Two-Dimensional Covalent Organic Frameworks with Cobalt(II)-Phthalocyanine Sites for Efficient Electrocatalytic Carbon Dioxide Reduction

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(18), P. 7104 - 7113

Published: May 3, 2021

The rapid development in synthesis methodology and applications for covalent organic frameworks (COFs) has been witnessed recent years. However, the of highly stable functional COFs still remains a great challenge. Herein two-dimensional polyimide-linked phthalocyanine (denoted as CoPc-PI-COF-1 CoPc-PI-COF-2) have devised prepared through solvothermal reaction tetraanhydrides 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato cobalt(II) with 1,4-phenylenediamine 4,4′-biphenyldiamine, respectively. resultant CoPc-PI-COFs four-connected sql net exhibit AA stacking configurations according to powder X-ray diffraction studies, showing permanent porosity, thermal stability above 300 °C, excellent resistance 12 M HCl aqueous solution 20 days. Current–voltage curves reveal conductivity CoPc-PI-COF-2 value 3.7 × 10–3 1.6 S m–1, Due same Co(II) electroactive sites together similar porosity CO2 adsorption capacity CoPc-PI-COFs, cathodes made up carbon black display CO2-to-CO Faradaic efficiency 87–97% at applied potentials between −0.60 −0.90 V (vs RHE) 0.5 KHCO3 solution. comparison CoPc-PI-COF-2&carbon electrode, counterpart provides larger current density (jCO) −21.2 mA cm–2 associated its higher conductivity. This cathode also high turnover number frequency, amounting 277 000 2.2 s–1 −0.70 during 40 h measurement. present result clearly discloses potential 2D porous crystalline solids electrocatalysis.

Language: Английский

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

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

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Three-Component Donor−π–Acceptor Covalent–Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8364 - 8374

Published: March 14, 2023

Two-dimensional covalent-organic frameworks (2D COFs) have recently emerged as great prospects for their applications new photocatalytic platforms in solar-to-hydrogen conversion; nevertheless, inefficient solar energy capture and fast charge recombination hinder the improvement of hydrogen production performance. Herein, two photoactive three-component donor-π-acceptor (TCDA) materials were constructed using a multicomponent synthesis strategy by introducing electron-deficient triazine electron-rich benzotrithiophene moieties into through sp2 carbon imine linkages, respectively. Compared with two-component COFs, novel TCDA-COFs are more convenient regulating inherent photophysical properties, thereby realizing outstanding activity evolution from water. Remarkably, first carbon-linked TCDA-COF displays an impressive rate 70.8 ± 1.9 mmol g-1 h-1 excellent reusability presence 1 wt % Pt under visible-light illumination (420-780 nm). Utilizing combination diversified spectroscopy theoretical prediction, we show that full π-conjugated linkage not only effectively broadens harvesting COFs but also enhances transfer separation efficiency.

Language: Английский

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Metalated covalent organic frameworks: from synthetic strategies to diverse applications

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

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Orthoquinone–Based Covalent Organic Frameworks with Ordered Channel Structures for Ultrahigh Performance Aqueous Zinc–Organic Batteries

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(12)

Published: Jan. 22, 2022

Elaborate molecular design on cathodes is of great importance for rechargeable aqueous zinc-organic batteries' performance elevation. Herein, we a novel orthoquinone-based covalent organic framework with an ordered channel structures (BT-PTO COF) cathode ultrahigh battery. The structure facilitates ions transfer and makes the COF follow redox pseudocapacitance mechanism. Thus, it delivers high reversible capacity 225 mAh g-1 at 0.1 A exceptional long-term cyclability (retention rate 98.0 % 5 (≈18 C) after 10 000 cycles). Moreover, co-insertion mechanism Zn2+ first followed by two H+ uncovered time. Significantly, this behaviour evolves to more insertion routes current density gives ultra-fast kinetics thus achieves unprecedented specific power 184 kW kg-1(COF) energy 92.4 Wh . Our work reports superior material zinc batteries provides idea future high-performance cathodes.

Language: Английский

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Covalent‐Organic Frameworks (COFs) as Proton Conductors

Advanced Energy Materials, Journal Year: 2021, Volume and Issue: 11(39)

Published: Sept. 1, 2021

Abstract Proton conductivity is the paramount property of proton‐conducting materials that are playing significant roles in diverse electrochemical devices with applications proton exchange membranes (PEMs) for fuel cells (PEMFCs). Considering scarcity fossil fuels, development clean and green renewable energy resources in‐demand across globe. Toward this direction, solid‐state conductors interest. The higher structural tunability, lower density, good crystallinity, accessible well‐defined pores, excellent thermal chemical stability covalent‐organic frameworks (COFs) make them versatile platforms as both under hydrous anhydrous conditions. Taking advantage such superior properties, reports on COFs have been increasing swiftly since 2014, which demands a summarization comprehensive discussion “at glance” visualization further development. In review, showcased newer class material. A presented by organizing strategies taken to develop COFs. Establishment structure–function relationships implementation discussed well. Moreover, challenges future prospects elaborately critically analyzed.

Language: Английский

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Facile construction of fully sp2-carbon conjugated two-dimensional covalent organic frameworks containing benzobisthiazole units

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Jan. 10, 2022

Abstract Developing a facile strategy for the construction of vinylene-linked fully π -conjugated covalent organic frameworks (COFs) remains huge challenge. Here, versatile condition Knoevenagel polycondensation constructing 2D COFs was explored. Three new examples ( BTH-1 , 2 3 ) containing benzobisthiazoles units as functional groups were successfully prepared under this and mild condition. The electron-deficient benzobisthiazole cyano-vinylene linkages both integrated into conjugated skeleton acted acceptor moieties. Interestingly, we found highly ordered D-A system is favorable photocatalytic activity. BTH-3 with benzotrithiophene donor strong effect exhibited an attractive HER 15.1 mmol h −1 g visible light irradiation.

Language: Английский

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Emerging porous organic polymers for biomedical applications

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(4), P. 1377 - 1414

Published: Jan. 1, 2022

This review summarizes and discusses the recent progress in porous organic polymers for diverse biomedical applications such as drug delivery, biomacromolecule immobilization, phototherapy, biosensing, bioimaging, antibacterial applications.

Language: Английский

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Porphyrin-Based Covalent Organic Frameworks Anchoring Au Single Atoms for Photocatalytic Nitrogen Fixation

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(11), P. 6057 - 6066

Published: March 8, 2023

The development of efficient photocatalysts for N2 fixation to produce NH3 under ambient conditions remains a great challenge. Since covalent organic frameworks (COFs) possess predesignable chemical structures, good crystallinity, and high porosity, it is highly significant explore their potential photocatalytic nitrogen conversion. Herein, we report series isostructural porphyrin-based COFs loaded with Au single atoms (COFX-Au, X = 1-5) fixation. porphyrin building blocks act as the docking sites immobilize well light-harvesting antennae. microenvironment catalytic center precisely tuned by controlling functional groups at proximal distal positions units. As result, COF1-Au decorated strong electron-withdrawing exhibits activity toward production rates 333.0 ± 22.4 μmol g-1 h-1 37.0 2.5 mmol gAu-1 h-1, which are 2.8- 171-fold higher than that COF4-Au electron-donating porphyrin-Au molecular catalyst, respectively. could be further increased 427.9 18.7 61.1 2.7 catalysis COF5-Au featuring two different kinds groups. structure-activity relationship analysis reveals introduction facilitates separation transportation photogenerated electrons within entire framework. This work manifests structures optoelectronic properties COF-based can finely through rational predesign level, thus leading superior evolution.

Language: Английский

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Piperazine-Linked Covalent Organic Frameworks with High Electrical Conductivity

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(7), P. 2873 - 2878

Published: Feb. 7, 2022

A new kind of piperazine-linked covalent organic framework (COF) was synthesized through the nucleophilic substitution reaction between octaminophthalocyanines and hexadecafluorophthalocyanines. The two-dimensional (2D) frameworks are in tetragonally shaped polygon sheets, which stack an AA stacking mode to constitute periodically ordered metallophthalocyanine columns one-dimensional (1D) microporous channels. COFs exhibit excellent chemical stability permanent porosity. By virtue neatly arrayed phthalocyanine inbuilt cationic radicals, highly conductive. conductivity values NiPc-NH-CoPcF8 COF reached up 2.72 12.7 S m-1 for pellet film samples, respectively. Moreover, this p-type conductive exhibited a high carrier mobility 35.4 cm2 V-1 s-1. Both electric set records COFs.

Language: Английский

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