Enhanced and synergistic catalytic activation by photoexcitation driven S−scheme heterojunction hydrogel interface electric field

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

Опубликована: Окт. 23, 2023

The regulation of heterogeneous material properties to enhance the peroxymonosulfate (PMS) activation degrade emerging organic pollutants remains a challenge. To solve this problem, we synthesize S-scheme heterojunction PBA/MoS2@chitosan hydrogel achieve photoexcitation synergistic PMS activation. constructed photoexcited carriers undergo redox conversion with through transfer pathway driven by directional interface electric field. Multiple pathways greatly reactive oxygen species generation, leading significant increase in doxycycline degradation rate. Meanwhile, 3D polymer chain spatial structure chitosan is conducive rapid capture and electron transport advanced oxidation process, reducing use transition metal activator limiting leaching ions. There reason believe that regulated will provide new perspective for future design research on enhancing heterologous catalysis process.

Язык: Английский

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Site Engineering of Covalent Organic Frameworks for Regulating Peroxymonosulfate Activation to Generate Singlet Oxygen with 100 % Selectivity

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(43)

Опубликована: Сен. 5, 2023

Singlet oxygen (1 O2 ) is an excellent reactive species (ROSs) for the selective conversion of organic matter, especially in advanced oxidation processes (AOPs). However, due to huge dilemma synthesizing single-site type catalysts, control and regulation 1 generation AOPs still challenging underlying mechanism remains largely obscure. Here, taking advantage well-defined flexibly tunable sites covalent frameworks (COFs), we report first achievement precisely regulating ROSs peroxymonosulfate (PMS)-based by site engineering COFs. Remarkably, COFs with bipyridine units (BPY-COFs) facilitate PMS activation via a nonradical pathway 100 % , whereas biphenyl-based (BPD-COFs) almost identical structures activate produce radicals (⋅OH SO4.- ). The BPY-COFs/PMS system delivers boosted performance degradation target pollutants from water, which ca. 9.4 times that its BPD-COFs counterpart, surpassing most reported PMS-based systems. Mechanism analysis indicated highly electronegative pyridine-N atoms on BPY-COFs provide extra adsorb terminal H PMS, resulting simultaneous adsorption O one pyridine ring, facilitates cleavage S-O bond generate .

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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Construction of Thiadiazole-Bridged sp²-Carbon-Conjugated Covalent Organic Frameworks with Diminished Excitation Binding Energy Toward Superior Photocatalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(2), С. 1318 - 1325

Опубликована: Янв. 5, 2024

Sp2-carbon-conjugated covalent organic frameworks (sp2c-COFs) have emerged as promising platforms for phototo–chemical energy conversion due to their tailorable optoelectronic properties, in-plane π-conjugations, and robust structures. However, the development of sp2c-COFs in photocatalysis is still highly hindered by limited linkage chemistry. Herein, we report a novel thiadiazole-bridged sp2c-COF (sp2c-COF-ST) synthesized thiadiazole-mediated aldol-type polycondensation. The resultant sp2c-COF-ST demonstrates high chemical stability under strong acids bases (12 M HCl or 12 NaOH). electro-deficient thiadiazole together with fully conjugated planar skeleton endows superior photoelectrochemical performance charge-carrier separation migration ability. As result, when employed photocathode, exhibits significant photocurrent up ∼14.5 μA cm–2 at 0.3 V vs reversible hydrogen electrode (RHE) visible-light irradiation (>420 nm), which much higher than those analogous COFs partial imine linkages (mix-COF-SNT ∼ 9.5 cm–2) full (imi-COF-SNNT 4.9 cm–2), emphasizing importance structure–property relationships. Further temperature-dependent photoluminescence spectra density functional theory calculations demonstrate that has smaller exciton binding well effective mass comparison mix-COF-SNT imi-COF-SNNT, suggests sp2c-conjugated enhances dissociation carrier light irradiation. This work highlights design preparation photocatalytic performance.

Язык: Английский

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Dissolved organic matter promotes photocatalytic degradation of refractory organic pollutants in water by forming hydrogen bonding with photocatalyst

Water Research, Год журнала: 2023, Номер 242, С. 120297 - 120297

Опубликована: Июль 2, 2023

Язык: Английский

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Highly-efficient photocatalytic H2O2 evolution using hydrothermal carbons with donor-acceptor furan couples

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 332, С. 122770 - 122770

Опубликована: Апрель 13, 2023

Язык: Английский

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Molecular‐Level Regulation Strategies Toward Efficient Charge Separation in Donor−Acceptor Type Conjugated Polymers for Boosted Energy‐Related Photocatalysis

Advanced Energy Materials, Год журнала: 2023, Номер 14(5)

Опубликована: Дек. 11, 2023

Abstract The development of efficient photocatalysts for artificial photocatalytic energy conversion is an intriguing strategy. Promisingly, conjugated polymers (CPs) have been actively investigated as alternatives to traditional inorganic semiconductors photocatalysis due their molecularly tunable optoelectronic properties, thus providing a great platform molecular design. Incorporating donor (D) and acceptor (A) units into the backbone CPs ensures adequate D−A interface, which essential facilitating charge separation. This approach also allows bandgaps leading significant progress in conversions recent years. Here, fundamentals D–A type are initially outlined, followed by advanced experimental methods density functional theory (DFT) calculations investigating carrier dynamics. Then, detailed exposition synthetic strategies carried out. Their extensive applications diverse energy‐related conversions, such hydrogen evolution, oxygen overall water splitting, CO 2 reduction, N H O evolution comprehensively presented. review provides new comprehensive insights molecular‐level design catalysts boosted conversion, expected further advance photocatalysis.

Язык: Английский

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Exciton dissociation and transfer behavior and surface reaction mechanism in Donor–Acceptor organic semiconductor photocatalytic separation of uranium

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 332, С. 122751 - 122751

Опубликована: Апрель 11, 2023

Язык: Английский

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Interfacial Mo–S bond modulated S-scheme Mn0.5Cd0.5S/Bi2MoO6 heterojunction for boosted photocatalytic removal of emerging organic contaminants

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Год журнала: 2025, Номер 68, С. 259 - 271

Опубликована: Янв. 1, 2025

Язык: Английский

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Molecular modification: A promising strategy for the design of donor-acceptor-type organic polymers photocatalyst

Applied Catalysis B Environment and Energy, Год журнала: 2024, Номер 352, С. 124043 - 124043

Опубликована: Апрель 21, 2024

Язык: Английский

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