Isoreticular Series of Two-Dimensional Covalent Organic Frameworks with the kgd Topology and Controllable Micropores DOI
Liuxiao Li, Qinbai Yun,

Chongzhi Zhu

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(14), P. 6475 - 6482

Published: April 4, 2022

Two-dimensional (2D) covalent organic frameworks (COFs) possess designable pore architectures but limited framework topologies. Until now, 2D COFs adopting the kgd topology with ordered and rhombic geometry have rarely been reported. Here, an isoreticular series of controllable size is synthesized by employing a C6-symmetric aldehyde, i.e., hexa(4-formylphenyl)benzene (HFPB), C3-symmetric amines tris(4-aminophenyl)amine (TAPA), tris(4-aminophenyl)trazine (TAPT), 1,3,5-tris[4-amino(1,1-biphenyl-4-yl)]benzene (TABPB), as building units, referred to HFPB-TAPA, HFPB-TAPT, HFPB-TABPB, respectively. The micropore dimension down 6.7 Å achieved in which among smallest reported COFs. Impressively, both in-plane network stacking sequence can be clearly observed low-dose electron microscopy. Integrating unique small micropores, these are endowed short molecular diffusion length favorable host-guest interaction, exhibiting potential for drug delivery high loading good release control ibuprofen.

Language: Английский

Recent advances in electrocatalysis with phthalocyanines DOI

Shaoxuan Yang,

Yihuan Yu,

Xinjin Gao

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(23), P. 12985 - 13011

Published: Jan. 1, 2021

Applications of phthalocyanines (Pcs) in electrocatalysis-including the oxygen reduction reaction (ORR), carbon dioxide (CO2RR), evolution (OER), and hydrogen (HER)-have attracted considerable attention recently. Pcs their derivatives are more attractive than many other macrocycles as electrocatalysts since, although they structurally related to natural porphyrin complexes, offer advantages low cost, facile synthesis good chemical stability. Moreover, high tailorability structural diversity mean have great potential for application electrochemical devices. Here we review structure composition Pcs, methods analogues, well applications Pc-based heterogeneous electrocatalysts. Optimization strategies materials electrocatalysis ORR, CO2RR, OER HER proposed, based on mechanisms different reactions. We also discuss structure/composition-catalytic activity relationships Pc order identify future practical applications. Finally, opportunities challenges use molecular discussed.

Language: Английский

Citations

255
Piperazine-Linked Metalphthalocyanine Frameworks for Highly Efficient Visible-Light-Driven H2O2 Photosynthesis DOI

Qianjun Zhi,

Wenping Liu, Rong Jiang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(46), P. 21328 - 21336

Published: Nov. 9, 2022

Artificial photosynthesis of H2O2 from O2 reduction provides an energy-saving, safe, and green approach. However, it is still critical to develop highly active selective 2e– oxygen reaction photocatalysts for efficient production owing the unsatisfactory productivity. Herein, two new two-dimensional piperazine-linked CoPc-based covalent organic frameworks (COFs), namely, CoPc-BTM-COF CoPc-DAB-COF, were afforded nucleophilic substitution hexadecafluorophthalocyaninato cobalt(II) (CoPcF16) with 1,2,4,5-benzenetetramine (BTM) or 3,3′-diaminobenzidine (DAB). Powder X-ray diffraction analysis in combination electron microscopy a series spectroscopic technologies reveals their crystalline porous framework fully conjugated structure eclipsed π-stacking model. Ultraviolet–visible diffuse reflectance absorption spectra unveil excellent light capacity wide range 400–1000 nm. This, together enhanced photo-induced charge separation transport efficiency as disclosed by photocurrent response photoluminescence measurements, endows as-prepared COFs superior photocatalytic activity toward O2-to-H2O2 conversion under visible-light irradiation (λ > 400 nm). In particular, exhibits record-high yield 2096 μmol h–1 g–1 among COF-based impressive apparent quantum 7.2% at 630 The present result should be helpful fabricating high-performance low-cost visible-light-driven photosynthesis.

Language: Английский

Citations

254
Computation-based regulation of excitonic effects in donor-acceptor covalent organic frameworks for enhanced photocatalysis DOI Creative Commons
Yunyang Qian, Yulan Han, Xiyuan Zhang

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 29, 2023

The strong excitonic effects widely exist in polymer-semiconductors and the large exciton binding energy (Eb) seriously limits their photocatalysis. Herein, density functional theory (DFT) calculations are conducted to assess band alignment charge transfer feature of potential donor-acceptor (D-A) covalent organic frameworks (COFs), using 1,3,5-tris(4-aminophenyl)triazine (TAPT) or 1,3,5-tris(4-aminophenyl)benzene (TAPB) as acceptors tereph-thaldehydes functionalized diverse groups donors. Given discernable D-A interaction strengths pairs, Eb can be systematically regulated with minimum TAPT-OMe. Guided by these results, corresponding COFs synthesized, where TAPT-OMe-COF possesses best activity photocatalytic H2 production trend other is associated that calculated for pairs. In addition, further alkyne cycloaddition imine linkage greatly improves stability resulting TAPT-OMe-alkyne-COF a substantially smaller exhibits ~20 times higher than parent COF.

Language: Английский

Citations

224
Porphyrin-based framework materials for energy conversion DOI Creative Commons

Jiawei Gu,

Yi Peng, Ting Zhou

et al.

Deleted Journal, Journal Year: 2022, Volume and Issue: 1, P. e9120009 - e9120009

Published: May 26, 2022

With the increasing demand for fuel causing serious environmental pollution, it is urgent to develop new and environmentally friendly energy conversion devices. These devices, however, require good, inexpensive materials electrodes so on. The multifunctional properties of porphyrins enable framework (e.g., metal-organic frameworks covalent organic frameworks) be applied in devices due their simple synthesis, high chemical stability, abundant metallic active sites, adjustable crystalline structure specific surface area. Herein, types porphyrin structural blocks are briefly reviewed. They can used as ligands or directly assembled with generate high-performance electro-/photo-catalysts. catalysts electro-/photo-catalytic water splitting, carbon dioxide reduction, electrocatalytic oxygen reduction also summarized introduced. At end article, we present challenges porphyrin-based above application corresponding solutions. We expect flourish coming years.

Language: Английский

Citations

222
Metalated covalent organic frameworks: from synthetic strategies to diverse applications DOI
Qun Guan, Lele Zhou, Yu‐Bin Dong

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(15), P. 6307 - 6416

Published: Jan. 1, 2022

This review highlights the recent advances of metalated covalent organic frameworks, including synthetic strategies and applications, discusses current challenges future directions.

Language: Английский

Citations

221
Covalent Organic Framework Based Functional Materials: Important Catalysts for Efficient CO2Utilization DOI
Meng Lu, Mi Zhang, Jiang Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(15)

Published: Jan. 21, 2022

As hot topics in the chemical conversion of CO2 , photo-/electrocatalytic reduction and use as a supporter for energy storage have shown great potential utilization . However, many obstacles still exist on road to realizing highly efficient conversion, such inefficient uptake/activation mass transport catalysts. Covalent organic frameworks (COFs), kind porous material, been widely explored catalysts owing their unique features. In particular, COF-based functional materials containing diverse active sites (such single metal sites, nanoparticles, oxides) offer storage. This Minireview discusses recent breakthroughs basic knowledge, mechanisms, pathways strategies that addition, challenges prospects are also introduced.

Language: Английский

Citations

192
Mesoporous Polyimide‐Linked Covalent Organic Framework with Multiple Redox‐Active Sites for High‐Performance Cathodic Li Storage DOI
Xiya Yang, Lei Gong, Xiaolin Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: May 31, 2022

Covalent organic frameworks (COFs) are gaining increasing attention as renewable cathode materials for Li-ion batteries. However, COF electrodes reported so far still exhibit unsatisfying capacity due to their limited active site density and insufficient utilization. Herein, a new two-dimensional polyimide-linked COF, HATN-AQ-COF with multiple redox-active sites storing Li+ ions, was designed fabricated from module of 2,3,8,9,14,15-hexacarboxyl hexaazatrinaphthalene trianhydrides 2,6-diaminoanthraquinone linker. possessing excellent stability, good conductivity, large pore size 3.8 nm enables the stable fast ion transport. This, in combination abundant redox sites, results high reversible 319 mAh g-1 at 0.5 C (1 C=358 mA ) electrode utilization 89 % cycle performance, representing one best performances among electrodes.

Language: Английский

Citations

144
Porphyrin and phthalocyanine based covalent organic frameworks for electrocatalysis DOI

Shengsheng Huang,

Kai Chen, Tingting Li

et al.

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 464, P. 214563 - 214563

Published: April 22, 2022

Language: Английский

Citations

136
Post-synthetic modification of covalent organic frameworks for CO2 electroreduction DOI Creative Commons
Minghao Liu, Shuai Yang, Xiubei Yang

et al.

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: June 26, 2023

To achieve high-efficiency catalysts for CO2 reduction reaction, various catalytic metal centres and linker molecules have been assembled into covalent organic frameworks. The amine-linkages enhance the binding ability of molecules, ionic frameworks enable to improve electronic conductivity charge transfer along However, directly synthesis with is hardly achieved due electrostatic repulsion predicament strength linkage. Herein, we demonstrate reaction by modulating linkers linkages template framework build correlation between performance structures Through double modifications, states are well tuned, resulting in controllable activity selectivity reaction. Notably, dual-functional achieves high a maximum CO Faradaic efficiency 97.32% turnover frequencies value 9922.68 h-1, which higher than those base single-modified Moreover, theoretical calculations further reveal that attributed easier formation immediate *CO from COOH*. This study provides insights developing

Language: Английский

Citations

129
Construction of Catalytic Covalent Organic Frameworks with Redox‐Active Sites for the Oxygen Reduction and the Oxygen Evolution Reaction DOI
Minghao Liu, Sijia Liu, Cheng‐Xing Cui

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(49)

Published: Oct. 14, 2022

Construction of catalytic covalent organic frameworks (COFs) for oxygen reduction reaction (ORR) and evolution (OER) is significant but rarely demonstrated. In this work, we have first constructed bifunctional COFs towards ORR OER by integrating diarylamine derivatives into the Co-porphyrin based frameworks. Both new (CoTAPP-PATA-COF CoTAPP-BDTA-COF) good ordered structures, high surface areas, robust chemical stability. The units, as a typical electron donor redox-active cores, promote intramolecular transport along improve electrochemically active areas. Thus, showed higher activities than that COF without units. CoTAPP-PATA-COF had halfwave potential 0.80 V ORR, delieved an overpotential 420 mV in 0.1 M KOH. theoretical calculation revealed introducing unites improved electrocatalysis.

Language: Английский

Citations

127