Postsynthetic Annulation of Three-Dimensional Covalent Organic Frameworks for Boosting CO₂ Photoreduction

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(28), С. 15473 - 15481

Опубликована: Июль 8, 2023

Three-dimensional covalent organic frameworks (3D COFs), with interconnected pores and exposed functional groups, provide new opportunities for the design of advanced materials through postsynthetic modification. Herein, we demonstrate successful annulation 3D COFs to construct efficient CO2 reduction photocatalysts. Two COFs, NJU-318 NJU-319Fe, were initially constructed by connecting hexaphenyl-triphenylene units pyrene- or Fe-porphyrin-based linkers. Subsequently, moieties within postsynthetically transformed into π-conjugated hexabenzo-trinaphthylene (pNJU-318 pNJU-319Fe) enhance visible light absorption photoreduction activity. The optimized photocatalyst, pNJU-319Fe, shows a CO yield 688 μmol g-1, representing 2.5-fold increase compared that unmodified NJU-319Fe. Notably, direct synthesis hexabenzo-trinaphthylene-based COF catalysts was unsuccessful due low solubility conjugated This study not only provides an effective method photocatalysts but also highlights unlimited tunability structural

Язык: Английский

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Multilevel-Regulated Metal–Organic Framework Platform Integrating Pore Space Partition and Open-Metal Sites for Enhanced CO₂ Photoreduction to CO with Nearly 100% Selectivity

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(50), С. 27728 - 27739

Опубликована: Дек. 6, 2023

Rational design and regulation of atomically precise photocatalysts are essential for constructing efficient photocatalytic systems tunable at both the atomic molecular levels. Herein, we propose a platform-based strategy capable integrating pore space partition (PSP) open-metal sites (OMSs) as foundational features high-performance photocatalysts. We demonstrate first structural prototype obtained from this strategy: pore-partitioned NiTCPE-pstp (TCPE = 1,1,2,2-tetra(4-carboxylphenyl)ethylene, pstp partitioned stp topology). Nonpartitioned NiTCPE-stp is constructed six-connected [Ni3(μ3–OH)(COO)6] trimer TCPE linker to form 1D hexagonal channels with six coplanar OMSs directed channel centers. After introducing triangular pore-partitioning ligands, half were retained, while other used PSP, leading unprecedented microenvironment structure. The resulting material integrates multiple advanced properties, including robustness, wider absorption range, enhanced electronic conductivity, high CO2 adsorption, all which highly desirable applications. Remarkably, exhibits excellent photoreduction activity CO generation rate 3353.6 μmol g–1 h–1 nearly 100% selectivity. Theoretical experimental studies show that introduction partitioning ligands not only optimizes structure promote separation transfer photogenerated carriers but also reduces energy barrier formation *COOH intermediates promoting activation desorption. This work believed be example integrate PSP strategies within metal–organic framework (MOF) photocatalysts, provides new insight well performance optimization MOF-based

Язык: Английский

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Advancements in catalytic, photocatalytic, and electrocatalytic CO2 conversion processes: Current trends and future outlook

Journal of CO2 Utilization, Год журнала: 2024, Номер 80, С. 102682 - 102682

Опубликована: Янв. 23, 2024

Climate change, which is caused by increasing greenhouse gas (GHG) emissions, poses a serious threat to humanity, impacting economies, societies, and the environment. Carbon dioxide (CO2), major contributor effect, responsible for climate change thus must be reduced. capture, conversion, storage (CCUS) technology, involves catalytic, photocatalytic, electrocatalytic conversions, promising method reducing CO2 emissions converting into valuable products. Recent advances in electrocatalytic, photocatalytic reduction of have highlighted potential environmental economic benefits these technologies. However, practical application techniques challenging requires scientific research engineering efforts develop efficient materials capable simultaneously capturing it Therefore, this review presents comprehensive analysis various catalytic systems capture conversion. This aims identify advantages limitations In addition, identified challenges future prospects proposed methods are outlined. Thus, article covers current trends perspectives field combating through management.

Язык: Английский

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Efficient Photocatalytic CO₂ Reduction in Ellagic Acid–Based Covalent Organic Frameworks

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(23), С. 16229 - 16236

Опубликована: Май 30, 2024

Employing covalent organic frameworks (COFs) for the photocatalytic CO2 reduction reaction (CDRR) to generate high-value chemical fuels and mitigate greenhouse gas emissions represents a sustainable catalytic conversion approach. However, achieving superior CDRR performance is hindered by challenges of low charge separation efficiency, poor stability, high preparation costs associated with COFs. Herein, in this work, we utilized perfluorinated metallophthalocyanine (MPcF16) biomolecule compound ellagic acid (EA) as building blocks actualize functional named EPM-COF (M = Co, Ni, Cu). The designed EPCo-COF, featuring cobalt metal active sites, demonstrated an impressive CO production rate selectivity (CDRR). Moreover, following alkaline treatment (EPCo-COF-AT), COF exposed carboxylic anion (COO–) hydroxyl group (OH), thereby enhancing electron-donating capability EA. This modification achieved heightened 17.7 mmol g–1 h–1 outstanding 97.8% efficient CDRR. Theoretical calculations further illustrated that EPCo-COF-AT functionalized COO– OH can effectively alleviate energy barriers involved process, which facilitates proton-coupled electron transfer processes enhances on sites within EPCo-COF-AT.

Язык: Английский

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Surface Engineered Single‐atom Systems for Energy Conversion

Advanced Materials, Год журнала: 2024, Номер 36(16)

Опубликована: Янв. 10, 2024

Abstract Single‐atom catalysts (SACs) are demonstrated to show exceptional reactivity and selectivity in catalytic reactions by effectively utilizing metal species, making them a favorable choice among the different active materials for energy conversion. However, SACs still early stages of conversion, problems like agglomeration low conversion efficiency hampering their practical applications. Substantial research focus on support modifications, which vital SAC stability due intimate relationship between atoms support. In this review, category supports variety surface engineering strategies employed SA systems summarized, including site (heteroatom doping, vacancy introducing, groups grafting, coordination tunning) structure (size/morphology control, cocatalyst deposition, facet engineering, crystallinity control). Also, merits single‐atom systematically introduced. Highlights comprehensive summary discussions utilization surface‐engineered diversified applications photocatalysis, electrocatalysis, thermocatalysis, devices. At end potential obstacles using field discussed. This review aims guide rational design manipulation target‐specific capitalizing characteristic benefits engineering.

Язык: Английский

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