Strong Interfacial Interaction in Polarized Ferroelectric Heterostructured Nanosheets for Highly Efficient and Selective Photocatalytic CO₂ Reduction

Small, Год журнала: 2025, Номер unknown

Опубликована: Янв. 19, 2025

Abstract Heterojunctions are sustainable solutions for the photocatalytic CO 2 reduction reaction (CO RR) by regulating charge separation behavior at interface. However, their efficiency and product selectivity severely hindered inflexible weak built‐in electric field electronic structure of two phases. Herein, ferroelectric‐based heterojunctions between polarized bismuth ferrite (BFO(P)) CdS constructed to enhance interfacial interactions catalytic activity. The intrinsic polarization depending on ferroelectric state causes significant electrostatic potential difference energy‐band bending. This helps overcome unsatisfactory redox that differs from classical mechanism, synergy heterostructure facilitates effective transfer photogenerated charges with an extended lifetime (>20 ns) significantly enhanced photovoltage (1002 times BFO). optimized carrier dynamics allow heterojunction achieve a much higher yield compared state‐of‐the‐art photocatalysts, 85.46 23.47 than those pristine BFO, respectively. Moreover, it maintains impressive 100% together excellent repeatability cycling. work not only sheds light how strong inherent polarity promotes performance photocatalysts but also provides new insights designing efficient RR.

Язык: Английский

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Hydroxyl-Functionalized Donor–Acceptor Covalent Organic Frameworks for Efficient Photocatalytic Hydrogen Peroxide Production under Visible Light

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 3584 - 3594

Опубликована: Фев. 13, 2025

Photocatalytic hydrogen peroxide (H2O2) production via the oxygen reduction reaction (ORR) provides a promising and energy-saving alternative to traditional energy-intensive anthraquinone process. Nevertheless, how decrease energy barrier of two-electron (2e–) ORR process photosynthesize H2O2 efficiently is still challenging. Herein, three hydroxyl-functionalized donor–acceptor covalent organic frameworks (COFs) are synthesized for photocatalytic under visible-light irradiation (420 ≤ λ 780 nm). It observed that dihydroxyl functionalization (2,5-DhaTph 2,3-DhaTph) facilitates transportation photogenerated carriers between acceptor donor units accelerates kinetics rate-limiting step when comparing with monohydroxyl (2-DhaTph). Further, 2,5-DhaTph para-position hydroxyl shows higher photosynthesis efficiency than 2,3-DhaTph (ortho-positioned hydroxyl), probably due greater exposure catalytically active sites. This supported by better structural symmetry 2,5-DhaTph, which contributes crystallinity specific surface areas. Electron paramagnetic resonance (EPR) spectra theoretical calculations show produces *OOH intermediates reduced barrier, resulting in high rate 2103.1 μmol h–1 g–1. Regulating amount substituents their location on COFs an effective strategy boost carrier transfer reduce O2-to-H2O2 conversion.

Язык: Английский

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Covalent Metal–Organic Frameworks: Fusion of Covalent Organic Frameworks and Metal–Organic Frameworks

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Фев. 21, 2025

ConspectusMetal-organic frameworks (MOFs) and covalent organic (COFs), as emerging porous crystalline materials, have attracted remarkable attention in chemistry, physics, materials science. MOFs are constructed by metal clusters (or ions) linkers through coordination bonds, while COFs prepared pure building blocks via bonds. Because of the nature linkages, their own shortcomings. Typically, relatively weak bond strengths bonds lead to poor chemical stability MOFs, which limits practical implementations. On other hand, due strong exhibit rather higher under harsh conditions, compared MOFs. However, lack open sites restricts functionalization application. Therefore, it is hypothesized that "cream-skimming" would address these drawbacks produce a new class material, namely, metal-organic (CMOFs), with unprecedented structural complexity advanced functionality. The CMOFs reveal synthetic approach for preparation reticular materials. Specifically, ions reacted chelating ligands assemble complexes or functional reactive (e.g., -CHO, -NH2), can be further connected form networked structures dynamic chemistry (DCC). isolated complex cluster precursors show enhanced prevents decomposition rearrangements during self-assembly process CMOFs. Since topology preassembled nodes well-defined, structure readily predicted upon directed networking Unaccessible from unstable highly ion/clusters traditional conditions DCC approach. Moreover, synergize advantages COFs, containing active ensuring various interesting properties, linkages allow high even conditions. In past few years, our group has specifically focused on development general strategies coinage (Cu, Ag, Au)-based cyclic trinuclear units (CTUs) DCC. CTUs trigonal planar functionalized sites, such -NH2 react afford Notably, also features properties including metallophilic attraction, π-acidity/basicity, luminescence, redox activity catalytic activity, incorporated into we envision promising platforms not only novel but potential applications many research fields gas absorption/separation, sensing, full-color display, catalysis, energy, biological applications. this Account, summarize recent studies CMOFs, starting linkage topological design, transformation, morphological control, fields. We discuss future opportunities challenges rapidly developed field hope Account may promote scientific discoveries CMOF-based technologies future.

Язык: Английский

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Inductive effect of charge transfer in ferroelectrics and plasmonic Ag heterojunctions for enhanced CO2 photoreduction

Applied Physics Letters, Год журнала: 2025, Номер 126(6)

Опубликована: Фев. 10, 2025

Converting carbon dioxide into fuel and chemicals by utilizing solar energy represents a cutting-edge approach to recovery renewal. The transfer behavior of photogenerated electrons built-in electric field photocatalysts greatly affect the efficiency photoreduction reaction. Herein, heterostructures composed bismuth sodium titanate (BNT) ferroelectrics silver nanoparticles (Ag NPs) are constructed promote photocatalytic CO2 performance. large spontaneous polarization BNT optimizes dynamics photoinduced holes causes band bending with strong intrinsic field. With aid Ag NPs, BNT@xAg heterojunctions exhibit intensified light absorption due phenomenon localized surface plasmon resonance (LSPR), which extends visible spectrum strengthens charge transfer. modified catalysts demonstrate improved separation capacity notably prolonged electron lifetime up 40.95 ns. synergistic effect LSPR significantly boosts together ultrahigh CO product selectivity, is outstanding among ferroelectric other representative photocatalysts. This study elucidates enhancement mechanism plasmonic decorated offers an alternative route for design efficient catalysts.

Язык: Английский

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Co and N para-doping modulates the electronic structure of CdIn2S4 to enhance CO2 adsorption, activation and photocatalytic reduction

Applied Catalysis B Environment and Energy, Год журнала: 2025, Номер 371, С. 125275 - 125275

Опубликована: Март 18, 2025

Язык: Английский

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Harnessing Hydrogen Spillover by Lattice Strain for Enhanced Photocatalytic Hydrogen Evolution of ZnIn₂S₄

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 2367 - 2379

Опубликована: Янв. 25, 2025

Язык: Английский

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Metal covalent organic frameworks-based laccase-like nanozyme for oxidative degradation and identification of phenolic pollutants

Journal of Hazardous Materials, Год журнала: 2025, Номер 487, С. 137142 - 137142

Опубликована: Янв. 7, 2025

Язык: Английский

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Porphyrin‐Based Covalent Organic Frameworks for CO₂ Photo/Electro‐Reduction

Angewandte Chemie International Edition, Год журнала: 2025, Номер unknown

Опубликована: Фев. 9, 2025

Photo/electro-catalytic CO2 reduction into high-value products are promising strategies for addressing both environmental problems and energy crisis. Duo to their advantageous visible light absorption ability, adjustable optic/electronic properties, definite active center, post-modification capability, excellent stability, porphyrin-based covalent organic frameworks (COFs) have emerged as attractive photo/electro-catalysts towards reduction. In this review, the research progress of COFs photo/electro-catalytic is summarized including design principles, catalytic performance, reaction mechanism. addition, review also presents some challenges prospects application in reduction, laying base fundamental efforts.

Язык: Английский

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Polarized microenvironment-modulated covalent organic frameworks with nickel single atoms for enhanced CO2 photoreduction

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 162084 - 162084

Опубликована: Март 1, 2025

Язык: Английский

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Geomimetic Interfacial Hydrothermal Synthesis of Crystalline Ionic Vinylene‐Linked Covalent Organic Frameworks

Small, Год журнала: 2025, Номер unknown

Опубликована: Фев. 5, 2025

Abstract Ionic vinylene‐linked covalent organic frameworks (ivCOFs) with ionic characteristics and highly conjugated structures have been promising functional materials. However, both the number of reported COFs its synthetic methodologies still be limited. Herein, two new kinds (named as COF‐NUC‐1 COF‐NUC‐2) are synthesized by novel geomimetic interfacial hydrothermal synthesis for first time. Due to insolubility aldehyde monomers in water, a molecule/water interface is created, where water‐soluble N‐ethyl‐2,4,6‐trimethylpyridinium bromide (ETMP‐Br) can react via interface‐confined Knoevenagel condensation reaction. The resultant show high crystallinity, chemical stability, hydrophilic nature. Benefiting from electron‐withdrawing redox properties pyridinium salts, as‐fabricated memristor based on film shows stable nonvolatile memory effects, featuring ON/OFF current ratio 0.66 × 10 3 small switch‐on voltage −0.68 V. This work expands realm ivCOFs deepens understanding synthesis.

Язык: Английский

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