Three-dimensional (3D) covalent organic frameworks (COFs) possess higher surface areas, more abundant pore channels, and lower density compared to their two-dimensional counterparts which makes the development of 3D COFs interesting from a fundamental practical point view. However, construction highly crystalline COF remains challenging. At same time, choice topologies in is limited by crystallization problem, lack availability suitable building blocks with appropriate reactivity symmetries, difficulties structure determination. Herein, we report two pto mhq-z designed rationally selecting rectangular-planar trigonal-planar conformational strains. The show large size 46 Å an extremely low calculated density. net topology solely constructed totally face-enclosed polyhedra displaying precise uniform micropore 1.0 nm. high CO2 adsorption capacity at room temperature can potentially serve as promising carbon capture adsorbents. This work expands accessible topologies, enriching structural versatility COFs.

Language: Английский

Citations

57
Oligo(phenylenevinylene)‐Based Covalent Organic Frameworks with Kagome Lattice for Boosting Photocatalytic Hydrogen Evolution DOI

Yuelin Zhong,

Wenbo Dong, Shijie Ren

et al.

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(1)

Published: Oct. 2, 2023

Covalent organic frameworks (COFs) have shown great advantages as photocatalysts for hydrogen evolution. However, the effect of linkage geometry and type on extent π-electron conjugation in plane framework photocatalytic properties COFs remains a significant challenge. Herein, two Kagome (kgm) topologic oligo(phenylenevinylene)-based are designed synthesized boosting evolution via "two one" strategy. Under visible light irradiation, COF-954 with 5 wt% Pt cocatalyst exhibits high rate (HER) 137.23 mmol g

Language: Английский

Citations

56
Postsynthetic Annulation of Three-Dimensional Covalent Organic Frameworks for Boosting CO2 Photoreduction DOI

Pengfei Dong,

Xinyu Xu, Rengan Luo

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(28), P. 15473 - 15481

Published: July 8, 2023

Three-dimensional covalent organic frameworks (3D COFs), with interconnected pores and exposed functional groups, provide new opportunities for the design of advanced materials through postsynthetic modification. Herein, we demonstrate successful annulation 3D COFs to construct efficient CO2 reduction photocatalysts. Two COFs, NJU-318 NJU-319Fe, were initially constructed by connecting hexaphenyl-triphenylene units pyrene- or Fe-porphyrin-based linkers. Subsequently, moieties within postsynthetically transformed into π-conjugated hexabenzo-trinaphthylene (pNJU-318 pNJU-319Fe) enhance visible light absorption photoreduction activity. The optimized photocatalyst, pNJU-319Fe, shows a CO yield 688 μmol g-1, representing 2.5-fold increase compared that unmodified NJU-319Fe. Notably, direct synthesis hexabenzo-trinaphthylene-based COF catalysts was unsuccessful due low solubility conjugated This study not only provides an effective method photocatalysts but also highlights unlimited tunability structural

Language: Английский

Citations

49