Metal‐Organic Frameworks for Photocatalytic Water Splitting and CO₂Reduction

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(15)

Опубликована: Янв. 23, 2023

Abstract Photocatalytic water splitting and carbon dioxide (CO 2 ) reduction provide promising solutions to global energy environmental issues. In recent years, metal‐organic frameworks (MOFs), a class of crystalline porous solids featuring well‐defined tailorable structures as well high surface areas, have captured great interest toward photocatalytic CO reduction. this review, the semiconductor‐like behavior MOFs is first discussed. We then summarize advances in over MOF‐based materials focus on unique advantage for clarifying structure‐property relationship photocatalysis. addition, some representative characterization techniques been presented unveil kinetics reaction intermediates systems. Finally, challenges, perspectives future directions are proposed.

Язык: Английский

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Copper(II) Schiff-Base Complex Modified UiO-66-NH₂(Zr) Metal–Organic Framework Catalysts for Knoevenagel Condensation–Michael Addition–Cyclization Reactions

Inorganic Chemistry, Год журнала: 2022, Номер 61(12), С. 4825 - 4841

Опубликована: Март 14, 2022

The synthesis of five- and six-membered oxygen- nitrogen-containing heterocycles has been regarded as the most fundamental issue in organic chemistry chemical industry because they are used producing high-value products. In this study, an efficient, economic, sustainable, green protocol for multicomponent developed. one-pot direct Knoevenagel condensation-Michael addition-cyclization sequences transformation aromatic aldehydes, malononitrile, 4-hydroxycoumarin or phthalhydrazide generate corresponding dihydropyrano[2,3-c]chromenes 1H-pyrazolo[1,2-b]phthalazine-5,10-diones over a novel mesoporous metal-organic framework-based supported Cu(II) nanocatalyst [UiO-66@Schiff-Base-Cu(II)] under ambient conditions. Moreover, complex efficiently catalyzed selectively large-scale target molecules with high yield large turnover numbers. As presented, catalyst demonstrates excellent reusability stability can be recycled up to six runs without noticeable loss activity. ICP-AES analysis showed that no leaching Cu occurred during recycling process heterogeneous nanocatalyst.

Язык: Английский

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Manipulating the Spin State of Co Sites in Metal–Organic Frameworks for Boosting CO₂ Photoreduction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(5), С. 3241 - 3249

Опубликована: Янв. 26, 2024

Photocatalytic CO2 reduction holds great potential for alleviating global energy and environmental issues, where the electronic structure of catalytic center plays a crucial role. However, spin state, key descriptor properties, is largely overlooked. Herein, we present simple strategy to regulate states Co centers by changing their coordination environment exchanging species into stable Zn-based metal–organic framework (MOF) afford Co-OAc, Co-Br, Co-CN photoreduction. Experimental DFT calculation results suggest that distinct sites give rise different charge separation abilities barriers adsorption/activation in photocatalysis. Consequently, optimized Co-OAc with highest spin-state presents an excellent photocatalytic activity 2325.7 μmol·g–1·h–1 selectivity 99.1% CO, which are among best all reported MOF photocatalysts, absence noble metal additional photosensitizer. This work underlines MOFs as ideal platform manipulation toward improved

Язык: Английский

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A Dual-Purpose Ce(III)–Organic Framework with Amine Groups and Open Metal Sites: Third-Order Nonlinear Optical Activity and Catalytic CO₂ Fixation

ACS Applied Materials & Interfaces, Год журнала: 2023, Номер 15(31), С. 37300 - 37311

Опубликована: Июль 27, 2023

The present work focuses on the synthesis and properties of a novel multifunctional cerium(III) MOF, [Ce2(data)3(DMF)4]·DMF (data2-: 2,5-diaminoterephthalate), abbreviated as NH2-Ce-MUM-2. Its crystal structure reveals an intricate 3D 4,5-connected framework with xah topology. This MOF features unique properties, such open metal sites, presence free amino groups, high stability. Two main applications NH2-Ce-MUM-2 were investigated: (i) heterogeneous catalyst in CO2 fixation into cyclic carbonates (ii) material third-order nonlinear optical activity. As model reaction, cycloaddition to propylene oxide give corresponding carbonate was explored under mild conditions, at atmospheric pressure carbon dioxide absence cocatalyst added solvent. Various reaction parameters investigated toward optimization exploration substrate scope, revealing up 99% product yields products. Besides, is highly stable, permitting its recyclability reusability further catalytic experiments. significant contributions groups sites within this particularly considered when proposing potential mechanism for reaction. Z-Scan measurements used evaluate (NLO) various laser intensities. A two-photon absorption (TPA) greater incident intensities shows that might be applicable switching devices. self-focusing effects highlighted by index refraction (n2). By reporting characterization along promising NLO behavior, current study introduces additional example growing family metal-organic frameworks.

Язык: Английский

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Porous framework materials for energy & environment relevant applications: A systematic review

Green Energy & Environment, Год журнала: 2023, Номер 9(2), С. 217 - 310

Опубликована: Янв. 3, 2023

Carbon peaking and carbon neutralization trigger a technical revolution in energy & environment related fields. Development of new technologies for green production storage, industrial saving efficiency reinforcement, capture, pollutant gas treatment is highly imperious demand. The emerging porous framework materials such as metal–organic frameworks (MOFs), covalent organic (COFs) hydrogen-bonded (HOFs), owing to the permanent porosity, tremendous specific surface area, designable structure customizable functionality, have shown great potential major energy-consuming processes, including sustainable catalytic conversion, energy-efficient separation storage. Herein, this manuscript presents systematic review global comprehensive applications, from macroscopic application perspective.

Язык: Английский

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Thermocatalytic Conversion of CO₂ to Valuable Products Activated by Noble‐Metal‐Free Metal‐Organic Frameworks

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(34)

Опубликована: Май 12, 2023

Thermocatalysis of CO2 into high valuable products is an efficient and green method for mitigating global warming other environmental problems, which Noble-metal-free metal-organic frameworks (MOFs) are one the most promising heterogeneous catalysts thermocatalysis, many excellent researches have been published. Hence, this review focuses on obtained from various conversion reactions catalyzed by noble-metal-free MOFs, such as cyclic carbonates, oxazolidinones, carboxylic acids, N-phenylformamide, methanol, ethanol, methane. We classified these published references according to types products, analyzed methods improving catalytic efficiency MOFs in reaction. The advantages using MOF were also discussed along text. This concludes with future perspectives challenges be addressed potential research directions. believe that will helpful readers attract more scientists join topic conversion.

Язык: Английский

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Linker Engineering of Sandwich‐Structured Metal–Organic Framework Composites for Optimized Photocatalytic H₂ Production

Advanced Materials, Год журнала: 2023, Номер 35(39)

Опубликована: Июль 8, 2023

While the microenvironment around catalytic sites is recognized to be crucial in thermocatalysis, its roles photocatalysis remain subtle. In this work, a series of sandwich-structured metal-organic framework (MOF) composites, UiO-66-NH2 @Pt@UiO-66-X (X means functional groups), rationally constructed for visible-light photocatalytic H2 production. By varying ─X groups UiO-66-X shell, Pt and photosensitive core can simultaneously modulated. Significantly, MOF composites with identical light absorption loading present distinctly different production rates, following group sequence ─H > ─Br ─NA (naphthalene) ─OCH3 ─Cl ─NO2 . @Pt@UiO-66-H demonstrates rate up 2708.2 µmol g-1 h-1 , ≈222 times that @Pt@UiO-66-NO2 Mechanism investigations suggest variation balance charge separation proton reduction ability Pt, leading an optimal activity at equilibrium point.

Язык: Английский

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Coordination engineering in single-site catalysts: General principles, characterizations, and recent advances

Chem, Год журнала: 2023, Номер 10(1), С. 48 - 85

Опубликована: Сен. 21, 2023

Язык: Английский

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Construction of Three-Dimensional Dendritic Hierarchically Porous Metal–Organic Framework Nanoarchitectures via Noncentrosymmetric Pore–Induced Anisotropic Assembly

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(30), С. 16498 - 16507

Опубликована: Июль 21, 2023

As a unique class of modular nanomaterials, metal-organic framework (MOF) nanoparticles have attracted widespread interest for use in various fields because their diverse chemical functionalities, intrinsic microporosity, and three-dimensional (3D) nanoarchitectures. However, endowing MOF nanomaterials with precisely controlled structural symmetries hierarchical macro/mesoporosities remains formidable challenge the researchers. Herein, we report facile noncentrosymmetric pore-induced anisotropic assembly strategy to prepare series 3D dendritic (UiO-66) highly controllable macro/meso/microporosities. The synthetic route these depends on nucleation spherical nanocones center-radial channels oriented growth isotropic nanospheres through continuous increase radius solid angle. This enables fabrication asymmetric nanostructures abundant geometries porous structures by regulating concentration amphiphilic triblock copolymer templates. Furthermore, average pore diameter resultant can be systematically manipulated wide range from 35 130 nm finely tuning reaction temperature. Meanwhile, also extended synthesize other similar architectures. Compared microporous UiO-66 nanocrystals, macro/meso/microporosities show enhanced catalytic activity CO2 cycloaddition reaction. methodology provides new insights into rational construction sophisticated open hierarchically MOFs many potential applications.

Язык: Английский

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Confinement-Induced Indium Oxide Nanolayers Formed on Oxide Support for Enhanced CO₂ Hydrogenation Reaction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5523 - 5531

Опубликована: Фев. 17, 2024

An enclosed nanospace often shows a significant confinement effect on chemistry within its inner cavity, while whether an open space can have this remains elusive. Here, we show that the surface of TiO2 creates confined environment for In2O3 which drives spontaneous transformation free nanoparticles in physical contact with into In oxide (InOx) nanolayers covering onto during CO2 hydrogenation to CO. The formed InOx are easy create oxygen vacancies but against over-reduction metallic H2-rich atmospheres, thus significantly enhanced activity and stability comparison pure catalyst. formation interfacial In–O–Ti bonding is identified drive dispersion stabilize metastable layers. overlayers distinct from their counterpart be various surfaces, demonstrating important at oxide/oxide interfaces.

Язык: Английский

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