Enhanced exciton dissociation through scandium-decorated conjugated polymers for artificial photosynthesis of hydrogen peroxide

Journal of Energy Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Язык: Английский

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Functional Groups‐Dependent Tp‐Based COF/MgIn₂S₄ S‐Scheme Heterojunction for Photocatalytic Hydrogen Evolution

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Март 3, 2025

Abstract An effective technique for improving the photocatalytic activity is functional‐group‐oriented approach of covalent organic frameworks (COFs). However, creation functional groups‐dependent COF‐based S‐scheme heterojunction has seldom been reported. In this study, two distinct Tp‐based COFs with different groups using a solvothermal technique, TpPa‐1 −H and TpPa‐2 −Me (methyl), respectively, synthesized. Moreover, COF/MgIn 2 S 4 (MIS) heterojunctions (i.e., TpPa‐1/MIS TpPa‐2/MIS) are created to clarify dynamics photoinduced charges boost H evolution. Notably, evolution optimum TpPa‐1/MIS‐5% (13.16 mmol g −1 h ) 4.3 times greater than that TpPa‐2/MIS‐5% (3.05 ), which attributed in could slow down interfacial photogenerated electron‐transfer make its surface less hydrophilic, resulting lower over TpPa‐2/MIS‐5%. On contrary, remarkable associated fast electron transfer from MIS due hydrophilic TpPa‐1, induced stronger internal electric field motivated by construction heterojunction.

Язык: Английский

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Ethynyl‐Linked Donor–Acceptor Covalent Organic Framework for Highly Efficient Photocatalytic H₂O₂ Production

Advanced Energy Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 19, 2025

Abstract Photocatalytic H 2 O synthesis from and is considered to be one of the most promising alternative approaches for manufacturing . Developing highly active selective photocatalysts significant in achieving efficient photosynthesis. Herein, an ethynyl‐linked donor–acceptor covalent organic framework (COF), named EBBT‐COF, prepared condensation reaction between electron‐deficient unit 4,4′,4″‐(1,3,5‐benzenetriyltri‐2,1‐ethynediyl)tris‐benzenamine electron‐rich benzo[1,2‐b:3,4‐b′:5,6‐b″]trithiophene‐2,5,8‐tricarboxaldehyde. Powder X‐ray diffraction N adsorption isotherm unveil crystalline porous hcb network EBBT‐COF with pores size centered at ca 2.3 nm. Spectroscopic characterizations demonstrate excellent visible‐light absorption capacity enhanced photo‐induced charge separation transport efficiency owing its architecture. Density functional theory calculations electrochemical tests indicate high activity selectivity toward 2e − reduction water oxidation triethynylbenzene trithiophene moieties accelerate ‐to‐H O‐to‐H conversion, respectively. These merits enable a photocatalyst generation yield rate 5 686 µmol g −1 h , optimal apparent quantum 15.14%, solar‐to‐chemical conversion 1.17% (λ > 400 nm), representing best performance among COF‐based reported thus far.

Язык: Английский

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Linkage Microenvironment Modulation in Triazine‐Based Covalent Organic Frameworks for Enhanced Photocatalytic Hydrogen Peroxide Production

Small, Год журнала: 2025, Номер unknown

Опубликована: Янв. 26, 2025

Abstract Covalent organic frameworks (COFs), known for the precise tunability of molecular structures, hold significant promise photocatalytic hydrogen peroxide (H 2 O ) production. Herein, by systematically altering quinoline (QN) linkages in triazine (TA)‐based COFs via multi‐component reactions, six R‐QN‐TA‐COFs are synthesized with identical skeletons but different substituents. The fine‐tuning optoelectronic properties and local microenvironment is allowed, thereby optimizing charge separation improving interactions dissolved oxygen. Consequently, MeO‐QN‐TA‐COF customized to achieve an impressive rate H production up 7384 µmol g⁻ 1 h⁻ under air atmosphere water without any sacrificial agents, surpassing most reported COF photocatalysts. Its high stability demonstrated through five consecutive recycling experiments characterization recovered COF. reaction mechanism further investigated using a suite quenching experiments, situ spectroscopic analysis, theoretical calculations. enhanced over 2e⁻ oxygen reduction oxidation pathways. Overall, crucial role linkage modulation design solar‐driven effective

Язык: Английский

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Donor–Acceptor Fully Sp²‐Carbon Conjugated Covalent Organic Frameworks for Photocatalytic H₂O₂ Production

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Март 4, 2025

Abstract Covalent organic frameworks (COFs) are promising for photocatalytic H₂O₂ generation. However, imine‐linked COFs often suffer from poor charge separation and low performance. Therefore, constructing sp 2 carbon‐linked with extended π‐conjugation is very significant in boosting the properties, but their synthesis challenging due to reversibility of C═C bond. Here, two vinylene‐linked COFs: BBT‐ACN COF‐1 COF‐2 designed. To investigate effects different structures on exciton binding energy ( E b ), designed possesses a Donor–Acceptor (D–A) structure electron‐deficient benzobisthiazole (BBT) as acceptor benzotrithiophene donor, while latter holds π‐A pyrene π‐unit BBT acceptor. Both show production activity two‐step 2e − oxygen reduction reaction (ORR). As anticipated, D–A structured exhibits lower value, its H O rate pure water air reaches up 2.50 mmol g⁻¹ h⁻¹, ≈3 times higher than that (0.91 h⁻¹). This study reveals fully ‐carbon‐linked beneficial production, which provides an effective approach designing high‐performance photocatalysts.

Язык: Английский

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Boosting Solar-to-H₂O₂ by Molecularly Tunable Heterostructured Pym-CN with an Enhanced Built-In Electric Field

ACS Catalysis, Год журнала: 2024, Номер 14(22), С. 17014 - 17024

Опубликована: Ноя. 4, 2024

Utilizing photocatalytic technology to achieve efficient production of H2O2 is a hot topic. Here, we synthesized material with strong built-in electric field, namely, Pym-CN, through hydrothermal-assisted thermal polymerization strategy, which effectively promotes the separation and transfer photoinduced charge carriers. A pyrimidine ring was successfully introduced into heptazine structure unit leads electron aggregation at N═C–N, benefiting for enhancing sorption activation capabilities oxygen. Under condition visible light wavelength greater than 400 nm (λ > nm), rate Pym-CN (2622.5 μmol/L/h) 7.6 times that BCN. detailed investigation reaction mechanism revealed follows two-step continuous process single-electron oxygen reduction (ORR). This work elucidates application prospects donor–acceptor (D–A) field in H2O2.

Язык: Английский

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Rational Regulation of Dipole Polarization in Donor–Acceptor Covalent Organic Frameworks for Enhanced Photocatalytic Efficiency

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 8284 - 8296

Опубликована: Май 2, 2025

Язык: Английский

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Lewis Acid‐Base Bifunctional Ionic Covalent Organic Frameworks for CO₂ Chemical Fixation

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Май 23, 2025

Abstract Ionic covalent organic frameworks (iCOFs) exhibit unique advantages as heterogeneous catalysts due to their permanent porosity, programmable charge transport, and tunable host‐guest interactions. Here, the fabrication of cationic iCOFs via direct solvothermal assembly integrate zinc ions (Zn(II))‐imine centers are reported construct bifunctional catalysts. The resultant catalyst, Zn@PD‐iCOF, achieves remarkable yields (up 99%) cyclic carbonates in carbon dioxide (CO 2 )‐epoxides cycloaddition reactions under mild conditions (at 80 °C, 0.1 MPa CO ) without need for co‐catalysts solvents, superior most previously ionic This exceptional performance stems from hierarchically ordered pores structure, fully exposed dual active sites (ion pair Lewis acid site), synergistic electronic coupling. Moreover, catalyst retains >90% activity over twelve consecutive cycles, demonstrating stability. study establishes a blueprint designing task‐specific COFs efficient chemical fixation.

Язык: Английский

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Photoenzyme Coupling System: Covalent Organic Frameworks In Situ Production of Hydrogen Peroxide Cascaded with Unspecific Peroxygenase to Achieve C–H Bonds Selective Activation

ACS Applied Materials & Interfaces, Год журнала: 2025, Номер unknown

Опубликована: Янв. 15, 2025

As an efficient, sustainable, and environmentally friendly semiconductor material, covalent organic frameworks (COFs) can generate hydrogen peroxide (H2O2) by photocatalysis, attracting wide attention in recent years. Herein, the effects of hydroxyl, methoxyl, vinyl groups imide-linked two-dimensional (2D) COFs on photocatalytic production H2O2 were studied theoretically experimentally. The introduction greatly promotes photogenerated charge separation migration COFs, providing more oxygen adsorption sites, stronger proton affinity, lower intermediate binding energy, which effectively facilitates rapid conversion to H2O2. Further, we have integrated properties situ generation continuous consumption unspecific peroxygenases (UPOs) construct a mild simple photoenzyme coupling system that achieve selective activation C–H bonds without need any external oxidants or sacrificial agents. This simple, stable, compatible avoids irreversible enzyme damage caused excessive exogenous utilization agents, thus efficient green pathway for fine chemical synthesis. not only breaks restriction supplementation UPO catalytic but also provides new practical application direction production.

Язык: Английский

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Functional Groups‐Regulated Organic Semiconductors for Efficient Artificial Photosynthesis of Hydrogen Peroxide

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Март 18, 2025

Abstract Hydrogen peroxide (H 2 O ) is an environmentally friendly reagent, and organic semiconductors (OSCs) are ideal photocatalysts for the synthesis of H due to their well‐defined molecular structure, strong donor‐acceptor interactions, efficient charge separation. This review discusses regulatory mechanisms functional group modifications in tuning photocatalytic performance OSCs, highlighting relationship between structure catalytic performance. For example, electron‐regulating groups, such as cyano halogen, induce dipoles, facilitating migration photogenerated electrons. Fluorine groups optimize band prolong carrier lifetime high electronegativity. π‐Conjugated extension like anthraquinone thiophene, expand conjugation, improve visible light capture, stabilize intermediates through redox cycles. Hydroxyl enhance surface hydrophilicity promote activation, while imine bond protonation adjusts distribution improves selectivity cycle stability. Multi‐active site sulfonic acid amide, accelerate reaction kinetics inhibit decomposition. Functional absorption, separation, reactions electronic regulation, intermediate adsorption optimization, proton‐electron transfer. Future work should integrate machine learning identify optimal combinations develop green functionalization strategies photocatalyst synthesis.

Язык: Английский

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