Engineering 2D Photocatalysts for Solar Hydrogen Peroxide Production

Advanced Energy Materials, Год журнала: 2024, Номер 14(23)

Опубликована: Апрель 3, 2024

Abstract Solar energy can be utilized in photocatalysis technology to realize light‐driven hydrogen peroxide (H 2 O ) production, a green chemical synthesis route. Designing high‐performance photocatalysts is critical achieving practical solar H production. During the past decade, significant research progress made photocatalytic materials for Particularly 2D materials‐based stand out due their unique physical and properties. This review highlights intricate relationship between material innovation photochemical It starts with fundamental principles of generation, focusing on crucial steps such as photon absorption, carrier dynamics, surface reactions, challenges that solve at each step. Then, various production are introduced detail. Engineering strategies optimize performance discussed afterward. Finally, future opportunities designing outlined. expected inspire engineering conversion other chemicals.

Язык: Английский

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Ambient Preparation of Benzoxazine‐based Phenolic Resins Enables Long‐term Sustainable Photosynthesis of Hydrogen Peroxide

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(23)

Опубликована: Март 25, 2023

Rational design of polymer structures at the molecular level promotes iteration high-performance photocatalyst for sustainable photocatalytic hydrogen peroxide (H2 O2 ) production from oxygen and water, which also lays basis revealing reaction mechanism. Here we report a benzoxazine-based m-aminophenol-formaldehyde resin (APFac) polymerized ambient conditions, exhibiting superior H2 yield long-term stability to most polymeric photocatalysts. Benzoxazine structure was identified as crucial active segment in APFac. Favorable adsorption oxygen/intermediates on benzoxazine commendable product selectivity accelerated kinetically stepwise single-electron reduction reaction. The proposed phenolic provides possibility batches industrial application, sheds light de novo analysis metal-free

Язык: Английский

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Twistedly hydrophobic basis with suitable aromatic metrics in covalent organic networks govern micropollutant decontamination

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Окт. 24, 2023

Abstract The pre-designable structure and unique architectures of covalent organic frameworks (COFs) render them attractive as active porous medium for water crisis. However, the effect functional basis with different metrics on regulation interfacial behavior in advanced oxidation decontamination remains a significant challenge. In this study, we pre-design fabricate molecular interfaces by creating ordered π skeletons, incorporating pore sizes, engineering hydrophilic or hydrophobic channels. These synergically break through adsorption energy barrier promote inner-surface renewal, achieving high removal rate typical antibiotic contaminants (like levofloxacin) BTT-DATP-COF, compared BTT-DADP-COF BTT-DAB-COF. experimental theoretical calculations reveal that such enable hole-driven levofloxacin at interface BTT fragments to occur, accompanying electron-mediated oxygen reduction terphenyl motif radicals, endowing it facilitate balanced extraction holes electrons.

Язык: Английский

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In-situ formatting donor-acceptor polymer with giant dipole moment and ultrafast exciton separation

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Фев. 13, 2024

Abstract Donor-acceptor semiconducting polymers present countless opportunities for application in photocatalysis. Previous studies have showcased their advantages through direct bottom-up methods. Unfortunately, these approaches often involve harsh reaction conditions, overlooking the impact of uncontrolled polymerization degrees on Besides, mechanism behind separation electron-hole pairs (excitons) donor-acceptor remains elusive. This study presents a post-synthetic method involving light-induced transformation building blocks hyper-cross-linked from donor-carbon-donor to donor-carbon-acceptor states, resulting polymer with substantial intramolecular dipole moment. Thus, excitons are efficiently separated transformed polymer. The utility this strategy is exemplified by enhanced photocatalytic hydrogen peroxide synthesis. Encouragingly, our observations reveal formation charge transfer states using time-resolved techniques, confirming transient exciton behavior and relaxation. not only guides development highly efficient photocatalysts but also applies various fields, including organic solar cells, light-emitting diodes, sensors.

Язык: Английский

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Efficient Photosynthesis of Hydrogen Peroxide by Cyano‐Containing Covalent Organic Frameworks from Water, Air and Sunlight

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(6)

Опубликована: Дек. 28, 2023

Abstract The insufficient exciton ( e − ‐ h + pair) separation/transfer and sluggish two‐electron water oxidation are two main factors limiting the H 2 O photosynthetic efficiency of covalent organic frameworks (COFs) photocatalysts. Herein, we present an alternative strategy to simultaneously facilitate reduce energy barrier in COFs via a dicyano functionalization. situ characterization theoretical calculations reveal that functionalization improves amount charge transfer channels between donor acceptor units from COF‐0CN without cyano three COF‐1CN with mono‐cyano four COF‐2CN functionalization, leading highest COF‐2CN. More importantly, group activates neighbouring C atom produce key *OH intermediate for effectively reducing rate‐determining photosynthesis. enhanced result high yield (1601 μmol g −1 ) oxygen using sacrificial reagent under visible‐light irradiation. can wide pH range, different real samples, scaled‐up reactor natural sunlight irradiation, continuous‐flow consecutively producing solution decontamination.

Язык: Английский

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Structural Regulation of Photocatalyst to Optimize Hydroxyl Radical Production Pathways for Highly Efficient Photocatalytic Oxidation

Advanced Materials, Год журнала: 2023, Номер 36(3)

Опубликована: Окт. 22, 2023

Ring-opening of phenol in wastewater is the pivotal step photocatalytic degradation. The highly selective generation catalytical active species (•OH) to facilitate this process presents a significant scientific challenge. Therefore, novel approach for designing photocatalysts with single-atom containment metal-covalent organic frameworks (M-COFs) proposed. selection imine-linked COFs containing abundant N and O-chelate sites provides solid foundation anchoring metal atom. These dispersed atom possess rapid accumulation transfer capabilities photogenerated electrons, while periodic π-conjugated structure 2D-COFs establishes an effective platform. Additionally, Lewis acid properties imine bonds can enhance adsorption capacity toward gases base properties, such as O

Язык: Английский

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Structural Motifs in Covalent Organic Frameworks for Photocatalysis

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Март 10, 2024

Abstract Covalent organic frameworks (COFs) attract significant attention due to their ordered, crystalline, porous, metal‐free, and predictable structures. These unique characteristics offer great opportunities for the diffusion transmission of photogenerated charges during photocatalysis. Currently, a considerable number COFs are used as metal‐free semiconductor photocatalysts. This review aims understand relationships between structure photocatalysis performance provides in‐depth insight into synthetic strategy improve performance. Subsequently, focuses on structural motif in sustainable photocatalytic hydrogen evolution, carbon dioxide reduction, peroxide generation, compound transformations. Last, conjunction with progress achieved challenges yet be overcome, candid discussion is undertaken regarding field COF photocatalysis, accompanied by presentation potential research avenues future directions. seeks provide readers comprehensive understanding pivotal role robust guidance innovative utilization

Язык: Английский

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

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 3396 - 3404

Опубликована: Янв. 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

Язык: Английский

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Vinyl‐Group‐Anchored Covalent Organic Framework for Promoting the Photocatalytic Generation of Hydrogen Peroxide

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(21)

Опубликована: Март 16, 2024

The artificial photosynthesis of H

Язык: Английский

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Keto-anthraquinone covalent organic framework for H2O2 photosynthesis with oxygen and alkaline water

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Март 26, 2024

Hydrogen peroxide photosynthesis suffers from insufficient catalytic activity due to the high energy barrier of hydrogen extraction H2O. Herein, we report that mechanochemically synthesized keto-form anthraquinone covalent organic framework which is able directly synthesize H2O2 (4784 μmol h-1 g-1 at λ > 400 nm) oxygen and alkaline water (pH = 13) in absence any sacrificial reagents. The strong alkalinity resulted formation OH-(H2O)n clusters water, were adsorbed on keto moieties within then dissociated into O2 active hydrogen, because was largely lowered. produced reacted with generate anthrahydroquinone, subsequently oxidized by produce H2O2. This study ultimately sheds light importance H2O for demonstrates synthesis achievable under conditions.

Язык: Английский

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