Robust dioxin-linked metallophthalocyanine tbo topology covalent organic frameworks and their photocatalytic properties DOI Creative Commons
Yucheng Jin,

Qianjun Zhi,

Hailong Wang

et al.

National Science Review, Journal Year: 2024, Volume and Issue: 12(1)

Published: Nov. 6, 2024

ABSTRACT Constructing 3D functional covalent organic frameworks (COFs) with both robust linkage and planar macrocycle building blocks still remains a challenge due to the difficulty in adjusting crystallinity dominant 2D structures. In addition, it is also challenging selectively convert inert C(sp3)–H bonds into value-added chemicals. Herein, COFs, USTB-28–M (M=Co, Ni, Cu), have been polymerized from nucleophilic aromatic substitution reaction of D3h-symmetric 2,3,6,7,14,15-hexahydroxyltriptycene D4h-symmetric hexadecafluorophthalocyanine (MPcF16) under solvothermal conditions. These chemically stable dioxin-linked COFs show isostructural tbo topology made up three kinds polyhedron subunits, exhibiting high Brunauer−Emmett−Teller surface areas ≤1477 m2 g−1. particular, multiple subunits could trap N-hydroxyphthalimide at their corners for easily forming phthalimide-N-oxyl radicals visible-light irradiation. The generated efficiently promote aerobic oxidation alkyl benzenes an bond various ketones. Among investigated USTB-28–Co radical initiator exhibits best photocatalytic activity, converting ethylbenzene acetophenone turnover frequency 63 h−1, which much higher than those monomer CoPcF16 (8 h−1) counterparts (13 h−1). This prolonged lifetime excited state based on femtosecond transient absorption result. present work not only presents connection permanent porosity, but illustrates uniqueness porous structures high-performance photocatalysis.

Language: Английский

Photocatalytic Decarboxylative Fluorination by Quinone-Based Isoreticular Covalent Organic Frameworks DOI
Ayan Jati, Ashok Kumar Mahato,

Durba Chanda

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(34), P. 23923 - 23932

Published: Aug. 16, 2024

The strategic incorporation of fluorine atoms into molecules has become a cornerstone modern pharmaceuticals, agrochemicals, and materials science. Herein, we have developed covalent organic framework (COF)-based, robust photocatalyst that enables the photofluorodecarboxylation reaction diverse carboxylic acids, producing alkyl fluorides with remarkable efficiency. catalytic activity an anthraquinone-based COF catalyst

Language: Английский

Citations

13
Reticular Materials for Photocatalysis DOI
Kang Sun, Yunyang Qian, Dandan Li

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 27, 2024

Abstract Photocatalysis leverages solar energy to overcome the thermodynamic barrier, enabling efficient chemical reactions under mild conditions. It can greatly reduce reliance on traditional sources and has attracted significant research interest. Reticular materials, including metal‐organic frameworks (MOFs) covalent organic (COFs), represent a class of crystalline materials constructed from molecular building blocks linked by coordination bonds, respectively. function as heterogeneous catalysts, combining well‐defined structures high tailorability akin homogeneous catalysts. In this review, regulation light absorption, charge separation, surface in photocatalytic process through precise molecular‐level design based features reticular is elaborated. Notably, for MOFsmicroenvironment modulation around catalytic sites affects performance delved, with emphasis their unique dynamic flexible microenvironments. For COFs, inherent excitonic effects due fully nature discussed highlight strategies regulate charge‐ and/or energy‐transfer‐mediated photocatalysis. Finally, current challenges future directions field, aiming provide comprehensive understanding how be optimized enhanced photocatalysis discussed.

Language: Английский

Citations

11
Molecular Engineering of Multivariate Porous Aromatic Frameworks for Recovery of Dispersed Uranium Resources DOI
Yue Ma, Lu Liu,

Shilei Zhao

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(52)

Published: Aug. 27, 2024

Abstract Uranium plays an indispensable role in the sustainable development of nuclear industry, and recovery uranium from wastewater is one way to solve shortage resources. However, resources remains a challenge due interfere coexisting ions. Herein, ratios adsorption group photocatalytic enrichment are well‐designed controllably assembled into porous aromatic frameworks (PAFs) using molecular engineering strategy realize high efficiency resistance interfering The optimally coordinated multivariate PAF material PAF‐AN 2 T 8 ‐AO exhibits bifunctions thus, achieves selectivity 99% under simulated sunlight irradiation. Compared PAFs with only or group, capacity optimized enhanced by 1.2 times 2.3 times, respectively. Mechanistic studies reveal that product on air‐stabilized solid crystal metastudtite ((UO )O ∙2H O). This work provides guiding method for designing adsorption‐photocatalytic bifunctional materials proposes more environmentally adaptable dispersed resource recovery.

Language: Английский

Citations

10
Selective Liquid Chemical Production in Waste Polyolefin Photorefinery by Controlling Reactive Species DOI
Xinlin Liu, Xianpeng Wang,

Mingyu Chu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 29, 2025

Photocatalytic upcycling of waste polyolefins into value-added chemicals provides promise in plastic management and resource utilization. Previous works demonstrate that can be converted carboxylic acids, with CO2 as the final oxidation product. It is still challenging to explore more transformation products, particularly mild-oxidation products such alcohols, because their instability compared polymer substrates, which are prone during catalytic reactions. In this work, we propose an efficient strategy regulate product type through precise control radicals, intermediates, reaction paths. Taking commonly used photocatalyst C3N4 example, its major acids CO2. When MoS2 introduced construct a Z-scheme heterostructure, gas significantly reduced alcohols appear high yield 1358.8 μmol gcat-1 selectivity up 80.3%. This primarily attributed presence •OH radicals from oxygen reduction, acting key role alcohol formation while simultaneously suppressing competing pathways •O2- 1O2, thus reducing overoxidation products. The β-scission C-C bonds chains generates intermediate alkyl species, followed by combination produce methanol, energetically favorable for MoS2/C3N4. contrast, species couple form formic acid, C3N4. work new approaches controlling types offers insights involved polyolefin photorefinery.

Language: Английский

Citations

2
Reactive oxygen species generation for catalysis and biotherapeutic applications based on crystalline porous materials DOI
Yunyang Qian, Bo Li, Muhammad Irfan

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 518, P. 216068 - 216068

Published: July 17, 2024

Language: Английский

Citations

7
Impact of Imine Bond Orientations and Acceptor Groups on Photocatalytic Hydrogen Generation of Donor–Acceptor Covalent Organic Frameworks DOI

Chao‐Qin Han,

Jiaxin Guo, Shuai Sun

et al.

Small, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 9, 2024

Abstract Covalent organic frameworks (COFs) have emerged as one of the most studied photocatalysts owing to their adjustable structure and bandgaps. However, there is limited research on regulating light‐harvesting capabilities acceptor building blocks in donor–acceptor (D–A) isomer COFs with different bond orientations. This investigation crucial for elucidating structure‐property‐performance relationship COF photocatalysts. Herein, a series D–A isostructural are synthesized imine orientations using benzothiadiazole its derivatives‐based units. Extended light absorption achieved groups that strong electron‐withdrawing capacities, although this resulted decreased hydrogen generation efficiency. Photocatalytic experiments indicated dialdehyde benzothiadiazole‐based COFs, HIAM‐0015, exhibit highest rate (17.99 mmol g −1 h ), which 15 times higher than isomer. The excellent photocatalytic performance HIAM‐0015 can be attributed fast charge separation migration. work provides insights into rational design synthesis achieve efficient activity.

Language: Английский

Citations

7
Vinylene‐Linking of Polycyclic Aromatic Hydrocarbons to π‐Extended Two‐Dimensional Covalent Organic Framework Photocatalyst for H2O2 Synthesis DOI Open Access

Xu Chi,

Zixing Zhang,

Mengqi Li

et al.

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

Published: Oct. 16, 2024

Polycyclic aromatic hydrocarbons (PAHs) hold the predominant role either as individual molecules or building blocks in field of organic semiconductors nanocarbons. Connecting PAHs via sp

Language: Английский

Citations

6
Photocatalytic Applications of Covalent Organic Frameworks: Synthesis, Characterization, and Utility DOI Creative Commons

Jared G. Doremus,

Bertha Lotsi,

Amit Sharma

et al.

Nanoscale, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

This review highlights the recent advances in utilizing covalent organic frameworks (COFs) for photocatalytic applications.

Language: Английский

Citations

6
Exploring the structural stability, thermal and mechanical properties of nanoporous carbon nitride nanosheets using a transferrable machine learning interatomic potential DOI Creative Commons
Bohayra Mortazavi, Timon Rabczuk, Xiaoying Zhuang

et al.

Machine learning for computational science and engineering, Journal Year: 2024, Volume and Issue: 1(1)

Published: Nov. 26, 2024

Abstract Nanoporous carbon nitride nanosheets (NPCNNs) currently stand as one of the most promising classes two-dimensional materials, exhibiting exceptional properties, wide range applications and continuous experimental realization novel structures. However, from a theoretical standpoint, detecting their stable configurations accurately evaluating mechanical thermal properties are challenging. To effectively address these obstacles, here for first time we have developed transferable machine learning interatomic potential (MLIP), capable substantially facilitating detection dynamically configurations. Through comprehensive analysis diverse NPCNNs, it is shown that model could with negligible computational cost remarkable accuracy reproduce directional-dependent stress–strain curves failure mechanisms predicted by density functional theory calculations. It furthermore conveniently detect complex corrugated configurations, moreover highlight resulting electronic might be considerably different unstable flat counterparts. The MLIP can thus offer an accurate fast solution to explore structural stability, responses at ground state, investigate temperature dependent deeper insights into physical applications.

Language: Английский

Citations

6
Intrareticular Exciton Effects Regulate Photocatalytic Activity in Donor–Acceptor Olefin‐Linked Covalent Organic Frameworks DOI
Jie Zhang,

Wenwen Zhou,

Jianfeng Zhao

et al.

Small, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 3, 2024

Abstract Olefin‐linked covalent organic frameworks (OL‐COFs) show great promise for visible‐light‐driven photocatalysis. Manipulating atomic‐level donor–acceptor interactions in OL‐COFs is key to understanding their exciton effects this system. Here, three are presented with orthorhombic lattice structures, synthesized via Knoevenagel polycondensation reaction of terephthalaldehyde and tetratopic monomers featuring phenyl, benzo[c][1,2,5]oxadiazole, benzo[c][1,2,5]thiadiazole moieties. These feature tunable interactions, making them ideal studying olefin‐linked systems. Comprehensive analyses, including temperature‐dependent photoluminescence spectra, ultrafast spectroscopy, theoretical calculations, reveal that stronger lead reduced binding energy ( E b ), accelerated dissociation, longer‐lived photogenerated charges, thereby enhancing photocatalytic performance. Notably, The TMO‐BDA COF, the lowest , demonstrates superior activity one‐pot sequential transformation excellent catalytic performance gram‐scale reactions, highlighting its potential practical applications. This work provides valuable insights into regulating effect at molecular level OL‐COFs, offering pathways enhance efficiency.

Language: Английский

Citations

5