Boosting CO₂ Photoreduction via Regulating Charge Transfer Ability in a One‐Dimensional Covalent Organic Framework

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(46)

Опубликована: Сен. 28, 2023

Two-dimensional (2D) imine-based covalent organic frameworks (COFs) hold potential for photocatalytic CO2 reduction. However, high energy barrier of imine linkage impede the in-plane photoelectron transfer process, resulting in inadequate efficiency photoreduction. Herein, we present a dimensionality induced local electronic modulation strategy through construction one-dimensional (1D) pyrene-based (PyTTA-COF). The dual-chain-like edge architectures 1D PyTTA-COF enable stabilization aromatic backbones, thus reducing loss during exciton dissociation and thermal relaxation, which provides energetic to traverse linkages. As result, exhibits significantly enhanced photoreduction activity under visible-light irradiation when coordinated with metal cobalt ion, yielding remarkable CO evolution 1003 μmol g-1 over an 8-hour period, surpasses that corresponding 2D counterpart by factor 59. These findings valuable approach address charge limitations COFs.

Язык: Английский

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Fully Conjugated 2D sp² Carbon‐Linked Covalent Organic Frameworks for Photocatalytic Overall Water Splitting

Advanced Materials, Год журнала: 2023, Номер 36(6)

Опубликована: Окт. 11, 2023

Abstract Covalent organic frameworks (COFs) hold great promise for solar‐driven hydrogen production. However, metal‐free COFs photocatalytic overall water splitting remain elusive, primarily due to challenges in simultaneously regulating their band structures and catalytic sites enable concurrent half‐reactions. Herein, two types of π‐conjugated containing the same donor–acceptor structure are constructed via Knoevenagel condensation Schiff base reaction afford cyanovinylene‐ imine‐bridged COFs, respectively. The difference linkage leads a remarkable activity toward splitting. 2D sp 2 carbon‐linked COF exhibits notable splitting, which can reach an apparent quantum efficiency 2.53% at 420 nm. In contrast, imine‐linked cannot catalyze water‐splitting reaction. Mechanistic investigations reveal that cyanovinylene is essential modulating promoting charge separation thereby enabling Moreover, it further shown crystallinity substantially impacts performance COFs. This study represents first successful example developing with high

Язык: Английский

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Insight into the Selectivity-Determining Step of Various Photocatalytic CO₂ Reduction Products by Inorganic Semiconductors

ACS Catalysis, Год журнала: 2024, Номер 14(14), С. 10760 - 10788

Опубликована: Июль 3, 2024

Язык: Английский

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A photocatalytic redox cycle over a polyimide catalyst drives efficient solar-to-H2O2 conversion

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

Опубликована: Июнь 22, 2024

Abstract Circumventing the conventional two-electron oxygen reduction pathway remains a great problem in enhancing efficiency of H 2 O photosynthesis. A promising approach to achieve outstanding photocatalytic activity involves utilization redox intermediates. Here, we engineer polyimide aerogel photocatalyst with photoreductive carbonyl groups for non-sacrificial production. Under photoexcitation, on surface are reduced, forming an anion radical intermediate. The produced intermediate is oxidized by produce and subsequently restores group. high catalytic ascribed cycle mediated anion, which not only promotes adsorption but also lowers energy barrier reaction generation. An apparent quantum yield 14.28% at 420 ± 10 nm solar-to-chemical conversion 0.92% achieved. Moreover, demonstrate that mere 0.5 m self-supported exposed natural sunlight 6 h yields significant production 34.3 mmol −2 .

Язык: Английский

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Defect-Induced Synergetic Effect of Bi-Based Compounds for One-Pot Conversion of Organic Pollutants into CO via Coupling Photodegradation of Carbamazepine with Photoreduction of CO₂

ACS Catalysis, Год журнала: 2024, Номер 14(4), С. 2134 - 2143

Опубликована: Янв. 25, 2024

The waste of carbon sources and greenhouse gas production during wastewater treatment have become extremely important environmental issues. Herein, the BiOBr/BiVO4 compounds with defect-induced frustrated Lewis acid–base pairs (DFLPs) internal charge transfer were fabricated to convert organic pollutants into CO nearly 100% selectivity. oxygen vacancy (Ov) induced built-in electric field in create directional from BiOBr BiVO4. Density functional theory (DFT) calculations prove that Ov combines its adjacent hydroxyls form DFLP active sites can additionally capture activate CO2. Meanwhile, reduce formation-free energy COOH* intermediates, which is key rate-limiting step CO2 high This system has achieved selective conversion value-added chemicals pollutant degradation provides a theoretical basis for actual recycling sources.

Язык: Английский

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Pt(II)/Pd(II)‐Based Metallosupramolecular Architectures as Light Harvesting Systems and their Applications

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(18)

Опубликована: Фев. 21, 2024

The development of artificial light-harvesting systems mimicking the natural photosynthesis method is an ever-growing field research. Numerous such as polymers, metal complexes, POFs, COFs, supramolecular frameworks etc. have been fabricated to accomplish more efficient energy transfer and storage. Among them, coordination complexes (SCCs) formed by non-covalent metal-ligand interaction, shown capacity not only undergo single multistep migration but also utilize harvested for a wide variety applications photocatalysis, tunable emissive systems, encrypted anti-counterfeiting materials, white light emitters This review sheds on behavior both 2D metallacycles 3D metallacages where design ingenuity has executed afford harvesting donor ligands well acceptors.

Язык: Английский

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Floatable artificial leaf to couple oxygen-tolerant CO2 conversion with water purification

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 2, 2025

Язык: Английский

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Decoupled Artificial Photosynthesis via a Catalysis-Redox Coupled COF||BiVO₄ Photoelectrochemical Device

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(32), С. 18141 - 18147

Опубликована: Авг. 7, 2023

Artificial photosynthesis is an attractive approach to direct fuel production from sunlight. However, the simultaneous O2 evolution reaction (OER) and CO2 reduction (CDRR) present challenges for product separation safety. Herein, we propose a strategy temporally decouple artificial through photoelectrochemical energy storage. We utilized covalent organic framework (DTCo-COF) with redox-active electron donors (−C–OH moieties) catalytically active acceptors (cobalt-porphyrin) enable reversible −C–OH/–C═O redox redox-promoted CO2-to-CO photoreduction. Integrating COF photocathode OER photoanode in device allows effective storage of OER-generated electrons protons by −C═O groups. These stored charges can be later employed CDRR while regenerating complete loop, thus enabling on-demand separate or solar fuels. Our work sets stage advancements decoupled development more efficient technologies.

Язык: Английский

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Photochargeable Semiconductors: in “Dark Photocatalysis” and Beyond

Advanced Functional Materials, Год журнала: 2023, Номер 33(45)

Опубликована: Авг. 3, 2023

Abstract Photochargeable semiconductors enable energy harvesting and storage in a single material. Charges separated upon absorption of photons can accumulate highly energetic trap states if morphology, size, chemical composition are appropriately chosen. For example, electrons survive for several hours hole scavengers used to prevent their recombination with photogenerated holes, negative charge is balanced by positive counter‐ions. The first database charge‐storing recently released, containing information from more than 50 publications within the past 40 years. Now, has been updated 90 entries latest works on topic. These materials have largely utilized context “dark photocatalysis”, that is, redox reactions enabled photocharged long after cessation light irradiation. Nevertheless, variety further potential applications not received enough visibility, including memory storage, steel anti‐corrosion, sensors, micromotors. In this review, key figures merit empirical relationships found between them highlighted. After showing advances dark photocatalysis, it discussed how other application fields may benefit these materials. each area, promising research directions based findings recommended.

Язык: Английский

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Advances in Defect Engineering of Metal Oxides for Photocatalytic CO₂ Reduction

Small, Год журнала: 2024, Номер unknown

Опубликована: Апрель 30, 2024

Abstract Photocatalytic CO 2 reduction technology, capable of converting low‐density solar energy into high‐density chemical energy, stands as a promising approach to alleviate the crisis and achieve carbon neutrality. Semiconductor metal oxides, characterized by their abundant reserves, good stability, easily tunable structures, have found extensive applications in field photocatalysis. However, wide bandgap inherent oxides contributes poor efficiency photocatalytic reduction. Defect engineering presents an effective strategy address these challenges. This paper reviews research progress defect enhance performance summarizing classifications, preparation methods, characterization techniques. The focus is on engineering, represented vacancies doping, for improving oxide photocatalysts. includes advancements expanding photoresponse range, enhancing photogenerated charge separation, promoting molecule activation. Finally, provides summary current issues challenges faced along with prospective outlook future development technology.

Язык: Английский

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