Metalated covalent organic frameworks: from synthetic strategies to diverse applications

Chemical Society Reviews, Год журнала: 2022, Номер 51(15), С. 6307 - 6416

Опубликована: Янв. 1, 2022

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

Язык: Английский

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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

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Direct Construction of Isomeric Benzobisoxazole–Vinylene-Linked Covalent Organic Frameworks with Distinct Photocatalytic Properties

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(30), С. 13953 - 13960

Опубликована: Июль 25, 2022

Vinylene/olefin-linked two-dimensional covalent organic frameworks (v-2D-COFs) have emerged as advanced semiconducting materials with excellent in-plane conjugation, high chemical stabilities, and precisely tunable electronic structures. Exploring new linkage chemistry for the reticular construction of v-2D-COFs remains in infancy challenging. Herein, we present a solid-state benzobisoxazole-mediated aldol polycondensation reaction two novel isomeric benzobisoxazole-bridged (v-2D-COF-NO1 v-2D-COF-NO2) trans cis configurations benzobisoxazole. Interestingly, benzobisoxazole linkers endow distinct optoelectronic electrochemical properties, ranging from light absorption emission to charge-transfer properties. When employed photocathode, v-2D-COF-NO1 exhibits photocurrent up ∼18 μA/cm2 under AM 1.5G irradiation at -0.3 V vs reversible hydrogen electrode (RHE), which is twice value v-2D-COF-NO2 (∼9.1 μA/cm2). With Pt cocatalyst, demonstrates photocatalytic evolution rate ∼1.97 mmol h-1 g-1, also clear contrast that (∼0.86 g-1) identical conditions. This work synthesis via structures

Язык: Английский

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Porous Dithiine-Linked Covalent Organic Framework as a Dynamic Platform for Covalent Polysulfide Anchoring in Lithium–Sulfur Battery Cathodes

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(20), С. 9101 - 9112

Опубликована: Май 11, 2022

Dithiine linkage formation via a dynamic and self-correcting nucleophilic aromatic substitution reaction enables the de novo synthesis of porous thianthrene-based two-dimensional covalent organic framework (COF). For first time, this organo-sulfur moiety is integrated as structural building block into crystalline layered COF. The structure new material deviates from typical planar interlayer π-stacking COF to form undulated layers caused by bending along C-S-C bridge, without loss aromaticity crystallinity overall structure. Comprehensive experimental theoretical investigations model compound, featuring thianthrene moiety, suggest partial delocalization sulfur lone pair electrons over backbone decreasing band gap promoting redox activity. Postsynthetic sulfurization allows for direct attachment polysulfides carbon afford molecular-designed cathode lithium-sulfur (Li-S) batteries with minimized polysulfide shuttle. fabricated coin cell delivers nearly 77% initial capacity even after 500 charge-discharge cycles at mA/g current density. This novel in chemistry an ideal motif designing materials studying advanced electrode Li-S on molecular level.

Язык: Английский

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Electronic State and Microenvironment Modulation of Metal Nanoparticles Stabilized by MOFs for Boosting Electrocatalytic Nitrogen Reduction

Advanced Materials, Год журнала: 2023, Номер unknown, С. 2210669 - 2210669

Опубликована: Март 4, 2023

Modulation of the local electronic structure and microenvironment catalytic metal sites plays a critical role in electrocatalysis, yet remains grand challenge. Herein, PdCu nanoparticles with an electron rich state are encapsulated into sulfonate functionalized metal-organic framework, UiO-66-SO3H (simply as UiO-S), their is further modulated by coating hydrophobic polydimethylsiloxane (PDMS) layer, affording [email protected]@PDMS. This resultant catalyst presents high activity toward electrochemical nitrogen reduction reaction (NRR, Faraday efficiency: 13.16%, yield: 20.24 µg h−1 mgcat.−1), far superior to corresponding counterparts. Experimental theoretical results jointly demonstrate that protonated supplies protons for NRR suppresses competitive hydrogen evolution reaction, electron-rich protected]@PDMS favorable formation N2H* intermediate reduce energy barrier NRR, thereby accounting its good performance.

Язык: Английский

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Efficient Adsorption of Acetylene over CO₂ in Bioinspired Covalent Organic Frameworks

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(33), С. 14992 - 14996

Опубликована: Авг. 5, 2022

Rational design of covalent organic frameworks (COFs) to broaden their diversity is highly desirable but challenging due the limited, expensive, and complex building blocks, especially compared with other easily available porous materials. In this work, we fabricated two novel bioinspired COFs, namely, NUS-71 NUS-72, using reticular chemistry ellagic acid triboronic acid-based blocks. Both COFs AB stacking mode exhibit high acetylene (C2H2) adsorption capacity excellent separation performance for C2H2/CO2 mixtures, which significant rarely explored COFs. The impressive affinities C2H2 appear be related sandwich structure formed by host framework via multiple host–guest interactions. This work not only represents a new avenue construction low-cost also expands variety COF family natural biochemicals as blocks broad application.

Язык: Английский

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Theory-guided electrocatalyst engineering: From mechanism analysis to structural design

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Год журнала: 2022, Номер 43(12), С. 2987 - 3018

Опубликована: Ноя. 9, 2022

Язык: Английский

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Fused-Ring-Linked Covalent Organic Frameworks

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(14), С. 6594 - 6603

Опубликована: Апрель 5, 2022

The development of linkage chemistry in the research area covalent organic frameworks (COFs) is fundamentally important for creating robust structures with high crystallinity and diversified functionality. We reach herein a new level complexity controllability by achieving first synthesis fused-ring-linked COFs. A series bicyclic pyrano[4,3-b]pyridine COFs have been constructed via cascade protocol involving Schiff-base condensation, intramolecular [4 + 2] cycloaddition, dehydroaromatization. With broad scope Brønsted or Lewis acids as catalyst, designed monomers, that is, O-propargylic salicylaldehydes multitopic anilines, were converted into one-pot fashion. obtained exhibited excellence terms purity, stability, crystallinity, comprehensively characterized solid-state nuclear magnetic resonance (NMR) spectroscopy, powder X-ray diffraction, high-resolution transmission electron microscopy, so on. Specifically, highly selective formation (>94%) was verified quantitative NMR measurements combined 13C-labeling synthesis. Moreover, fused-ring possesses fully locked conformation, which benefits to observed these Advancing from solo bonds single rings fused rings, this study has opened up possibilities concise construction sophisticated COF controllability.

Язык: Английский

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Efficient Electron Transfer from an Electron‐Reservoir Polyoxometalate to Dual‐Metal‐Site Metal‐Organic Frameworks for Highly Efficient Electroreduction of Nitrogen

Advanced Functional Materials, Год журнала: 2023, Номер 33(28)

Опубликована: Апрель 4, 2023

Abstract Precise design and construction of catalysts with satisfied performance for ambient electrolytic nitrogen reduction reaction (e‐NRR) is extremely challenging. By in situ integrating an electron‐rich polyoxometalates (POMs) into stable metal organic frameworks (MOFs), five POMs‐based MOFs formulated as [Fe x Co y (Pbpy) 9 (ox) 6 (H 2 O) ][P W 18 O 62 ]·3H (abbreviated Fe MOF‐P ) are created directly used e‐NRR. Their electrocatalytic performances remarkably improved thanks to complementary advantages promising possibilities POMs. In particular, NH 3 yield rates 47.04 µg h −1 mg cat. Faradaic efficiency 31.56% by FeCoMOF‐P e‐NRR significantly enhanced a factor 4 3, respectively, compared the 0.5 (Pbpy)(ox)] ·(Pbpy) . The cyclic voltammetry curves, density functional theory calculations Fourier‐transform infrared spectroscopy confirm that there directional electron channel from P unit accelerate transfer electrons. And introduction bimetals ‐based can reduce energy *N H step, thereby increasing production More importantly, this POM embedding strategy be extended create other performances, which opens new avenue future breakthrough bottleneck

Язык: Английский

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Porous framework materials for energy & environment relevant applications: A systematic review

Green Energy & Environment, Год журнала: 2023, Номер 9(2), С. 217 - 310

Опубликована: Янв. 3, 2023

Carbon peaking and carbon neutralization trigger a technical revolution in energy & environment related fields. Development of new technologies for green production storage, industrial saving efficiency reinforcement, capture, pollutant gas treatment is highly imperious demand. The emerging porous framework materials such as metal–organic frameworks (MOFs), covalent organic (COFs) hydrogen-bonded (HOFs), owing to the permanent porosity, tremendous specific surface area, designable structure customizable functionality, have shown great potential major energy-consuming processes, including sustainable catalytic conversion, energy-efficient separation storage. Herein, this manuscript presents systematic review global comprehensive applications, from macroscopic application perspective.

Язык: Английский

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