Covalent Organic Frameworks for Energy Conversion in Photocatalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(34)

Опубликована: Апрель 24, 2023

Abstract Intensifying energy crises and severe environmental issues have led to the discovery of renewable sources, sustainable conversion, storage technologies. Photocatalysis is a green technology that converts eco‐friendly solar into high‐energy chemicals. Covalent organic frameworks (COFs) are porous materials constructed by covalent bonds show promising potential for converting chemicals owing their pre‐designable structures, high crystallinity, porosity. Herein, we highlight recent progress in synthesis COF‐based photocatalysts applications water splitting, CO 2 reduction, H O production. The challenges future opportunities rational design COFs advanced discussed. This Review expected promote further development toward photocatalysis.

Язык: Английский

---

Functional nanomaterials for selective uranium recovery from seawater: Material design, extraction properties and mechanisms

Coordination Chemistry Reviews, Год журнала: 2023, Номер 483, С. 215097 - 215097

Опубликована: Март 6, 2023

Язык: Английский

---

2D Covalent Organic Frameworks: From Synthetic Strategies to Advanced Optical‐Electrical‐Magnetic Functionalities

Advanced Materials, Год журнала: 2022, Номер 34(17)

Опубликована: Янв. 20, 2022

Abstract Covalent organic frameworks (COFs), an emerging class of crystalline polymers with highly oriented structures and permanent porosity, can adopt 2D or 3D architectures depending on the different topological diagrams monomers. Notably, COFs have particularly gained much attention due to extraordinary merits their extended in‐plane π‐conjugation topologically ordered columnar π‐arrays. These properties together high crystallinity, large surface area, tunable porosity distinguish as ideal candidate for fabrication functional materials. Herein, this review surveys recent research advances in special emphasis preparation COF powders, single crystals, thin films, well advanced optical, electrical, magnetic functionalities. Some challenging issues potential outlook are also provided promoting development terms structure, synthesis,

Язык: Английский

---

Three-Dimensional Covalent Organic Frameworks with Ultra-Large Pores for Highly Efficient Photocatalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(5), С. 3248 - 3254

Опубликована: Янв. 31, 2023

Benefiting from their unique structural merits, three-dimensional (3D) large-pore COF materials demonstrate high surface areas and interconnected large channels, which makes these promising in practical applications. Unfortunately, functionalization strategies application research are still absent structures. To this end, a series of functional 3D stp-topologized COFs designed based on porphyrin or metalloporphyrin moieties, named JUC-640-M (M = Co, Ni, H). Interestingly, JUC-640-H exhibits record-breaking low crystal density (0.106 cm3 g-1) among all crystalline materials, along with the largest pore size (4.6 nm) COFs, area (2204 m2 g-1), abundant exposed moieties (0.845 mmol g-1). Inspired by characteristics photoelectrical performance, JUC-640-Co is utilized for photoreduction CO2 to CO demonstrates production rate (15.1 g-1 h-1), selectivity (94.4%), stability. It should be noted that has exceeded those reported COF-based materials. This work not only produces novel channels but also provides new guidance applications COFs.

Язык: Английский

---

Constitutional isomerism of the linkages in donor–acceptor covalent organic frameworks and its impact on photocatalysis

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Окт. 23, 2022

When new covalent organic frameworks (COFs) are designed, the main efforts typically focused on selecting specific building blocks with certain geometries and properties to control structure function of final COFs. The nature linkage (imine, boroxine, vinyl, etc.) between these naturally also defines their properties. However, besides type, orientation, i.e., constitutional isomerism linkages, has rarely been considered so far as an essential aspect. In this work, three pairs constitutionally isomeric imine-linked donor-acceptor (D-A) COFs synthesized, which different in orientation imine bonds (D-C=N-A (DCNA) D-N=C-A (DNCA)). isomers show substantial differences photophysical consequently photocatalytic performance. Indeed, all DCNA enhanced H2 evolution performance than corresponding DNCA Besides shown here, it can be concluded that proposed concept linkages is quite universal should when designing tuning

Язык: Английский

---

Nanoscale porous organic polymers for drug delivery and advanced cancer theranostics

Chemical Society Reviews, Год журнала: 2021, Номер 50(23), С. 12883 - 12896

Опубликована: Янв. 1, 2021

Finding a personalized nano theranostics solution, nanomedicine for cancer diagnosis and therapy, is among the top challenges of current medicinal science. Porous organic polymers (POPs) are permanent porous materials prepared by linking relatively rigid multidimensional building blocks. POP nanoparticles have remarkable advantage owing to their specific physicochemical characteristics such as high surface area, convincing pore size engineering, stimuli-responsive degradability, negligible toxicity, open covalent post-synthesis modification possibilities etc. POPs crystalline non-crystalline characteristics; popularly known frameworks (COFs), shown potential application across research areas in The early development on applications nanoscale has tremendous future clinical translation. This tutorial review highlights recently developed promising nPOPs drug loading, targeted delivery, endogenous exogenous release, imaging combination regardless poorly properties. will provide platform translation solving fundamental nanomedicines loading efficiency, size-optimization, biocompatibility, dispersibility cell uptake ability.

Язык: Английский

---

Transformation of Porous Organic Cages and Covalent Organic Frameworks with Efficient Iodine Vapor Capture Performance

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(27), С. 12390 - 12399

Опубликована: Июнь 29, 2022

The reaction of 5,5′-([2,2′-bipyridine]-5,5′-diyl)diisophthalaldehyde (BPDDP) with cyclohexanediamine and [benzidine (BZ)/[2,2′-bipyridine]-5,5′-diamine (BPDA)], respectively, affords a nitrogen-rich porous organic cage BPPOC two two-dimensional (2D) covalent frameworks (COFs), USTB-1 USTB-2 (USTB = University Science Technology Beijing), under suitable conditions. Interestingly, single-crystal X-ray diffraction structure is able to successfully transform into (newly converted COFs denoted as USTB-1c USTB-2c, respectively) upon exchange the imine unit in by BZ BPDA. Such transformation also enables isolation analogous (USTB-3c USTB-4c) on basis an isostructural cage, BTPOC, which derived from 5,5′-([2,2′-bithiophene]-4,4′-diyl)diisophthalaldehyde (BTDDP) cyclohexanediamine. However, conventional solvothermal between BTDDP BPDA leads impure phase USTB-4 containing incompletely aldehyde groups due limited solubility building block. newly prepared have been characterized nuclear magnetic resonance spectroscopy, Fourier infrared scanning electron microscopy, transmission microscopy. In particular, absorb iodine vapor uptake 5.64 g g–1, breaking cage's (POC's) record value 3.78 g–1. Nevertheless, cage-derived exhibit improved adsorption capability comparison directly synthesized counterparts, highest 5.80 g–1 for USTB-1c. mechanism investigation unveils superiority nitrogen atoms sulfur POCs capture assistance definite crystal structures. This, combination porosity, synergistically influences capacity COFs.

Язык: Английский

---

Photocatalytic Hydrogen Production on a sp²‐Carbon‐Linked Covalent Organic Framework

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(42)

Опубликована: Авг. 27, 2022

Abstract Two‐dimensional covalent organic frameworks (2D‐COFs) have emerged as attractive platforms for solar‐to‐chemical energy conversion. In this study, we implemented a gradient heating strategy to synthesize sp 2 ‐carbon‐linked triazine‐based COF, COF‐JLU100, exhibiting high crystallinity, large surface area, good durability and carrier mobility solar‐driven photocatalytic hydrogen evolution. The Pt‐doped COF‐JLU100 demonstrated evolution rate of over 100 000 μmol g −1 h water splitting under visible‐light illumination (λ>420 nm). Experimental theoretical studies corroborate that the cyano‐vinylene segments in extend π‐delocalization enable fast charge transfer separation rates well dispersion water. Moreover, can be prepared by low‐cost easily available monomers has excellent stability, which is desirable practical production.

Язык: Английский

---

Photoelectron Transfer Mediated by the Interfacial Electron Effects for Boosting Visible-Light-Driven CO₂ Reduction

ACS Catalysis, Год журнала: 2022, Номер 12(6), С. 3550 - 3557

Опубликована: Март 4, 2022

Imine-linked covalent organic frameworks (COFs) are popular candidates for photocatalytic CO2 reduction, but high polarization of the imine bond is less efficient π-electron delocalization between linked building units, leading to low intramolecular electron transfer and poor efficiency. Herein, we present a structural electronic engineering strategy through integrating imine-linked COF consisting Zn–porphyrin Co–bipyridyl units with cadmium sulfide (CdS) nanowires form CdS@COF core–shell structure. The experimental theoretical results have validated that CdS serves as channel interfacial effects, which induces photoelectron from subsequent injection into reduction. as-prepared generates 4057 μmol g–1 CO in 8 h under visible-light irradiation, considerably higher than those its neat counterparts. This work provides protocols tackle charge across polar linkages photosensitizers active sites solar-to-chemical energy conversion.

Язык: Английский

---

Macrocycle-derived hierarchical porous organic polymers: synthesis and applications

Chemical Society Reviews, Год журнала: 2021, Номер 50(20), С. 11684 - 11714

Опубликована: Янв. 1, 2021

This review article specifically highlights the synthetic strategies and promising applications of macrocycle-derived hierarchical porous organic polymers (POPs).

Язык: Английский

---