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

Gold(I)-Organic Frameworks as Catalysts for Carboxylation of Alkynes with CO2 DOI
Rong‐Jia Wei, Mo Xie, Ri‐Qin Xia

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(41), P. 22720 - 22727

Published: Oct. 4, 2023

Construction of gold-based metal-organic frameworks (Au-MOFs) would bring the merits gold chemistry into MOFs. However, it still remains challenging because cations are easily reduced to metallic under solvothermal conditions. Herein, we present first example Au-MOFs prepared from networking cyclic trinuclear gold(I) complexes by formal transimination reaction in a rapid (<15 min) and scalable (up 1 g) fashion ambient condition. The feature uniform porosity, high crystallinity, superior chemical stability toward base (i.e., 20 M NaOH). With open Au(I) sites skeleton, as heterogeneous catalysts delivered good performance substrate tolerance for carboxylation reactions alkynes with CO2. This work demonstrates facile approach reticularly synthesize combining coordination dynamic covalent chemistry.

Language: Английский

Citations

34
Hydrothermal synthesis of polyimide-linked covalent organic frameworks towards ultrafast and stable cathodic sodium storage DOI
Xiya Yang, Lei Gong, Zhixin Liu

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(4), P. 1300 - 1310

Published: Jan. 8, 2024

Language: Английский

Citations

16
3D Covalent Organic Frameworks with 16-Connectivity for Photocatalytic C(sp3)–C(sp2) Cross-Coupling DOI
Meng Lu, Shuai‐Bing Zhang, Run‐Han Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25832 - 25840

Published: Sept. 4, 2024

The connectivity (valency) of building blocks for constructing 3D covalent organic frameworks (COFs) has long been limited to 4, 6, 8, and 12. Developing a higher remains great challenge in the field COF structural design. Herein, this work reports hierarchical expansion strategy making 16-connected construct COFs with sqc topology. [16 + 2] construction achieved by condensation between carbazolyl dicyanobenzene-based block (CzTPN) linear diamino linkers (BD or Bpy) affords two (named CzBD CzBpy COF). Furthermore, attributed well-organized donor-acceptor (D-A) heterojunction, Ni chelated (Ni@CzBpy COF) exhibits excellent performance photoredox/Ni dual catalytic C(sp

Language: Английский

Citations

13
Precise Regulation of Interlayer Stacking Modes in Trinuclear Copper Organic Frameworks for Efficient Photocatalytic Reduction of Uranium(VI) DOI Creative Commons

Zhi Qiang Gao,

Sijia Lv,

Yue Wang

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 27, 2024

Abstract The interlayer stacking modes of 2D covalent‐organic frameworks (COFs) directly influence their structural features, ultimately determining functional output. However, controllably modulating the structure in traditional metal‐free COFs, based on same building blocks, remains challenging. Here, two trinuclear copper organic are synthesized successfully with different structures: eclipsed AA Cu 3 ‐PA‐COF‐AA and staggered ABC ‐PA‐COF‐ABC, using monomers. Remarkably, various functionalities, including porosity electronic optical properties, can be effectively regulated by stacking. As a result, ‐PA‐COF‐ABC exhibit significantly activities toward photoreduction U(VI), presenting promising strategy for removing radioactive uranium pollution. Due to its broader visible‐light absorption range superior photogenerated carrier migration separation efficiency, achieves U(VI) removal ratio 93.6% without additional sacrificial agents an air atmosphere—≈2.2 times higher than that (42.0%). To best knowledge, this is first study elucidate effect COFs photocatalytic activity reduction. This finding may inspire further exploration structure‐function relationship as photocatalysts potential photoinduced radionuclides.

Language: Английский

Citations

9
Pyridyl‐Imine‐Functionalized Donor–Acceptor Covalent Organic Frameworks for Optimal Photosynthesis of Hydrogen Peroxide DOI Open Access
Zixuan Li,

Bingzi Cai,

Ying Zou

et al.

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

Published: Feb. 3, 2025

Abstract The artificial photosynthesis of hydrogen peroxide (H 2 O ) using semiconductor photocatalysts is gaining attention as an eco‐friendly and energy‐efficient method. Covalent organic frameworks (COFs) show great promise in enhancing photocatalytic H production due to their tunable structures functional diversity. However, the efficiency generation close photoelectric properties COFs microenvironment active sites. Herein, synthesis pyridyl‐imine‐functionalized (PyIm‐COFs) featuring donor–acceptor (D–A) moieties improve reported. By employing benzothiadiazole (BT) units with varied fluorine substitutions, electronic environment sites, optimizing selective two‐electron (2e − oxygen reduction reaction (ORR), tuned. Among synthesized COFs, PyIm‐BT_F exhibits highest activity, achieving a rate 5342 µmol g −1 h . importance D–A rational design COF‐based photocatalysts, providing novel strategy for sustainable through optimized site environments, underscored.

Language: Английский

Citations

1
Covalent organic frameworks embedding single cadmium sites for efficient carboxylative cyclization of CO2with propargylic amines DOI

Yize Zhang,

Hangshuai Li,

Xingyue He

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(14), P. 5557 - 5565

Published: Jan. 1, 2023

Single cadmium sites on covalent organic frameworks promote adsorption and activation of CO 2 to efficiently catalyze cyclization propargylic amines.

Language: Английский

Citations

21
Covalent Organic Frameworks: Opportunities for Rational Materials Design in Cancer Therapy DOI Open Access
Lele Zhou, Qun Guan, Yu‐Bin Dong

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(8)

Published: Nov. 21, 2023

Nanomedicines are extensively used in cancer therapy. Covalent organic frameworks (COFs) crystalline porous materials with several benefits for therapy, including porosity, design flexibility, functionalizability, and biocompatibility. This review examines the use of COFs therapy from perspective reticular chemistry function-oriented design. First, modification sites functionalization methods discussed, followed by their potential as multifunctional nanoplatforms tumor targeting, imaging, integrating functional components. Finally, some challenges clinical translation presented hope promoting development COF-based anticancer nanomedicines bringing closer to trials.

Language: Английский

Citations

18
Constructing 2D Phthalocyanine Covalent Organic Framework with Enhanced Stability and Conductivity via Interlayer Hydrogen Bonding as Electrocatalyst for CO2 Reduction DOI

Mingrun Li,

Bin Han,

Senzhi Li

et al.

Small, Journal Year: 2024, Volume and Issue: 20(30)

Published: Feb. 20, 2024

Abstract Fabricating COFs‐based electrocatalysts with high stability and conductivity still remains a great challenge. Herein, 2D polyimide‐linked phthalocyanine COF (denoted as NiPc‐OH‐COF) is constructed via solvothermal reaction between tetraanhydrides of 2,3,9,10,16,17,23,24‐octacarboxyphthalocyaninato nickel(II) 2,5‐diamino‐1,4‐benzenediol (DB) other two analogous COFs NiPc‐OMe‐COF NiPc‐H‐COF) synthesized for reference. In comparison NiPc‐H‐COF, NiPc‐OH‐COF exhibits enhanced stability, particularly in strong NaOH solvent 1.5 × 10 −3 S m −1 due to the incorporation additional interlayer hydrogen bonding interaction O−H DB hydroxy “O” atom adjacent layers. This turn endows electrode ultrahigh CO 2 ‐to‐CO faradaic efficiency (almost 100%) wide potential range from −0.7 −1.1 V versus reversible (RHE), large partial current density −39.2 mA cm −2 at RHE, turnover number well frequency, amounting 45 000 0.76 −0.80 RHE during 12 h lasting measurement.

Language: Английский

Citations

7
Nanostructurally Engineering Covalent Organic Frameworks for Boosting CO2 Photoreduction DOI
Tianyu Zheng,

Xu Ding,

Tingting Sun

et al.

Small, Journal Year: 2023, Volume and Issue: 20(15)

Published: Nov. 27, 2023

Abstract Herein, a series of imine‐linked covalent organic frameworks (COFs) are developed with advanced ordered mesoporous hollow spherical nanomorphology and ultra‐large mesopores (4.6 nm in size), named OMHS‐COF‐M (M = H, Co, Ni). The is revealed to be formed via an Ostwald ripening mechanism based on one‐step self‐templated strategy. Encouraged by its unique structural features outstanding photoelectrical property, the OMHS‐COF‐Co material applied as photocatalyst for CO 2 ‐to‐CO reduction. Remarkably, it delivers impressive production rate high 15 874 µmol g −1 h , large selectivity 92.4%, preeminent cycling stability. From in/ex situ experiments density functional theory (DFT) calculations, excellent photoreduction performance ascribed desirable cooperation host abundant isolated Co active sites, enhancing activation, improving electron transfer kinetics well reducing energy barriers intermediates *COOH generation desorption.

Language: Английский

Citations

15
Structural survey of metal-covalent organic frameworks and covalent metal-organic frameworks DOI

Chaozhi Xiong,

Zhen‐Wu Shao,

Jia’nan Hong

et al.

International Journal of Minerals Metallurgy and Materials, Journal Year: 2023, Volume and Issue: 30(12), P. 2297 - 2309

Published: Dec. 1, 2023

Language: Английский

Citations

12