Integrating Bifunctionality and Chemical Stability in Covalent Organic Frameworks via One-Pot Multicomponent Reactions for Solar-Driven H₂O₂ Production

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(5), P. 2975 - 2984

Published: Jan. 25, 2023

Multicomponent reactions (MCRs) can be used to introduce different functionalities into highly stable covalent organic frameworks (COFs). In this work, the irreversible three-component Doebner reaction is utilized synthesize four chemically quinoline-4-carboxylic acid DMCR-COFs (DMCR-1-3 and DMCR-1NH) equipped with an acid-base bifunctionality. These show superior photocatalytic H2O2 evolution (one of most important industrial oxidants) compared imine COF analogue (Imine-1). This achieved sacrificial oxidants but also in pure water under oxygen or air atmosphere. Furthermore, high photostability, durability, recyclability. MCR-COFs thus provide a viable materials' platform for solar chemical energy conversion.

Language: Английский

---

Imine and imine-derived linkages in two-dimensional covalent organic frameworks

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(12), P. 881 - 898

Published: Nov. 11, 2022

Language: Английский

---

Covalent organic frameworks towards photocatalytic applications: Design principles, achievements, and opportunities

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 475, P. 214882 - 214882

Published: Oct. 14, 2022

Language: Английский

---

Construction of Covalent Organic Frameworks via Multicomponent Reactions

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(3), P. 1475 - 1496

Published: Jan. 16, 2023

Multicomponent reactions (MCRs) combine at least three reactants to afford the desired product in a highly atom-economic way and are therefore viewed as efficient one-pot combinatorial synthesis tools allowing one significantly boost molecular complexity diversity. Nowadays, MCRs no longer confined organic have found applications materials chemistry. In particular, can be used prepare covalent frameworks (COFs), which crystalline porous assembled from monomers exhibit broad range of properties applications. This synthetic approach retains advantages small-molecule MCRs, not only strengthening skeletal robustness COFs, but also providing additional driving forces for their crystallization, has been series robust COFs with diverse The present perspective article provides general background discusses types employed COF date, addresses related critical challenges future perspectives inspire MCR-based design new promote further progress this emerging field.

Language: Английский

---

Construction of Crystalline Nitrone-Linked Covalent Organic Frameworks Via Kröhnke Oxidation

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(28), P. 15465 - 15472

Published: July 7, 2023

Developing diverse synthetic routes to prepare various crystalline covalent organic frameworks (COFs) and enrich the family of COFs is very important highly desirable. In this research, we demonstrate that Kröhnke oxidation (originally developed carbonyl compounds) can be employed as an efficient method construct two nitrone-linked (CityU-1 CityU-2) through ingenious design polynitroso-containing precursors well exquisite control polymerization conditions. The formation structure nitrone-based linkage units have been confirmed a mode reaction. as-obtained characterized by Fourier transform infrared X-ray photoelectron spectroscopy, powder diffraction patterns, scanning electron microscopy. Notably, CityU-1 exhibits BET specific surface area 497.9 m2g-1 with I2 capture capacity 3.0 g g-1 at 75 °C. Our research would provide more chances for applications.

Language: Английский

---

Covalent organic frameworks for CO₂ capture: from laboratory curiosity to industry implementation

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(18), P. 6294 - 6329

Published: Jan. 1, 2023

Synergistic developments of covalent organic frameworks and engineering processes can expedite the qualitative leap for net-zero carbon emissions.

Language: Английский

---

Construction of Covalent Organic Frameworks via a Visible-Light-Activated Photocatalytic Multicomponent Reaction

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(9), P. 4951 - 4956

Published: Feb. 27, 2023

Multicomponent reactions (MCRs), as a powerful one-pot combinatorial synthesis tool, have been recently applied to the of covalent organic frameworks (COFs). Compared with thermally driven MCRs, photocatalytic MCR-based COF has not yet investigated. Herein, we first report construction COFs by multicomponent reaction. Upon visible-light irradiation, series excellent crystallinity, stability, and permanent porosity are successfully synthesized via photoredox-catalyzed Petasis reaction under ambient conditions. Additionally, obtained Cy-N3-COF exhibits photoactivity recyclability for visible-light-driven oxidative hydroxylation arylboronic acids. The concept polymerization only enriches methodology but also opens new avenue that might be possible existing synthetic methods based on MCRs.

Language: Английский

---

Robust links in photoactive covalent organic frameworks enable effective photocatalytic reactions under harsh conditions

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 10, 2024

Abstract Developing heterogeneous photocatalysts for the applications in harsh conditions is of high importance but challenging. Herein, by converting imine linkages into quinoline groups triphenylamine incorporated covalent organic frameworks (COFs), two photosensitive COFs, namely TFPA-TAPT-COF-Q and TFPA-TPB-COF-Q, are successfully constructed. The obtained quinoline-linked COFs display improved stability photocatalytic activity, making them suitable reactions under conditions, as verified recyclable acid involving oxidative decarboxylation base benzylamine coupling. Under strong condition, show a efficiency up to 11831.6 μmol·g −1 ·h long-term usability production H 2 O , while pristine imine-linked less catalytically active easily decomposed these conditions. results demonstrate that enhancing linkage robustness photoactive promising strategy construct catalysts

Language: Английский

---

Post-synthetic modifications of covalent organic frameworks (COFs) for diverse applications

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(78), P. 11631 - 11647

Published: Jan. 1, 2023

Covalent organic frameworks (COFs) are porous and crystalline polymers, which have found usage in various fields. These tailorable through the introduction of diverse functionalities into platform. Indeed, functionality plays a key role their different applications. However, sometimes functional groups not compatible with reaction conditions or can compete interfere other monomers direct synthetic method. Also, pre-synthesis bulky moieties COFs negatively affect crystal formation. To avoid these problems post-synthetic modification (PSM) approach is helpful tactic. assistance this strategy size be tunable stability improved without considerable effect on crystallite. In addition, conductivity, hydrophobicity/ hydrophilicity, chirality among features that reformed review, types PSM strategies based recent articles been divided four categories: (i) post-functionalization, (ii) post-metalation, (iii) chemical locking, (iv) host-guest post-modifications. Post-functionalization locking methods covalent bond formation while post-metalation post-modifications, non-covalent bonds formed. potential post-modified energy storage conversion (lithium-sulfur batteries, hydrogen storage, proton-exchange membrane fuel cells, water splitting), heterogeneous catalysts, food safety evaluation, gas separation, environmental domains (greenhouse capture, radioactive element uptake, remediation), biological applications (drug delivery, biosensors, biomarker chiral column chromatography, solid-state smart nanochannels) discussed.

Language: Английский

---

Electrochemical Interfacial Polymerization toward Ultrathin COF Membranes for Brine Desalination

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(13)

Published: Feb. 4, 2023

Ultrathin covalent organic framework (COF) membranes are urgently demanded in molecular/ionic separations. Herein, we reported an electrochemical interfacial polymerization strategy to fabricate ultrathin COF with thickness of 85 nm, by actively manipulate self-healing effect and self-inhibiting effect. The resulting membrane exhibited superior performance brine desalination the permeation flux 92 kg m-2 h-1 rejection 99.96 %. Our enriches fabrication approach facilitates rational design membranes.

Language: Английский

---