Hydrogen‐bond‐regulated mechanochemical synthesis of covalent organic frameworks: cocrystal precursor strategy for confined assembly DOI Open Access
Hongguang Chen, Daming Feng, Fengxia Wei

et al.

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

Published: Oct. 8, 2024

Abstract Two‐dimensional imine covalent organic frameworks (2D imine‐COFs) are crystalline porous materials with broad application prospects. Despite the efforts into their design and synthesis, mechanisms of formation still not fully understood. Herein, a one‐pot two‐step mechanochemical cocrystal precursor synthetic strategy is developed for efficient construction 2D imine‐COFs. The mechanistic investigation demonstrated that precursors 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)trianiline ( TAPT ) p ‐toluenesulphonic acid PTSA sufficiently regulate structure COF. Evidenced by characterizations theoretical studies, helical hydrogen‐bond network was constructed N−H⋅⋅⋅O supramolecular synthons between amino sulfonic groups in TAPT‐PTSA , demonstrating role cocrystals promoting organized stacking interlayer π–π interactions, layer arrangement, spacing, thus facilitating orderly assembly COFs. Moreover, protonation degree amines, which tuned nucleophilic directionality, enabled sequential progression intra‐ condensation reactions, inhibiting amorphous polymers. transformation from to COFs achieved through comprehensive control hydrogen bond sites. This work significantly advances concept hydrogen‐bond‐regulated COF its method synthesis imine‐COFs, further elucidating aspects synthesis.

Language: Английский

Direct Laser Scribing of All‐Solid‐State In‐Plane Proton Microsupercapacitors on Ionic Covalent Organic Framework Films DOI Open Access
X Li, Dong‐Dong Han,

Ye‐Can Zhang

et al.

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

Published: March 10, 2025

Abstract Proton microsupercapacitors (MSCs) are promising energy storage devices for cutting‐edge applications. However, all‐solid‐state designs face challenges due to the need synergistic innovations in electrolytes, electrodes, and interface engineering. Herein, direct laser scribing of metal‐free in‐plane proton MSCs reported on ionic covalent organic framework (iCOF) films. The solid‐state AA‐stacked iCOF electrolytes with perfect 2D channels ( d = 0.33 nm) prepared by vacuum filtration, exhibiting conductivities from 0.23 4.7 mS cm −1 depending humidity. Furthermore, patterned carbon electrodes fabricated via situ carbonization iCOFs, forming a seamless electrolyte‒electrode interface. To reveal photophysical features insulating iCOFs conductive laser‐treated femtosecond transient absorption experiments carried out. multiphysics simulation indicates that electric field is uniformly distributed at electrode−electrolyte Notably, resulting MSC exhibits an ultrahigh specific capacitance (≈10.13 mF −2 101.3 F −3 ), high volumetric density (2.52 mWh rapid scan rate (1000 mV s excellent cycling stability (no degradation after 50 000 cycles). This approach provides high‐performance MSCs, revealing great potential applications intelligent microsystems.

Language: Английский

Citations

3
Improving Active Site Local Proton Transfer in Porous Organic Polymers for Boosted Oxygen Electrocatalysis DOI
Qian Zhao, Qingxin Zhang, Yuhan Xu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(47)

Published: Aug. 15, 2024

Abstract Improving proton transfer is vital for electrocatalysis with porous materials. Although several strategies are reported to assist in channels, few studies dedicated improving at the local environments of active sites Herein, we report on new Co‐corrole‐based organic polymers (POPs) improved electrocatalytic oxygen reduction reaction (ORR) and evolution (OER). By tuning pore sizes installing relays Co corrole sites, designed synthesized POP‐2‐OH both channels sites. This POP shows remarkable activity ORR E 1/2 =0.91 V vs RHE OER η 10 =255 mV. Therefore, this work significant present a strategy improve site materials highlight key role such structural functionalization boosting electrocatalysis.

Language: Английский

Citations

6
Hydrogen‐bond‐regulated mechanochemical synthesis of covalent organic frameworks: cocrystal precursor strategy for confined assembly DOI
Hongguang Chen, Daming Feng, Fengxia Wei

et al.

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

Published: Oct. 8, 2024

Abstract Two‐dimensional imine covalent organic frameworks (2D imine‐COFs) are crystalline porous materials with broad application prospects. Despite the efforts into their design and synthesis, mechanisms of formation still not fully understood. Herein, a one‐pot two‐step mechanochemical cocrystal precursor synthetic strategy is developed for efficient construction 2D imine‐COFs. The mechanistic investigation demonstrated that precursors 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)trianiline ( TAPT ) p ‐toluenesulphonic acid PTSA sufficiently regulate structure COF. Evidenced by characterizations theoretical studies, helical hydrogen‐bond network was constructed N−H⋅⋅⋅O supramolecular synthons between amino sulfonic groups in TAPT‐PTSA , demonstrating role cocrystals promoting organized stacking interlayer π–π interactions, layer arrangement, spacing, thus facilitating orderly assembly COFs. Moreover, protonation degree amines, which tuned nucleophilic directionality, enabled sequential progression intra‐ condensation reactions, inhibiting amorphous polymers. transformation from to COFs achieved through comprehensive control hydrogen bond sites. This work significantly advances concept hydrogen‐bond‐regulated COF its method synthesis imine‐COFs, further elucidating aspects synthesis.

Language: Английский

Citations

4
Efficient Electrosynthesis of Hydrogen Peroxide Enabled by a Hierarchical Hollow RE–P–O (RE = Sm, La, Gd) Architecture with Open Channels DOI Creative Commons
Zhiwei Liu, Zhaowu Wang, Dong-Jun Lv

et al.

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

Published: Jan. 2, 2025

Abstract The electrochemical two‐electron oxygen reduction reaction (2e − ORR) offers a sustainable pathway for the production of H 2 O ; however, development electrocatalysts with exceptional activity, selectivity, and long‐term stability remains challenging task. Herein, novel approach is presented to addressing this challenge by synthesizing hierarchical hollow SmPO 4 nanospheres open channels via two‐step hydrothermal treatment. produced compound demonstrates remarkable 2e exceeding 93% across wide potential range 0.0–0.6 V in 0.1 m KOH, peak 96% at 0.45 V. When employed as cathode flow cell, synthesized exhibits impressive 100 mA cm −2 12 h, consistently achieving Faradaic efficiency above 90%. Using X‐ray absorption, situ Raman Fourier‐transform infrared spectroscopies, theoretical calculations, post‐ORR assessments, it found that possesses intrinsic characterized optimal metal atomic spacing, structural compositional stabilities. These factors significantly enhance thermodynamics, kinetics, ORR process. Notably, also outstanding performance neutral environments. Furthermore, strategy can be extended other rare‐earth–P–O compounds, demonstrating excellent under both alkaline conditions.

Language: Английский

Citations

0
Randomly oriented covalent organic framework membrane for selective Li+ sieving from other ions DOI Creative Commons

Shiwen Bao,

Zhaoyu Ma, Lei Yu

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 24, 2025

Language: Английский

Citations

0
Artificial Proton Channel Membrane with Self-Amplified Selectivity for Simultaneous Waste Acid Recovery and Power Generation DOI

Min Jian,

Xuan Ding, Decheng Li

et al.

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: April 26, 2025

Proton channels have both high permeability and selectivity, a property that remains unparalleled by artificial materials yet is highly demanded in many applications, including acid recovery power generation. This work takes inspiration from the structure surface chemistry of biological proton presents method to construct covalent organic framework (COF) membranes consisting high-performance channels. The membrane was purposefully rendered amorphous, which eliminates most nanoscale pores induces steric hindrance ions. On other hand, were functionalized with hydrogen-donating groups, allowing protons hop fast. Interestingly, we found presence hydrated causes additional ions thus self-amplifies selectivity. Consequently, selectivity against toxic heavy metal up 104, significantly surpassing commercial acid-recovery membranes. comparable (a few mol m-2 h-1). Such allow us recycle industrial waste brines simple diffusion dialysis process without risk ion leakage. At same time, entropy released can be harvested generate power, achieving density superior previously reported for osmotic energy harvesting.

Language: Английский

Citations

0
Engineering Bipolar Covalent Organic Framework Membranes for Selective Acid Extraction DOI
Di Wu, Zhiwei Xing, Qing Guo

et al.

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: April 29, 2025

Nitric acid (HNO3) is a vital industrial chemical, and its recovery from complex waste streams essential for sustainability resource optimization. This study demonstrates the effectiveness of bipolar covalent organic framework (COF) membranes with tunable ionic site distributions as solution this challenge. The are fabricated by layering anionic COF nanosheets on cationic layers, supported porous substrate. resulting exhibit significant rectifying behavior, driven asymmetric charge polarity intrinsic electric field, which enhances HNO3 transport. transmembrane diffusion coefficient 2.74 × 10-5 cm2 s-1 exceeds self-diffusion rate NO3 -, leading to increased flux selectivity compared individual membranes. optimized membrane configuration achieves remarkable separation factors, ranging 22 242,000 HNO₃, in comparison other solutes such HCl, H2SO4, H3PO4, various metal salts an eight-component mixed stream. results substantial increase HNO₃ purity, 12.5% 94.1% after single separation. With broad range materials versatility proposed design, work represents advancement chemical technologies.

Language: Английский

Citations

0
Engineering Bipolar Covalent Organic Framework Membranes for Selective Acid Extraction DOI
Di Wu, Zhiwei Xing, Qing Guo

et al.

Angewandte Chemie, Journal Year: 2025, Volume and Issue: unknown

Published: April 29, 2025

Abstract Nitric acid (HNO 3 ) is a vital industrial chemical, and its recovery from complex waste streams essential for sustainability resource optimization. This study demonstrates the effectiveness of bipolar covalent organic framework (COF) membranes with tunable ionic site distributions as solution this challenge. The are fabricated by layering anionic COF nanosheets on cationic layers, supported porous substrate. resulting exhibit significant rectifying behavior, driven asymmetric charge polarity intrinsic electric field, which enhances HNO transport. transmembrane diffusion coefficient 2.74 × 10 −5 cm 2 s −1 exceeds self‐diffusion rate NO − , leading to increased flux selectivity compared individual membranes. optimized membrane configuration achieves remarkable separation factors, ranging 22 242,000 HNO₃, in comparison other solutes such HCl, H SO 4 PO various metal salts an eight‐component mixed stream. results substantial increase HNO₃ purity, 12.5% 94.1% after single separation. With broad range materials versatility proposed design, work represents advancement chemical technologies.

Language: Английский

Citations

0
Improving Active Site Local Proton Transfer in Porous Organic Polymers for Boosted Oxygen Electrocatalysis DOI Open Access
Qian Zhao, Qingxin Zhang, Yuhan Xu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(47)

Published: Aug. 15, 2024

Abstract Improving proton transfer is vital for electrocatalysis with porous materials. Although several strategies are reported to assist in channels, few studies dedicated improving at the local environments of active sites Herein, we report on new Co‐corrole‐based organic polymers (POPs) improved electrocatalytic oxygen reduction reaction (ORR) and evolution (OER). By tuning pore sizes installing relays Co corrole sites, designed synthesized POP‐2‐OH both channels sites. This POP shows remarkable activity ORR E 1/2 =0.91 V vs RHE OER η 10 =255 mV. Therefore, this work significant present a strategy improve site materials highlight key role such structural functionalization boosting electrocatalysis.

Language: Английский

Citations

1
Hydrogen‐bond‐regulated mechanochemical synthesis of covalent organic frameworks: cocrystal precursor strategy for confined assembly DOI Open Access
Hongguang Chen, Daming Feng, Fengxia Wei

et al.

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

Published: Oct. 8, 2024

Abstract Two‐dimensional imine covalent organic frameworks (2D imine‐COFs) are crystalline porous materials with broad application prospects. Despite the efforts into their design and synthesis, mechanisms of formation still not fully understood. Herein, a one‐pot two‐step mechanochemical cocrystal precursor synthetic strategy is developed for efficient construction 2D imine‐COFs. The mechanistic investigation demonstrated that precursors 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)trianiline ( TAPT ) p ‐toluenesulphonic acid PTSA sufficiently regulate structure COF. Evidenced by characterizations theoretical studies, helical hydrogen‐bond network was constructed N−H⋅⋅⋅O supramolecular synthons between amino sulfonic groups in TAPT‐PTSA , demonstrating role cocrystals promoting organized stacking interlayer π–π interactions, layer arrangement, spacing, thus facilitating orderly assembly COFs. Moreover, protonation degree amines, which tuned nucleophilic directionality, enabled sequential progression intra‐ condensation reactions, inhibiting amorphous polymers. transformation from to COFs achieved through comprehensive control hydrogen bond sites. This work significantly advances concept hydrogen‐bond‐regulated COF its method synthesis imine‐COFs, further elucidating aspects synthesis.

Language: Английский

Citations

0