Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Generation

ACS Materials Letters, Journal Year: 2024, Volume and Issue: 6(5), P. 2007 - 2049

Published: April 17, 2024

Hydrogen peroxide (H2O2), a valuable chemical, is widely used as powerful oxidizing agent in chemical synthesis, pharmaceuticals, medical disinfection, and environmental treatment industries. Currently, over 95% of H2O2 produced industrially using the anthraquinone process, which associated with its high energy consumption hazardous byproducts. Therefore, photochemical synthesis from water oxygen covalent organic framework based photocatalysts have attracted considerable attention. This review aims to outline recent achievements, challenges future prospects COFs heterogeneous for sustainable generation. We summarize chronological development COFs, different mechanisms involved, detailed experiments quantification methods photocatalytic The puts forward an outlook, highlighting advantages limitations anticipate that this will provide insight into current progress inspire next-generation production.

Language: Английский

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Emerging MOFs, COFs, and their derivatives for energy and environmental applications

The Innovation, Journal Year: 2025, Volume and Issue: 6(2), P. 100778 - 100778

Published: Jan. 18, 2025

Traditional fossil fuels significantly contribute to energy supply, economic development, and advancements in science technology. However, prolonged extensive use of has resulted increasingly severe environmental pollution. Consequently, it is imperative develop new, clean, pollution-free sources with high density versatility as substitutes for conventional fuels, although this remains a considerable challenge. Simultaneously, addressing water pollution critical concern. The design, optimization functional nanomaterials are pivotal advancing new solutions pollutant remediation. Emerging porous framework materials such metal-organic frameworks (MOFs) covalent organic (COFs), recognized exemplary crystalline materials, exhibit potential applications due their specific surface area, adjustable pore sizes structures, permanent porosity, customizable functionalities. This work provides comprehensive systematic review the MOFs, COFs, derivatives emerging technologies, including oxygen reduction reaction, evolution hydrogen lithium-ion batteries, remediation carbon dioxide reaction management. In addition, strategies performance adjustment structure-effect relationships these explored. Interaction mechanisms summarized based on experimental discussions, theoretical calculations, advanced spectroscopy analyses. challenges, future prospects, opportunities tailoring presented.

Language: Английский

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Hydrazone‐Linked Covalent Organic Frameworks

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(31)

Published: May 14, 2024

Hydrazone-linked covalent organic frameworks (COFs) with structural flexibility, heteroatomic sites, post-modification ability and high hydrolytic stability have attracted great attention from scientific community. COFs, as a subclass of Schiff-base was firstly reported in 2011 by Yaghi's group later witnessed prosperous development various aspects. Their adjustable structures, precise pore channels plentiful sites hydrazone-linked structures possess much potential diverse applications, for example, adsorption/separation, chemical sensing, catalysis energy storage, etc. Up to date, the systematic reviews about COFs are still rare. Therefore, this review, we will summarize their preparation methods, characteristics related discuss opportunity or challenge COFs. We hope review could provide new insights exploring more appealing functions applications.

Language: Английский

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Ionic Liquid‐Induced Product Switching in CO₂ Electroreduction on Copper Reaction Interface

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

Published: May 13, 2024

Abstract The electrochemical reduction of CO 2 (CO RR) mainly occurs at the three‐phase interface, and properties an interface can directly affect RR pathway. Cu‐based materials produce considerable amounts alcohols hydrocarbons, but it is hard to precisely regulate reaction obtain specific target products. Herein, Cu surface through a facile strategy ionic liquid modification are successfully adjusted. According theoretical calculations in situ Raman FTIR spectra characterizations, revealed that introduction liquids (e.g., [Bmim][PF 6 ]) control energy barriers distribution density key intermediates on thus totally change pathway electroreduction. Consequently, dominant products from catalyst will be dramatically switched between C H 4 with 71.1% Faraday efficiency (FE) CH 67.2% FE. It rarely seen previous reports fundamentally changed simple modifications. This work offers straightforward approach tune interfacial understand mechanisms various electrocatalytic reactions.

Language: Английский

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Constructing Co₄(SO₄)₄ Clusters within Metal–Organic Frameworks for Efficient Oxygen Electrocatalysis

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(38)

Published: Aug. 3, 2024

Abstract Multinuclear metal clusters are ideal candidates to catalyze small molecule activation reactions involving the transfer of multiple electrons. However, synthesizing active is a big challenge. Herein, on constructing an unparalleled Co 4 (SO ) cluster within porphyrin‐based metal–organic frameworks (MOFs) and electrocatalytic features such for oxygen evolution reaction (OER) reduction (ORR) reported. The II sulfate complexes tetrakis(4‐pyridyl)porphyrin under solvothermal conditions afforded ‐M‐MOFs (M═Co, Cu, Zn). Crystallographic studies revealed that these have same framework structure, having connected by metalloporphyrin units through Co─N pyridyl bonds. In cluster, four ions chemically symmetrically equivalent each coordinated with O atoms give distorted cube‐like structure. Electrocatalytic showed all OER ORR. Importantly, regulating activity units, it confirmed electrocatalysis. With use porphyrins as connecting ‐Co‐MOF displays highest in this series MOFs showing 10 mA cm −2 current density at 357 mV overpotential ORR half‐wave potential 0.83 V versus reversible hydrogen electrode (RHE). Theoretical synergistic effect two proximal facilitating formation O─O This work fundamental significance present construction structures electrocatalysis demonstrate cooperation between during bond process.

Language: Английский

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Value‐Added Cascade Synthesis Mediated by Paired‐Electrolysis Using an Ultrathin Microenvironment‐Inbuilt Metalized Covalent Organic Framework Heterojunction

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(27)

Published: April 25, 2024

Abstract Energy‐saving and value‐added management in advanced catalysis is highly desirable but challenged by the limitations of multifunctional catalysts catalytic modules. Herein, an azo‐linked phthalocyanine‐porphyrin covalent organic framework (COF) with ultrathin layered nanostructure grown on carbon nanotubes (NiPc‐azo‐H2Pp@CNTs) has been designed synthesized, which can serve as a active stable bifunctional heterojunction electrocatalyst for selective paired‐electrosynthesis through coupling anodic iodide oxidation reaction cathodic CO 2 conversion. Particularly, inbuilt local microenvironment conferred dihydroporphyrin moieties COF act proton reservoir to promote relay at interface during electrocatalytic process. Moreover, cascade construction dual electrocatalytic/organocatalytic modules, cathode‐generated be further converted dimethyl carbonate yield 6.21 mmol L −1 h , while anode‐produced iodine derived into iodoform hundred‐milligram scale. It worth noting that synthesis mediated paired‐electrolysis using distinctive high‐powered electrocatalysts will help advance sustainable development industrial intelligent manufacturing.

Language: Английский

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Improving Active Site Local Proton Transfer in Porous Organic Polymers for Boosted Oxygen Electrocatalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(47)

Published: Aug. 15, 2024

Abstract Improving proton transfer is vital for electrocatalysis with porous materials. Although several strategies are reported to assist in channels, few studies dedicated improving at the local environments of active sites Herein, we report on new Co‐corrole‐based organic polymers (POPs) improved electrocatalytic oxygen reduction reaction (ORR) and evolution (OER). By tuning pore sizes installing relays Co corrole sites, designed synthesized POP‐2‐OH both channels sites. This POP shows remarkable activity ORR E 1/2 =0.91 V vs RHE OER η 10 =255 mV. Therefore, this work significant present a strategy improve site materials highlight key role such structural functionalization boosting electrocatalysis.

Language: Английский

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Electromagnetic Attenuation of Sm‐Doped Alloys Modified by Interface Exchange Coupling and Magnetocrystalline Stress Anisotropy

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Abstract The narrow resonance width of magnetic alloys limits their application as wide frequency electromagnetic wave absorbers within the gigahertz range. To address this issue, study proposes engineering homogeneous interfaces and enhancing anisotropy through Sm doping in FeCo alloy, thereby giving rise to a broadened an increased loss. results show that Sm‐doping produces abundant grain boundaries strengthening charge transfer (0.16 ev) moment (0.34 µ B ), which ultimately heightens interfacial exchange coupling coefficient by six times. Furthermore, magnetocrystalline constant rises from 4.1 × 10 5 3.0 10⁶ J m − 3 , stress expands four fold, owing induced 4f electron spin‐orbit lattice distortion. Consequently, natural are elevated 10.4 6.4 GHz, separately. Eventually, with loss angle above 0.5 over 7–14 GHz present ultra‐wide absorption. This work provides new approach homointerface improve absorption alloys.

Language: Английский

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Boosting oxygen-resistant CO₂ electroreduction reaction in acidic media over conjugated frameworks

Journal of Materials Chemistry A, Journal Year: 2024, Volume and Issue: 12(16), P. 9486 - 9493

Published: Jan. 1, 2024

A cobalt polyphthalocyanine framework coated by polyaniline shows excellent oxygen-resistant CO 2 electroreduction performance with high selectivity of up to 87.4% and an industry-level j −270 mA cm −2 under 5% O feed gas in acidic media.

Language: Английский

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Pore size modulation of cobalt-corrole-based porous organic polymers for boosted electrocatalytic oxygen reduction reaction

Materials Today Catalysis, Journal Year: 2024, Volume and Issue: 5, P. 100050 - 100050

Published: April 21, 2024

The highly active and selective oxygen reduction reaction (ORR) is vital to promote the performance of advanced energy conversion systems, such as fuel cells other electrochemical devices. Porous framework materials have capability combine catalytic units with their porous characteristics, making them promising catalysts. However, due difficulty in designing synthesizing units, pore size modulation primarily achieved by altering linkers. We herein report design synthesis three cobalt-corrole-based organic polymers (Co-POP-1, Co-POP-2 Co-POP-3) different sizes, which were obtained extending 5,15-meso substituents Co corroles. Compared Co-POP-1 Co-POP-2, Co-POP-3 has largest size. Benefiting from enhanced mass transfer exposed sites, displayed remarkably boosted activity for four-electron/four-proton (4e−/4H+) ORR a half-wave potential E1/2 = 0.89 V versus reversible hydrogen electrode (RHE) 0.1 M KOH solutions. This work not only presents polymer catalyst high selectivity but also provides new strategy moderate materials.

Language: Английский

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