Redox‐Active Metal‐Covalent Organic Frameworks for Dendrite‐Free Lithium Metal Batteries DOI

Wenliang Qin,

Diandian Han,

Xiaowei Zhang

et al.

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

Abstract Lithium (Li) metal has gained attention as an anode material for lithium‐metal batteries (LMBs) owing to its low electrochemical potential, high specific capacity, and density. However, the accumulation of Li dendrites unstable solid electrolyte interphases, caused by sluggish + migration uneven deposition, limit practical LMB applications. This study presents first report on redox‐active metal–covalent organic frameworks (MCOFs) with dual‐active centers functional separators LMBs. These MCOFs facilitate homogeneous nucleation accelerate ion transport. The synergistic effects diarylamine units trinuclear copper clusters modulate local electron‐cloud density, regulating microenvironment ions ensuring nucleation. MCOF‐based separator's well‐defined 1D channels in separator enable uniform flux, promote resulting transference number 0.93 ionic conductivity 2.01 mS cm −1 at room temperature. Li|Cu cell demonstrates a barrier 16 mV, while symmetric exhibits stable plating/stripping over 1600 h 0.5 mA −2 . When coupled LiFePO 4 cathodes, assembled capacity retention ≈98%. work paves way dendrite‐free anodes high‐performance

Language: Английский

Multilevel-Regulated Metal–Organic Framework Platform Integrating Pore Space Partition and Open-Metal Sites for Enhanced CO2 Photoreduction to CO with Nearly 100% Selectivity DOI Creative Commons
Huili Zheng, Jian-Qiang Zhao, Yayong Sun

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(50), P. 27728 - 27739

Published: Dec. 6, 2023

Rational design and regulation of atomically precise photocatalysts are essential for constructing efficient photocatalytic systems tunable at both the atomic molecular levels. Herein, we propose a platform-based strategy capable integrating pore space partition (PSP) open-metal sites (OMSs) as foundational features high-performance photocatalysts. We demonstrate first structural prototype obtained from this strategy: pore-partitioned NiTCPE-pstp (TCPE = 1,1,2,2-tetra(4-carboxylphenyl)ethylene, pstp partitioned stp topology). Nonpartitioned NiTCPE-stp is constructed six-connected [Ni3(μ3–OH)(COO)6] trimer TCPE linker to form 1D hexagonal channels with six coplanar OMSs directed channel centers. After introducing triangular pore-partitioning ligands, half were retained, while other used PSP, leading unprecedented microenvironment structure. The resulting material integrates multiple advanced properties, including robustness, wider absorption range, enhanced electronic conductivity, high CO2 adsorption, all which highly desirable applications. Remarkably, exhibits excellent photoreduction activity CO generation rate 3353.6 μmol g–1 h–1 nearly 100% selectivity. Theoretical experimental studies show that introduction partitioning ligands not only optimizes structure promote separation transfer photogenerated carriers but also reduces energy barrier formation *COOH intermediates promoting activation desorption. This work believed be example integrate PSP strategies within metal–organic framework (MOF) photocatalysts, provides new insight well performance optimization MOF-based

Language: Английский

Citations

48
Relative Local Electron Density Tuning in Metal‐Covalent Organic Frameworks for Boosting CO2 Photoreduction DOI
Mi Zhang, Pei Huang,

Jia‐Peng Liao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 15, 2023

The high local electron density and efficient charge carrier separation are two important factors to affect photocatalytic activity, especially for the CO2 photoreduction reaction. However, systematic studies on structure-functional relationship regarding above based precisely structure model rarely reported. Herein, as a proof-of-concept, we developed new strategy evaluation of by controlling relative electron-deficient (ED) electron-rich (ER) intensity monomer at molecular level three rational-designed vinylene-linked sp2 carbon-covalent organic frameworks (COFs). As expected, as-prepared carbon-conjugated metal-covalent framework (MCOFs) (VL-MCOF-1) with junction exhibited excellent activities -to-HCOOH conversion (283.41 μmol g-1 h-1 ) selectivity 97.1 %, much higher than VL-MCOF-2 g-C34 N6 -COF, which is due synergistic effect multi-electronic metal clusters (Cu3 (PyCA)3 (PyCA=pyrazolate-4-carboxaldehyde) strong ER roles cyanopyridine units ED active sites, well boosted photo-induced efficiency vinyl connection increased light utilization ability. These results not only provide regulating electron-density distribution photocatalysts but also offers profound insights clusters-based COFs effective conversion.

Language: Английский

Citations

44
Covalent Organic Frameworks for Photocatalytic Reduction of Carbon Dioxide: A Review DOI
Jinglun Yang, Zihao Chen, Lei Zhang

et al.

ACS Nano, Journal Year: 2024, Volume and Issue: 18(33), P. 21804 - 21835

Published: Aug. 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.

Language: Английский

Citations

32
Covalent Organic Framework with Donor1‐Acceptor‐Donor2 Motifs Regulating Local Charge of Intercalated Single Cobalt Sites for Photocatalytic CO2 Reduction to Syngas DOI
Xingwang Lan,

Hangshuai Li,

Yuemeng Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 22, 2024

Covalent organic framework (COF) has attracted increasing interest in photocatalytic CO

Language: Английский

Citations

27
Regulating local charge distribution of single Ni sites in covalent organic frameworks for enhanced photocatalytic CO2 reduction DOI

Yize Zhang,

Yuemeng Liu,

Hangshuai Li

et al.

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 489, P. 151479 - 151479

Published: April 19, 2024

Language: Английский

Citations

26
12 Connecting Sites Linked Three‐dimensional Covalent Organic Frameworks with Intrinsic Non‐interpenetrated shp Topology for Photocatalytic H2O2 Synthesis DOI
Xinxin Wang, Yucheng Jin, Ning Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Feb. 9, 2024

Developing high connectivity (>8) three-dimensional (3D) covalent organic frameworks (COFs) towards new topologies and functions remains a great challenge owing to the difficulty in getting building blocks. This however represents most important step promoting diversity of COFs due still limited dynamic bonds available for constructing at this stage. Herein, highly connected phthalocyanine-based (Pc-based) 3D MPc-THHI-COFs (M=H

Language: Английский

Citations

23
Vinylene‐linked Donor‐π‐Acceptor Metal‐Covalent Organic Framework for Enhanced Photocatalytic CO2 Reduction DOI Open Access
Shanshan Li, Chaomin Gao, Haihan Yu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(48)

Published: Sept. 3, 2024

Abstract Intramolecular charge separation driving force and linkage chemistry between building blocks are critical factors for enhancing the photocatalytic performance of metal‐covalent organic framework (MCOF) based photocatalyst. However, robust achieving both simultaneously has yet to be challenging despite ongoing efforts. Here we develop a fully π‐conjugated vinylene‐linked multivariate donor‐π‐acceptor MCOF (D‐π‐A, termed UJN‐1) by integrating benzyl cyanides linker with multiple functional electron‐rich triphenylamine electron‐deficient copper‐cyclic trinuclear units (Cu‐CTUs) moieties, featuring strong intramolecular force, extended conjugation degree skeleton, abundant active sites. The incorporation Cu‐CTUs acceptor electron‐withdrawing ability concomitantly giant can efficiently accelerate photogenerated electrons transfer from Cu‐CTUs, revealing experiments theoretical calculations. Benefiting synergistically effect D‐π‐A configuration vinylene linkage, highly‐efficient spatial is achieved. Consequently, UJN‐1 exhibits an excellent CO formation rate 114.8 μmol g −1 in 4 h without any co‐catalysts or sacrificial reagents under visible light, outperforming those analogous MCOFs imine‐linked (UJN‐2, 28.9 ) COF Cu‐CTU sites (UJN‐3, 50.0 ), emphasizing role designing novel COFs‐based

Language: Английский

Citations

21
Covalent Organic Framework Stabilized Single CoN4Cl2 Site Boosts Photocatalytic CO2 Reduction into Tunable Syngas DOI Open Access
Ping Fu, Cailing Chen, Chao Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 28, 2024

Solar carbon dioxide (CO

Citations

18
Morpholine-linked metal-phthalocyanine covalent organic frameworks for enhanced photocatalytic CO2 reduction DOI

Fu‐Wen Lin,

Wan Lin,

Jing Lin

et al.

Journal of Materials Chemistry A, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Innovative morpholine-linked metal-phthalocyanine covalent organic frameworks were constructed. The electron delocalization properties of Co-DB-COF accelerate the charge transfer rate, improving photocatalytic CO 2 reduction reaction performance.

Language: Английский

Citations

2
Covalent Metal–Organic Frameworks: Fusion of Covalent Organic Frameworks and Metal–Organic Frameworks DOI
Rong‐Jia Wei, Xiao Luo, Guo‐Hong Ning

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 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.

Language: Английский

Citations

2