Manipulating p‐π Resonance through Methoxy Group Engineering in Covalent Organic Frameworks for an Efficient Photocatalytic Hydrogen Evolution DOI
Zhipeng Luo,

Shipeng Zhu,

Haizhou Xue

et al.

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

Published: Dec. 23, 2024

Abstract Kinetic factors frequently emerge as the primary constraints in photocatalysis, exerting a critical influence on efficacy of polymeric photocatalysts. The diverse conjugation systems within covalent organic frameworks (COFs) can significantly impact photon absorption, energy level structures, charge separation and migration kinetics. Consequently, these limitations often manifest unsatisfactory kinetic behavior, which adversely affects photocatalytic activity COFs. To address challenges, we propose methoxy (−OMe) molecular engineering strategy designed to enhance carrier kinetics mitigate mass transfer resistance. Through strategic modulation position quantity −OMe units, effectively manipulate p‐π conjugation, thereby enhancing migration. Moreover, COFs enriched with moieties exhibit enhanced dynamics due hydrophilic nature groups, facilitate diffusion reactants products porous structure. This approach is hypothesized drive an efficient hydrogen evolution reaction.

Language: Английский

Dual–Acceptor Engineering in Pyrene‐Based Covalent Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution DOI

Nengyi Liu,

Shuailei Xie, Yuxing Huang

et al.

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(40)

Published: July 18, 2024

Abstract The integration of electron donor (D) and acceptor (A) units into covalent organic frameworks (COFs) has received increasing interest due to its potential for efficient photocatalytic hydrogen (H 2 ) evolution from water. Nevertheless, the advancement D–A COFs is still constrained by limited investigations on engineering, which enables highly effective charge transfer pathways in deliver photoexcited electrons a preferential orientation enhance performance. Herein, two systems with D–A–A configurations based molecular engineering strategy are proposed construct three distinct COFs. Specifically, TAPPy‐DBTDP‐COF merging one pyrene‐based benzothiadiazole acceptors realized an average H rate 12.7 mmol h −1 g under visible light, among highest ever reported typical D–A‐type COF systems. combination experimental theoretical analysis signifies crucial role dual‐acceptor arrangement promoting exciton dissociation carrier migration. These findings underscore significant structural design, conducive separation holes resulting superior activities.

Language: Английский

Citations

31
Programming Tetrathiafulvalene‐Based Covalent Organic Frameworks for Promoted Photoinduced Molecular Oxygen Activation DOI

Hetao Xu,

Shuling Xia,

Chunlei Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: May 6, 2024

Abstract Despite the pivotal role of molecular oxygen (O 2 ) activation in artificial photosynthesis, efficiency is often restricted by sluggish exciton dissociation and charge transfer kinetics within polymer photocatalysts. Herein, we propose two tetrathiafulvalene (TTF)‐based imine‐linked covalent organic frameworks (COFs) with tailored donor‐acceptor (D–A) structures, TTF‐PDI‐COF TTF‐TFPP‐COF, to promote O activation. Because enhanced electron push‐pull interactions that facilitated separation behavior, exhibited superior photocatalytic activity electron‐induced reactions over TTF‐TFPP‐COF under visible light irradiation, including photosynthesis ( E )‐3‐amino‐2‐thiocyano‐ α , β ‐unsaturated compounds H . These findings highlight significant potential rational design COFs D–A configurations as suitable candidates for advanced applications.

Language: Английский

Citations

22
Thermally triggered topological polymerization in diacetylene-functionalized covalent organic framework toward enhanced memristive properties DOI
Pan‐Ke Zhou, Yuxing Huang, Ziyue Yu

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 3, 2025

Language: Английский

Citations

1
Engineering Titanium Dioxide/Titanocene-Polysulfide Interface for Flexible, Optical-Modulated, and Thermal-Tolerant Multilevel Memristor DOI
Pan‐Ke Zhou, Xi Lin,

Yiqun Gao

et al.

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

Published: Feb. 7, 2025

Multifunctional memristors with a high memory density, low power consumption, flexibility, programmability, and environmental robustness are essential for next-generation memories. In this work, titanocene-polysulfide complex (Cp2TiS5) strong S···S interactions hydrogen bonds was synthesized integrated TiO2 to create novel Cu/TiO2/Cp2TiS5/Ag memristor. This device shows bipolar nonvolatile performance remarkable ON/OFF ratio (104.8), switching voltages (VSET, -0.16 V; VRESET, +0.15 V), consumption (2.7 × 10-4 μW). It exhibits multilevel behavior, optical modulation (VSET decreases from -1.35 -0.17 V decreasing irradiation wavelength), thermal tolerance (up 200 °C). The electron-rich Cp2TiS5 layer protects the Ag-CFs, while TiO2's oxygen vacancies unsaturated Ti atoms interact sulfur Cp2TiS5, lowering Schottky barrier facilitating charge transport. work offers promising opportunities in flexible memristive devices neuromorphic computing under extreme conditions.

Language: Английский

Citations

1
Programming Tetrathiafulvalene‐Based Covalent Organic Frameworks for Promoted Photoinduced Molecular Oxygen Activation DOI

Hetao Xu,

Shuling Xia,

Chunlei Li

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(29)

Published: May 6, 2024

Abstract Despite the pivotal role of molecular oxygen (O 2 ) activation in artificial photosynthesis, efficiency is often restricted by sluggish exciton dissociation and charge transfer kinetics within polymer photocatalysts. Herein, we propose two tetrathiafulvalene (TTF)‐based imine‐linked covalent organic frameworks (COFs) with tailored donor‐acceptor (D–A) structures, TTF‐PDI‐COF TTF‐TFPP‐COF, to promote O activation. Because enhanced electron push‐pull interactions that facilitated separation behavior, exhibited superior photocatalytic activity electron‐induced reactions over TTF‐TFPP‐COF under visible light irradiation, including photosynthesis ( E )‐3‐amino‐2‐thiocyano‐ α , β ‐unsaturated compounds H . These findings highlight significant potential rational design COFs D–A configurations as suitable candidates for advanced applications.

Language: Английский

Citations

5
2D photocatalysts for hydrogen peroxide synthesis DOI
Liyong Ding, Zhenhua Pan, Qian Wang

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(12), P. 110125 - 110125

Published: June 18, 2024

Language: Английский

Citations

5
Self-Template Hydrothermal Synthesis of Vinylene-Linked Covalent Organic Framework Nanosheets Confined at the Molecule/Water Interface for an Organic Memristor DOI
Hao Wang, Dongchuang Wu, Kexin Chen

et al.

ACS Materials Letters, Journal Year: 2024, Volume and Issue: unknown, P. 3376 - 3383

Published: July 1, 2024

Vinylene-linked covalent organic frameworks (COFs) are traditionally synthesized through solvothermal methods using solvents. However, the laborious process of optimizing solvent ratios and environmental harm caused by solvents constrain facile large-scale synthesis COFs. Consequently, employing water as an environmentally benign reaction medium is highly desirable for synthesizing chemically stable vinylene-linked COF materials. In this study, we report a novel self-template hydrothermal approach preparing nanosheets via molecule/water interfacial Knoevenagel condensation. These exhibit substantial resistance to both acids alkalis. The COF-based memristor demonstrated characteristic nonvolatile rewritable memory effects, featuring small switch-on voltage −0.65 V ultrafast switching speed 120 ns. Benefiting from chemical durability nanosheets, maintained excellent stability in retention performance after acid base treatments. Moreover, memristors successfully performed "AND" "OR" logic operations, demonstrating their potential advanced computing applications.

Language: Английский

Citations

4
Dual Redox‐active Covalent Organic Framework‐based Memristors for Highly‐efficient Neuromorphic Computing DOI Open Access

Qiongshan Zhang,

Qiang Che,

Dongchuang Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: Aug. 6, 2024

Abstract Organic memristors based on covalent organic frameworks (COFs) exhibit significant potential for future neuromorphic computing applications. The preparation of high‐quality COF nanosheets through appropriate structural design and building block selection is critical the enhancement memristor performance. In this study, a novel room‐temperature single‐phase method was used to synthesize Ta−Cu 3 COF, which contains two redox‐active units: trinuclear copper triphenylamine. resultant were dispersed acid‐assisted exfoliation subsequently spin‐coated fabricate film an indium tin oxide (ITO) substrate. synergistic effect dual centers in film, combined with its distinct crystallinity, significantly reduces redox energy barrier, enabling efficient modulation 128 non‐volatile conductive states Al/Ta−Cu COF/ITO memristor. Utilizing convolutional neural network (CNN) these conductance states, image recognition ten representative campus landmarks successfully executed, achieving high accuracy 95.13 % after 25 training epochs. Compared devices binary exhibits 45.56 improvement enhances efficiency computing.

Language: Английский

Citations

4
Covalent organic framework nanomaterials: Syntheses, architectures, and applications DOI
Qing Li, Yuanyuan Zhu,

Tao Pan

et al.

Advances in Colloid and Interface Science, Journal Year: 2025, Volume and Issue: 339, P. 103427 - 103427

Published: Feb. 6, 2025

Language: Английский

Citations

0
Emerging Artificial Synaptic Devices Based on Organic Semiconductors: Molecular Design, Structure and Applications DOI
Yunchao Xu, Yuan He, Dongyong Shan

et al.

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

In modern computing, the Von Neumann architecture faces challenges such as memory bottleneck, hindering efficient processing of large datasets and concurrent programs. Neuromorphic inspired by brain's architecture, emerges a promising alternative, offering unparalleled computational power while consuming less energy. Artificial synaptic devices play crucial role in this paradigm shift. Various material systems, from organic to inorganic, have been explored for neuromorphic devices, with materials attracting attention their excellent photoelectric properties, diverse choices, versatile preparation methods. Organic semiconductors, particular, offer advantages over transition-metal dichalcogenides, including ease flexibility, making them suitable large-area films. This review focuses on emerging artificial based discussing different branches within semiconductor system, various fabrication methods, device structure designs, applications synapse. Critical considerations achieving truly human-like dynamic perception systems semiconductors are also outlined, reflecting ongoing evolution computing.

Language: Английский

Citations

0