Integrating Dual-Metal Sites into Covalent Organic Frameworks for Enhanced Photocatalytic CO₂ Reduction

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 4316 - 4329

Published: March 15, 2023

Photocatalytic CO2 reduction holds great promise for synchronously addressing carbon neutrality and producing fuels, although enhancing the photocatalyst activity tuning product selectivity remain enormous challenges. Herein, we synthesized four crystalline porous benzothiadiazole-based covalent organic frameworks (COFs) with different carbonyl groups reported a dual metalation strategy to fabricate Co Ni dual-metal sites anchored on COFs by interaction between metal thiadiazole high-performance photoreduction. Among as-synthesized metalated Co/Ni sites, CoNi–COF-3 achieved an impressive CO generation rate of 2567 μmol g–1 h–1 92.2%, which were significantly higher than those single sites. Experimental theoretical results revealed that superior photocatalytic performance was attributed synergic effect fully β-ketoenamine-tautomerized COF-3 configuration not only facilitated photogenerated charge carrier dynamics but also reduced energy barriers *COOH formation promoted adsorption desorption. This work provides valuable insights into future design improved COF photocatalysts conversion.

Language: Английский

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Reticular framework materials for photocatalytic organic reactions

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(22), P. 7949 - 8004

Published: Jan. 1, 2023

Photocatalytic organic reactions, harvesting solar energy to produce high value-added chemicals, have attracted increasing attention as a sustainable approach address the global crisis and environmental issues. Reticular framework materials, including metal-organic frameworks (MOFs) covalent (COFs), are widely considered promising candidates for photocatalysis owing their crystallinity, tailorable pore environment extensive structural diversity. Although design synthesis of MOFs COFs been intensively developed in last 20 years, applications photocatalytic transformations still preliminary stage, making systematic summary necessary. Thus, this review aims provide comprehensive understanding useful guidelines exploration suitable MOF COF photocatalysts towards appropriate reactions. The commonly used reactions categorized facilitate identification reaction types. From practical viewpoint, fundamentals experimental design, active species, performance evaluation external conditions, discussed detail easy experimentation. Furthermore, latest advances COFs, composites, comprehensively summarized according actual sites, together with discussion structure-property relationship. We believe that study will be helpful researchers novel reticular various synthetic applications.

Language: Английский

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Covalent organic frameworks and their composites as multifunctional photocatalysts for efficient visible-light induced organic transformations

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 472, P. 214774 - 214774

Published: Aug. 23, 2022

Language: Английский

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Three-Motif Molecular Junction Type Covalent Organic Frameworks for Efficient Photocatalytic Aerobic Oxidation

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3396 - 3404

Published: Jan. 24, 2024

Covalent organic frameworks (COFs), with the features of flexible structure regulation and easy introduction functional groups, have aroused broad interest in field photocatalysis. However, due to low light absorption intensity, photoelectron conversion efficiency, lack suitable active sites, it remains a great challenge achieve efficient photocatalytic aerobic oxidation reactions. Herein, based on reticular chemistry, we rationally designed series three-motif molecular junction type COFs, which formed dual photosensitizer coupled redox junctions containing multifunctional COF photocatalysts. Significantly, strong adsorption ability units integrated reduction features, PY-BT exhibited highest activity for oxidation. Especially, achieved benzylamine efficiency 99.9% 2.5 h, is much higher than that two-motif only one or unit lacking COFs. The mechanism selective was studied through comprehensive experiments density theory calculations. results showed photoinduced electron transfer occurred from PY then triphenylamine BT. Furthermore, thermodynamics energy lower others, confirmed synergistic effect This work provided new strategy design COFs also represented insight into catalytic

Language: Английский

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Engineering high-coordinated cerium single-atom sites on carbon nitride nanosheets for efficient photocatalytic amine oxidation and water splitting into hydrogen

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 462, P. 142084 - 142084

Published: Feb. 23, 2023

Language: Английский

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Design and synthesis of broadband absorption covalent organic framework for efficient artificial photocatalytic amine coupling

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 7, 2024

Developing highly active materials that efficiently utilize solar spectra is crucial for photocatalysis, but still remains a challenge. Here, we report new donor-acceptor (D-A) covalent organic framework (COF) with wide absorption range from 200 nm to 900 (ultraviolet-visible-near infrared light). We find the thiophene functional group accurately introduced into electron acceptor units of TpDPP-Py (TpDPP: 5,5'-(2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo [3,4-c]pyrrole-1,4-diyl)bis(thiophene-2-carbaldehyde), Py: 1,3,6,8-tetrakis(4-aminophenyl)pyrene) COFs not only significantly extends its spectral capacity also endows them two-photon and three-photon effects, greatly enhancing utilization rate sunlight. The selective coupling benzylamine as target reactant used assess photocatalytic activity COFs, showing high conversion 99% selectivity 98% in 20 min. Additionally, exhibit universality other imine derivatives ~100% efficiency. Overall, this work brings significant strategy developing enhance activity.

Language: Английский

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A critical review on surface-modified nano-catalyst application for the photocatalytic degradation of volatile organic compounds

Environmental Science Nano, Journal Year: 2021, Volume and Issue: 9(1), P. 61 - 80

Published: Dec. 8, 2021

Surface modified nano-catalysts to improve the performance of photocatalytic degradation VOC.

Language: Английский

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A novel triazine-based covalent organic framework combined with AuNPs and reduced graphene oxide as an electrochemical sensing platform for the simultaneous detection of uric acid, dopamine and ascorbic acid

Colloids and Surfaces A Physicochemical and Engineering Aspects, Journal Year: 2021, Volume and Issue: 634, P. 127928 - 127928

Published: Nov. 20, 2021

Language: Английский

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Construction of Hydrazone-Linked Macrocycle-Enriched Covalent Organic Frameworks for Highly Efficient Photocatalysis

Chemistry of Materials, Journal Year: 2022, Volume and Issue: 34(12), P. 5726 - 5739

Published: June 9, 2022

Covalent organic frameworks (COFs) are an emerging class of crystalline porous materials with tailor-made functionalities for improved photocatalytic activity. However, limited choice building blocks greatly restricts the photochemical performance and application scope COFs in photocatalysis. Herein, a covalent hybridization approach is reported to address these issues by knitting rigid macrocyclic struts, namely, pillararenes, into extended network COFs. Varying different ratios pillararenes unique conformations electron-rich cavities can not only generate confined molecular space exciton migration carrier transport but also create new interfaces interplay photogenerated charge carriers, leading high promoting efficient oxidation amines imines. This work paves way constructing macrocycle-derived provides promising platform photocatalysis through predesign functionalization pore surface.

Language: Английский

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Enhanced Carrier Separation in Visible-Light-Responsive Polyoxometalate-Based Metal–Organic Frameworks for Highly Efficient Oxidative Coupling of Amines

ACS Applied Materials & Interfaces, Journal Year: 2022, Volume and Issue: 14(24), P. 27882 - 27890

Published: June 8, 2022

Photocatalytic technology is widely studied, while it comes with drawbacks such as low sunlight utilization efficiency and high carrier recombination rates. Herein, for the first time, we present two crystalline polyoxometalate (POM)-based metal-organic frameworks (POMOFs), {[Cd(DMF)2Ru(bpy)2(dcbpy)]2(POMs)(DMF)2} xDMF (PMo-1, POMs = [PMoVI11MoVO40]4-, x 5; SiW-2, [SiW12O40]4-, 4) through assembling photosensitizer [Ru(bpy)2(H2dcbpy)]Cl2 into a single framework. The assembly not only enhances light absorption in visible regime but also improves separation efficiency; atop of that, both POMOFs demonstrate activities photocatalytic oxidative coupling amines. Particularly, PMo-1 enables quantitative completion benzylamine reaction within 30 min (yield 99.6%) turnover frequency (TOF 6631.6 h-1). To our knowledge, catalyst outperforms any other photocatalysts previously reported similar use cases where TOF values were usually obtained <2000 h-1.

Language: Английский

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