Small Conjugated Organic Ligand-Modified Polyoxometalate-Based Hybrid Materials for Boosting Photocatalytic CO₂ Reduction

Inorganic Chemistry, Год журнала: 2024, Номер 63(36), С. 16791 - 16798

Опубликована: Авг. 27, 2024

Photocatalytic carbon dioxide (CO

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Metal‐Ion‐Coordinated Microenvironments in Covalent Organic Frameworks for Enhanced Photocatalytic CO₂ Reduction

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 27, 2024

Abstract Metal‐coordinated covalent organic frameworks (M‐COFs) have garnered significant attention for their potential in carbon dioxide (CO 2 ) photoreduction. However, the efficient conversion of CO to (carbon monoxide) remains challenging because strong exciton effects from Coulombic interactions electron‐hole pairs within metal‐associated coordination environment. Herein, three benzoxazole (BBO)‐based COF photocatalysts coordinated with cobalt (Co) ions featuring distinct geometries: Co‒N‒O , 3 and Co‒N ‒O are strategically designed. The dissociation is precisely modulated photocatalytic reduction enhanced. Among them, BBO‐COF BPY ‐Co demonstrates a increase production rate 5, 024.87 10, 552.15 µmol g −1 h an improvement selectivity 80% 91%, coupled excellent stability. Spectral characterizations density functional theory (DFT) theoretical calculations elucidate that judicious tuning Co atom environment optimized local electronic structure BBO‐COFs which significantly boosts dissociation, facilitates charge carrier migration framework, mitigates recombination photogenerated pairs, reduce energy barrier rate‐determining step. This study provides insight into pivotal role metal microenvironments enhancing process paving way new strategies regulation COFs.

Язык: Английский

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Molecular Copper–Anthraquinone Photocatalysts for Robust Hydrogen Production

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(46), С. 31901 - 31910

Опубликована: Ноя. 7, 2024

The development of robust and inexpensive photocatalysts for H2 production under visible light irradiation remains a significant challenge. This study presents series square planar copper anthraquinone complexes (R4N)CuL2 (R = ethyl, L alizarin dianion (CuAA); R n-butyl, purpurin (CuPP), (2-hydroxyanthraquinone)formamide (CuAHA)) as molecular to achieve high long-term stability in visible-light-driven production. These are self-sensitized by the ligands serve proton reduction without additional photosensitizers or catalysts. Under blue light, complex CuAA produces mixture H2O/DMF with undiminished activity over 42 days, giving turnover number exceeding 6800. Electrochemical UV–vis studies consistent an EECC mechanism (E: electron transfer C: protonation) catalytic cycle. initial photochemical steps involve conversion both hydroquinones. Further light-driven reductions hydroquinones followed two protonation results formation H2. Dependence rate on concentration H2O suggests that either generation CuII–H intermediate heterocoupling between H+ produce is turnover-limiting step catalysis.

Язык: Английский

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Highly Efficient Photocatalytic CO2‐to‐CO on Ni‐Based Cationic Polymer with TiO2‐Assisted Exfoliation and Stabilization

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Дек. 31, 2024

Abstract Porous organic polymers have shown great potential in photocatalytic CO 2 reduction due to their unique tunable structure favoring gas adsorption and metal sites integration. However, efficient photocatalysis porous is greatly limited by the low surface reactivity electron mobility of bulk structure. Herein, we incorporate TiO nanoparticles Ni(II) into a layered cationic imidazolium polymer (IP), which moieties free anions can stabilize key intermediates enhance reaction kinetics reduction. During reaction, /NiIP situ exfoliated nanosheets (NSs) with more accessible active shorten transport pathways. The formed /NiIP‐NSs exhibit an impressively high production rate as 54.9 mmol ⋅ g −1 h selectivity 99.9 %. embedding could improve efficiency so facilitate photochemical stripping process polymer. Moreover, assistance possess excellent stability during recycling experiments comparison rapidly declined activity NiIP‐NSs. This work presents new strategy construct highly photocatalysts for

Язык: Английский

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Constructing strong built-in electric field in lead-free halide-perovskite-based heterojunction to boost charge separation for efficient CO2 photoreduction

Applied Catalysis B Environment and Energy, Год журнала: 2024, Номер unknown, С. 125012 - 125012

Опубликована: Дек. 1, 2024

Язык: Английский

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