Tris(triazolo)triazine‐Based Covalent Organic Frameworks for Efficiently Photocatalytic Hydrogen Peroxide Production

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(45)

Опубликована: Июль 1, 2024

Abstract Two‐dimensional covalent organic frameworks (2D‐COFs) have recently emerged as fascinating scaffolds for solar‐to‐chemical energy conversion because of their customizable structures and functionalities. Herein, two tris(triazolo)triazine‐based COF materials (namely COF‐JLU51 COF‐JLU52) featuring large surface area, high crystallinity, excellent stability photoelectric properties were designed constructed the first time. Remarkably, gave an outstanding H 2 O production rate over 4200 μmol g −1 h with reusability in pure water under one standard sun light, that higher than its isomorphic COF‐JLU52 most reported metal‐free materials, owing to superior generation, separation transport photogenerated carriers. Experimental theoretical researches prove photocatalytic process undergoes a combination indirect 2e − reduction reaction (ORR) 4e oxidation (WOR). Specifically, ultrahigh yield 7624.7 apparent quantum 18.2 % was achieved 1 : ratio benzyl alcohol system. This finding contributes novel, nitrogen‐rich high‐quality also designate bright future solar transformations.

Язык: Английский

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Tris(triazolo)triazine‐Based Covalent Organic Frameworks for Efficiently Photocatalytic Hydrogen Peroxide Production

Angewandte Chemie, Год журнала: 2024, Номер 136(45)

Опубликована: Июль 1, 2024

Abstract Two‐dimensional covalent organic frameworks (2D‐COFs) have recently emerged as fascinating scaffolds for solar‐to‐chemical energy conversion because of their customizable structures and functionalities. Herein, two tris(triazolo)triazine‐based COF materials (namely COF‐JLU51 COF‐JLU52) featuring large surface area, high crystallinity, excellent stability photoelectric properties were designed constructed the first time. Remarkably, gave an outstanding H 2 O production rate over 4200 μmol g −1 h with reusability in pure water under one standard sun light, that higher than its isomorphic COF‐JLU52 most reported metal‐free materials, owing to superior generation, separation transport photogenerated carriers. Experimental theoretical researches prove photocatalytic process undergoes a combination indirect 2e − reduction reaction (ORR) 4e oxidation (WOR). Specifically, ultrahigh yield 7624.7 apparent quantum 18.2 % was achieved 1 : ratio benzyl alcohol system. This finding contributes novel, nitrogen‐rich high‐quality also designate bright future solar transformations.

Язык: Английский

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Hydrogen Peroxide Fuel Cells and Self-Powered Electrochemical Sensors Based on the Principle of a Fuel Cell with Biomimetic and Nanozyme Catalysts

Biosensors, Год журнала: 2025, Номер 15(2), С. 124 - 124

Опубликована: Фев. 19, 2025

The operating principle of a fuel cell is attracting increasing attention in the development self-powered electrochemical sensors (SPESs). In this type sensor, chemical energy analyzed substance converted into electrical galvanic through spontaneous reactions, directly generating an analytical signal. Unlike conventional (amperometric, voltammetric, and impedimetric) sensors, no external form applied potential required for redox detection reactions to occur. SPESs therefore have several important advantages over sensors. They do not require power supply modulation system, which saves costs. devices also offer greater simplicity are more compatible applications wearable sensor as well vivo situ use. Due dual properties hydrogen peroxide, it possible develop membraneless cells fuel-cell-based peroxide SPESs, sample used only source energy, both oxidant reductant (fuel). This suppresses dependence on availability oxygen. Electrode catalyst materials different reaction pathways at cathode anode one-compartment key technology implementation characteristics SPESs. article provides overview designs H2O2-H2O2 H2O2 focusing biomimetic nanozyme catalysts, highlights recent innovations prospects hydrogen-peroxide-based (bio)electrochemical analysis.

Язык: Английский

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Singlet‐Oxygen‐Driven Cooperative Photocatalytic Coupling of Biomass Valorization and Hydrogen Peroxide Production Using Covalent Organic Frameworks

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Март 11, 2025

Abstract Traditional H 2 O photocatalysis primarily depends on photoexcited electrons and holes to drive oxygen reduction water oxidation, respectively. However, singlet ( 1 ), often underappreciated, plays a pivotal role in production. Meanwhile, photocatalytic biomass conversion has attracted attention, yet studies combining synthesis with valorization remain rare typically yield low‐value products. Herein, strategy of furfuryl alcohol (FFA) coupled the efficient co‐production is reported, enabled by covalent organic frameworks (COFs) induced, ‐participated Achmatowicz rearrangement. This study introduces polyimide‐based COF‐N 0‐3 tailored nitrogen content, representing an unprecedently platform for Remarkably, reducing content COF enhances production, significantly boosting generation rate. In FFA, primary pathway production rearrangement, achieving rate ten times higher than that reliant reaction pure water, reaching 4549 µmol g⁻¹ h⁻¹. Mechanism revealed selectively engaged bypassing hole oxidation trigger producing valuable 6‐hydroxy‐(2H)‐pyranone 99% 92% selectivity. work establishes coupling simultaneous biochemicals, offering transformative approach sustainable photocatalysis.

Язык: Английский

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Celebrating Ten Years of Covalent Organic Frameworks for Solar Energy Conversion: Past, Present and Future

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(49)

Опубликована: Авг. 22, 2024

Abstract Accelerated anthropogenic emission of greenhouse gases due to increasing energy demands has created a negative impact on our planet. Therefore, the replacement fossil by renewable resources become paramount interest, both societally and scientifically. It is within this setting that organic photocatalysts have emerged as new generation earth‐abundant catalysts for conversion solar radiation into chemical energy. In 2014, first example covalent framework (COF) photocatalyst hydrogen evolution reaction was reported group, which not only marked beginning COF photocatalysis fuel production but also helped accelerate research “soft photocatalysis” based porous polymers in general. last decade, significant progress been made toward developing COFs robust, molecularly precise platforms emulating artificial photosynthesis. This mini‐review commemorates 10th anniversary gives brief historical overview milestones field since its inception 2014. We review development related photocatalytic transformations, including evolution, oxygen overall water splitting, CO 2 reduction, N fixation, alcohol oxidation. discuss lessons learned design structure‐property‐function relationships photocatalysts, future perspectives challenges are given.

Язык: Английский

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Stable and emissive covalent organic frameworks as highly sensitive and selective sensors for hydrazine

Microporous and Mesoporous Materials, Год журнала: 2025, Номер 386, С. 113506 - 113506

Опубликована: Янв. 11, 2025

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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Molecular regulation on covalent triazine frameworks for boosting H2O2 photosynthesis in air atmosphere

Journal of Catalysis, Год журнала: 2025, Номер unknown, С. 115990 - 115990

Опубликована: Янв. 1, 2025

Язык: Английский

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Soluble polymer microenvironments promote photocatalytic hydrogen peroxide production and self-Fenton reactions

Chem Catalysis, Год журнала: 2025, Номер unknown, С. 101260 - 101260

Опубликована: Фев. 1, 2025

Язык: Английский

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Fully Conjugated Benzobisoxazole‐Bridged Covalent Organic Frameworks for Boosting Photocatalytic Hydrogen Evolution

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

Опубликована: Март 6, 2025

2D covalent organic frameworks (2D-COFs) have attracted extensive interest in solar energy to hydrogen conversion. However, insufficient light harvesting and difficult exciton dissociation severely limit the improvement of photocatalytic activity for COFs, thereby impeding progression this advanced field. In work, two benzobisoxazole-bridged fully conjugated 2D-COFs with triazine (COF-JLU44) pyrene (COF-JLU45) units were constructed first time via Knoevenagel polycondensation, they hold long-range ordered structures, largely acceptable surface area, fascinating photoelectric properties. Significantly, COF-JLU45 exhibits an impressive evolution rate 272.5 mmol g-1 h-1 superior reusability presence 1.0 wt% Pt under irradiation, coupled a remarkable apparent quantum yield 12.9% at long wavelength 600 nm. Multiple spectroscopy theoretical simulation demonstrate ingenious design widen its absorption effectively promote dissociation. This finding contributes valuable insights constructing metal-free photocatalysts conversion utilization.

Язык: Английский

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