Integration of Perylene Diimide into a Covalent Organic Framework for Photocatalytic Oxidation

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(46)

Опубликована: Июль 31, 2024

Abstract Perylene diimides (PDIs) have garnered considerable attention due to their immense potential in photocatalysis. However, manipulating the molecular packing within aggregates and enhancing efficiency of photogenerated carrier recombination remain significant challenges. In this study, we demonstrate incorporation a PDI unit into covalent organic framework (COF), named PDI‐PDA, by linking an ortho‐substituted with p ‐phenylenediamine (PDA) control its intermolecular aggregation. The enables precise modulation electron‐transfer dynamics, leading ten‐fold increase photocatalytic oxidation thioether sulfoxide PDI‐PDA compared counterpart, yields exceeding 90 %. Electron property studies density functional theory calculations show that well‐defined crystal structure, enhances π–π stacking lowers electron transition barrier. Moreover, strong electron‐withdrawing ability promotes spatial separation valency band maximum conduction minimum suppressing rapid electron‐hole pairs improving charge‐separation give high efficiency. This study provides brief but effective way for commonly used PDI‐based dyes integrating them skeleton.

Язык: Английский

---

Engineering Polyheptazine and Polytriazine Imides for Photocatalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(49)

Опубликована: Авг. 27, 2024

Abstract As organic semiconductor materials gain increasing prominence in the realm of photocatalysis, two carbon‐nitrogen materials, poly (heptazine imide) (PHI) and (triazine (PTI), have garnered extensive attention applications owing to their unique structure properties. This review elaborates on distinctive physical chemical features PHI PTI, emphasizing formation mechanisms ensuing Furthermore, it elucidates intricate correlation between energy band structures various photocatalytic reactions. Additionally, outlines primary synthetic strategies for constructing along with characterization techniques identification. It also summarizes enhancing performance whose advantages are discussed. Finally, highlights promising prospects challenges PTI as photocatalysts.

Язык: Английский

---

Single Ru Sites on Covalent Organic Framework‐Coated Carbon Nanotubes for Highly Efficient Electrocatalytic Hydrogen Evolution

Small, Год журнала: 2023, Номер 20(3)

Опубликована: Сен. 8, 2023

Abstract Covalent organic frameworks (COFs) with precisely controllable structures and highly ordered porosity possess great potential as electrocatalysts for hydrogen evolution reaction (HER). However, the catalytic performance of pristine COFs is limited by poor active sites low electron transfer. Herein, to address these issues, conductive carbon nanotubes (CNTs) are coated a defined structure RuBpy(H 2 O)(OH)Cl in bipyridine‐based COF (TpBpy). And this composite single site Ru incorporated can be used HER electrocatalyst alkaline conditions. A series crucial issues carefully discussed through experiments density functional theory (DFT) calculations, such coordination atomically dispersion ions, mechanism embedded site, effect CNTs on electrocatalytic properties. According DFT act H generation. Benefitting from increasing catalyst conductivity charge transfer, as‐prepared c‐CNT‐0.68@TpBpy‐Ru shows an excellent overpotential 112 mV at 10 mA cm −2 under conditions well durability up 12 h, which superior that most reported solution.

Язык: Английский

---

Contemporary Progress on Photo-induced Green Hydrogen Evolution: Potential, Challenges, and Perspectives for the Hydrogen Energy based Economy -An Updated Review

Fuel, Год журнала: 2023, Номер 361, С. 130654 - 130654

Опубликована: Дек. 22, 2023

Язык: Английский

---

Creating Order in Ultrastable Phosphonate Metal–Organic Frameworks via Isolable Hydrogen-Bonded Intermediates

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(39), С. 21263 - 21272

Опубликована: Сен. 22, 2023

The stability presented by trivalent metal-organic frameworks (MOFs) makes them an attractive class of materials. With phosphonate-based ligands, crystallization is a challenge, as there are significantly more binding motifs that can be adopted due to the extra oxygen tether compared carboxylate counterparts and self-assembly processes less reversible. Despite this, we have reported charge-assisted hydrogen-bonded (HMOFs) consisting [Cr(H2O)6]3+ phosphonate which were crystallographically characterized. We sought use these HMOFs crystalline intermediate synthesize ordered Cr(III)-phosphonate MOFs. This done dehydrating HMOF remove aquo ligands around Cr(III) center, forcing metal-phosphonate coordination. Herein, new porous HMOF, H-CALF-50, synthesized then dehydrated yield MOF CALF-50. CALF-50 ordered, although it not single crystalline. It does, however, exceptional stability, maintaining crystallinity surface area after boiling in water for 3 weeks soaking 14.5 M H3PO4 24 h 9 HCl 72 h. Computational methods used study transformation give insight into nature structure degree heterogeneity.

Язык: Английский

---

Chemical conversion of imine- into quinoline-linked covalent organic frameworks for photocatalytic oxidation

Journal of Colloid and Interface Science, Год журнала: 2023, Номер 655, С. 709 - 716

Опубликована: Ноя. 14, 2023

Язык: Английский

---

Lateral functionalization of a one-dimensional covalent organic framework for efficient photocatalytic hydrogen evolution from water

Journal of Materials Chemistry A, Год журнала: 2024, Номер 12(26), С. 16063 - 16069

Опубликована: Янв. 1, 2024

Exterior functionalization of a one-dimensional (1D) covalent organic framework (COF) was achieved by introducing terpyridine units on its edges to anchor Pt( ii ) cations. It exhibits high photocatalytic activity for hydrogen evolution from water.

Язык: Английский

---

Continuous flow synthesis and post-synthetic conversion of single-crystalline covalent organic frameworks

Chemical Science, Год журнала: 2024, Номер 15(20), С. 7545 - 7551

Опубликована: Янв. 1, 2024

Single-crystalline 2D covalent organic frameworks were synthesized in flow with laboratory scale rates of more than 1 g h −1 .

Язык: Английский

---

Molecular engineering of novel D−A1−A2 conjugated microporous polymers by efficient electron donor for highly enhanced photocatalytic hydrogen generation

Separation and Purification Technology, Год журнала: 2025, Номер unknown, С. 132454 - 132454

Опубликована: Март 1, 2025

Язык: Английский

---

Synthesis and Applications of Cage-Based Covalent Organic Frameworks

Crystal Growth & Design, Год журнала: 2024, Номер 24(14), С. 6081 - 6094

Опубликована: Июль 1, 2024

Due to their unique structural characteristics, molecular cages have become pivotal components in supramolecular chemistry and materials science. These possess the remarkable ability encapsulate guest molecules metal nanoparticles within cavities, fostering intriguing host–guest interactions demonstrating significant potential across various domains, including recognition, drug delivery, catalysis, material synthesis. Integrating these with highly porous crystalline covalent organic frameworks (COFs) constitutes a strategic avenue for enhancing both porosity functional sites. This transition from COF involves precise orchestration of individual into extended, covalently bonded structures well-defined porosity. unlocks novel pathways design applications, significantly enriching landscape review comprehensively summarizes synthetic strategies employed fabricating cage-based COFs, explores diverse provides insights future prospects growth this rapidly evolving field.

Язык: Английский

---