Rational Design of Covalent Organic Frameworks with Redox-Active Catechol Moieties for High-Performance Overall Photosynthesis of Hydrogen Peroxide

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(10), P. 7736 - 7745

Published: May 2, 2024

Covalent organic frameworks (COFs) have emerged as promising candidates for solar-driven photosynthesis of hydrogen peroxide (H2O2), yet the development high-performance COFs tailored practical applications presents substantial challenges. This research introduces integration redox-active catechol moiety into a series (TPE-COF-OH, TPB-COF-OH, and TPP-COF-OH), serving pivotal active site photocatalytic oxygen (O2) reduction to H2O2 through reversible catechol-quinone interconversion mechanism. process facilitates transformation o-benzoquinone in presence molecular O2, while photoexcited electrons are utilized revert catechol, reducing energy barrier synthesis. Notably, TPB-COF-OH demonstrates an unparalleled production rate 6608 μmol h–1 g–1, outperforming its counterpart, TPB-COF-OMe, which lacks unit. Furthermore, achieves solar-to-chemical conversion efficiency 0.84%, marking highest value among COF-based photocatalysts production. investigation not only underscores critical role engineering enhancing COF performance but also broadens horizon technologies.

Language: Английский

---

One‐Dimensional Covalent Organic Framework‐Based Multilevel Memristors for Neuromorphic Computing

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: March 21, 2024

Abstract Memristors are essential components of neuromorphic systems that mimic the synaptic plasticity observed in biological neurons. In this study, a novel approach employing one‐dimensional covalent organic framework (1D COF) films was explored to enhance performance memristors. The unique structural and electronic properties two 1D COF (COF‐4,4′‐methylenedianiline (MDA) COF‐4,4′‐oxydianiline (ODA)) offer advantages for multilevel resistive switching, which is key feature computing applications. By further introducing TiO 2 layer on COF‐ODA film, built‐in electric field between COF‐TiO interfaces could be generated, demonstrating feasibility utilizing COFs as platform constructing memristors with tunable states. nanochannels these structures contributed efficient modulation electrical conductance, enabling precise control over weights circuits. This study also investigated potential COF‐based achieve energy‐efficient high‐density memory devices.

Language: Английский

---

1D Covalent Organic Frameworks Triggering Highly Efficient Photosynthesis of H₂O₂ via Controllable Modular Design

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(12)

Published: Feb. 1, 2024

The topological diversity of covalent organic frameworks (COFs) enables considerable space for exploring their structure-performance relationships. In this study, we report a sequence novel 1D COFs (EO, ES, and ESe-COF) with typical 4-c sql topology that can be interconnected VIA group elements (O, S, Se) via modular design strategy. It is found the electronic structures, charge delivery property, light harvesting ability, hydrophilicity these profoundly influenced by bridge-linked atom ordinal. Finally, EO-COF, possessing highest quantity active sites, longest lifetime electron, strongest interaction O

Language: Английский

---

Rational Design of Organic Electrocatalysts for Hydrogen and Oxygen Electrocatalytic Applications

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(25)

Published: March 8, 2024

Abstract Efficient electrocatalysts are pivotal for advancing green energy conversion technologies. Organic electrocatalysts, as cost‐effective alternatives to noble‐metal benchmarks, have garnered attention. However, the understanding of relationships between their properties and electrocatalytic activities remains ambiguous. Plenty research articles regarding low‐cost organic started gain momentum in 2010 been flourishing recently though, a review article both entry‐level experienced researchers this field is still lacking. This underscores urgent need elucidate structure–activity relationship design suitable electrode structures, leveraging unique features like controllability compatibility real‐world applications. classified into four groups: small molecules, oligomers, polymers, frameworks, with specific structural physicochemical serving activity indicators. To unlock full potential five strategies discussed: integrated surface property modulation, membrane technologies, electrolyte affinity regulation, addition anticorrosion species, all aimed at enhancing charge efficiency, mass transfer, long‐term stability during reactions. The offers comprehensive overview current state practical applications, bridging gap paving way future developments more efficient

Language: Английский

---

Multicomponent Synthesis of Imidazole‐Linked Fully Conjugated 3D Covalent Organic Framework for Efficient Electrochemical Hydrogen Peroxide Production

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Oct. 26, 2023

The semiconducting properties and applications of three dimensional (3D) covalent organic frameworks (COFs) are greatly hampered because their long-ranged non-conjugated skeletons relatively unstable linkages. Here, a robust imidazole-linked fully conjugated 3D framework (BUCT-COF-7) is synthesized through the one-pot multicomponent Debus-Radziszewski reaction saddle-shaped aldehyde-substituted cyclooctatetrathiophene, pyrene-4,5,9,10-tetraone, ammonium acetate. BUCT-COF-7, as metal-free catalyst, shows excellent two electron oxygen reduction (ORR) activity in alkaline medium with high hydrogen peroxide (H2 O2 ) selectivity 83.4 %. When BUCT-COF-7 cathode catalyst assembled into electrolyzer, devices showed electrochemical production rate H2 up to 326.9 mmol g-1 h-1 . accumulative amount could totally degrade dye methylene blue via Fenton for wastewater treatment. This first report about intrinsic COFs efficient synthesis , revealing promising environment-related field.

Language: Английский

---

Linkage engineering in covalent organic frameworks as metal-free oxygen reduction electrocatalysts for hydrogen peroxide production

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 340, P. 123216 - 123216

Published: Aug. 23, 2023

Language: Английский

---

A B←N framework based on 1D dative B←N polymers for exclusive recognition and separation of benzene from its azeotrope

Chem, Journal Year: 2023, Volume and Issue: 9(12), P. 3532 - 3543

Published: Aug. 22, 2023

Language: Английский

---

Robust Covalent Organic Frameworks for Photosynthesis of H₂O₂: Advancements, Challenges and Strategies

Small, Journal Year: 2024, Volume and Issue: 20(44)

Published: July 6, 2024

Abstract Since 2020, covalent organic frameworks (COFs) are emerging as robust catalysts for the photosynthesis of hydrogen peroxide (H 2 O ), benefiting from their distinct advantages. However, current efficiency H production and solar‐to‐chemical energy conversion (SCC) remain suboptimal due to various constraints in reaction mechanism. Therefore, there is an imperative propose improvement strategies accelerate development this system. This comprehensive review delineates recent advances, challenges, utilizing COFs photocatalytic production. It explores fundamentals challenges (e.g., oxygen (O ) mass transfer rate, adsorption capacity, response sunlight, electron‐hole separation efficiency, charge selectivity, desorption) associated with process, well advantages, applications, classification, preparation purpose. Various enhance performance highlighted. The aims stimulate further advancements discusses potential prospects, application areas field.

Language: Английский

---

Covalent organic frameworks for efficient hydrogen peroxide production

EnergyChem, Journal Year: 2024, Volume and Issue: 6(2), P. 100121 - 100121

Published: March 1, 2024

Language: Английский

---

Synergistic Modulating Interlayer Space and Electron‐Transfer of Covalent Organic Frameworks for Oxygen Reduction Reaction

Small, Journal Year: 2024, Volume and Issue: 20(28)

Published: Feb. 13, 2024

Abstract Covalent organic frameworks (COFs) are an ideal template to construct high‐efficiency catalysts for oxygen reduction reaction (ORR) due their predictable properties. However, the closely parallel‐stacking manner and lacking intramolecular electron transfer ability of COFs limit atomic utilization efficiency intrinsic activity. Herein, constructed with large interlayer distances enhanced electronic by side‐chain functionalization. Long chains electron‐donating features not only enlarge distance, but also narrow bandgap. The resulting DPPS‐COF displays higher electrochemical surface areas provide more exposed active sites, despite <1/10 areas. exhibits excellent electrocatalytic ORR activity half‐wave potential 0.85 V, which is 30 60 mV positive than those Pt/C DPP‐COF, record among reported COFs. employed as cathode electrocatalyst zinc‐air battery a maximum power density 185.2 mW cm −2 , superior Pt/C. Theoretical calculation further reveals that longer electronic‐donating facilitate formation intermediate OOH* from O 2 promote intermediates desorption thus leading

Language: Английский

---