Single-atom catalysts for photocatalytic energy conversion

Joule, Год журнала: 2022, Номер 6(1), С. 92 - 133

Опубликована: Янв. 1, 2022

Artificial photocatalytic energy conversion represents a highly intriguing strategy for solving the crisis and environmental problems by directly harvesting solar energy. The development of efficient photocatalysts is central task pushing real-world application reactions. Due to maximum atomic utilization efficiency distinct advantages outstanding catalytic activity, single-atom catalysts (SACs) have emerged as promising candidates photocatalysts. In current review, recent progresses challenges on SACs systems are presented. Fundamental principles focusing charge separation/transfer molecular adsorption/activation photocatalysis systemically explored. We outline how isolated reactive sites facilitate photogenerated electron–hole transfer promote construction photoactivation cycles. widespread adoption in diverse reactions also comprehensively introduced. By presenting these advances addressing some future with potential solutions related integral over SACs, we expect shed light forthcoming research conversion.

Язык: Английский

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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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Porphyrin-based framework materials for energy conversion

Deleted Journal, Год журнала: 2022, Номер 1, С. e9120009 - e9120009

Опубликована: Май 26, 2022

With the increasing demand for fuel causing serious environmental pollution, it is urgent to develop new and environmentally friendly energy conversion devices. These devices, however, require good, inexpensive materials electrodes so on. The multifunctional properties of porphyrins enable framework (e.g., metal-organic frameworks covalent organic frameworks) be applied in devices due their simple synthesis, high chemical stability, abundant metallic active sites, adjustable crystalline structure specific surface area. Herein, types porphyrin structural blocks are briefly reviewed. They can used as ligands or directly assembled with generate high-performance electro-/photo-catalysts. catalysts electro-/photo-catalytic water splitting, carbon dioxide reduction, electrocatalytic oxygen reduction also summarized introduced. At end article, we present challenges porphyrin-based above application corresponding solutions. We expect flourish coming years.

Язык: Английский

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Water-Stable Nickel Metal–Organic Framework Nanobelts for Cocatalyst-Free Photocatalytic Water Splitting to Produce Hydrogen

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(6), С. 2747 - 2754

Опубликована: Фев. 2, 2022

Development of water-stable metal-organic frameworks (MOFs) for promising visible-light-driven photocatalytic water splitting is highly desirable but still challenging. Here we report a novel p-type nickel-based MOF single crystal (Ni-TBAPy-SC) and its exfoliated nanobelts (Ni-TBAPy-NB) that can bear wide range pH environment in aqueous solution. Both experimental theoretical results indicate feasible electron transfer from the H4TBAPy ligand (light-harvesting center) to Ni-O cluster node (catalytic center), on which produce hydrogen be efficiently driven free cocatalyst. Compared crystal, two-dimensional (2D) show more efficient charge separation due shortened distance remarkably enhanced active surface areas, resulting 164 times promoted reduction activity. The optimal H2 evolution rate nanobelt reaches 98 μmol h-1 (ca. 5 mmol g-1) showing benchmarked apparent quantum efficiency (AQE) 8.0% at 420 nm among MOFs photocatalysts.

Язык: Английский

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Carbon Nitride Photocatalysts with Integrated Oxidation and Reduction Atomic Active Centers for Improved CO₂Conversion

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(34)

Опубликована: Июнь 18, 2022

Single-atom active-site catalysts have attracted significant attention in the field of photocatalytic CO2 conversion. However, designing active sites for reduction and H2 O oxidation simultaneously on a photocatalyst combining corresponding half-reaction system is still difficult. Here, we synthesized bimetallic single-atom with two compatible centers Mn Co carbon nitride (Mn1 Co1 /CN). Our experimental results density functional theory calculations showed that center promotes by accumulating photogenerated holes. In addition, activation increasing bond length angle molecules. Benefiting from synergistic effect atomic centers, Mn1 /CN exhibited CO production rate 47 μmol g-1 h-1 , which significantly higher than single-metal photocatalyst.

Язык: Английский

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Single atoms meet metal–organic frameworks: collaborative efforts for efficient photocatalysis

Energy & Environmental Science, Год журнала: 2022, Номер 15(9), С. 3722 - 3749

Опубликована: Янв. 1, 2022

MOF-supported single atom materials offer great potential for design and engineering of advanced photocatalysts energy conversion applications. State-of-the-art prospects in recent breakthroughs are presented this review.

Язык: Английский

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Isolating Single and Few Atoms for Enhanced Catalysis

Advanced Materials, Год журнала: 2022, Номер 34(39)

Опубликована: Май 17, 2022

Abstract Atomically dispersed metal catalysts have triggered great interest in the field of catalysis owing to their unique features. Isolated single or few atoms can be anchored on substrates via chemical bonding space confinement maximize atom utilization efficiency. The key challenge lies precisely regulating geometric and electronic structure active centers, thus significantly influencing catalytic properties. Although several reviews been published preparation, characterization, application single‐atom (SACs), comprehensive understanding SACs, dual‐atom (DACs), atomic clusters has never systematically summarized. Here, recent advances engineering local environments state‐of‐the‐art DACs, for enhanced performance are highlighted. Firstly, various synthesis approaches presented. Then, special attention is focused elucidation terms state coordination structure. Furthermore, a summary isolated applications thermocatalysis, electrocatalysis, photocatalysis provided. Finally, potential challenges future opportunities this emerging This review will pave way regulate microenvironment site boosting processes.

Язык: Английский

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Modified UiO-66 as photocatalysts for boosting the carbon-neutral energy cycle and solving environmental remediation issues

Coordination Chemistry Reviews, Год журнала: 2022, Номер 458, С. 214428 - 214428

Опубликована: Фев. 3, 2022

Язык: Английский

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A General Strategy to Immobilize Single‐Atom Catalysts in Metal–Organic Frameworks for Enhanced Photocatalysis

Advanced Materials, Год журнала: 2021, Номер 34(6)

Опубликована: Дек. 9, 2021

Single-atom catalysts (SACs) are witnessing rapid development due to their high activity and selectivity toward diverse reactions. However, it remains a grand challenge in the general synthesis of SACs, particularly featuring an identical chemical microenvironment on same support. Herein, universal synthetic protocol is developed immobilize SACs metal-organic frameworks (MOFs). Significantly, by means SnO2 as mediator or adaptor, not only different single-atom metal sites, such Pt, Cu, Ni, etc., can be installed, but also MOF supports changed (for example, UiO-66-NH2 , PCN-222, DUT-67) afford M1 /SnO2 /MOF architecture. Taking representative, Pt1 exhibits approximately five times higher photocatalytic H2 production than corresponding Pt nanoparticles (≈2.5 nm) stabilized /UiO-66-NH2 . Remarkably, despite parameters support catalyst possesses hydrogen evolution rate 2167 µmol g-1 h-1 superior Cu1 Ni1 counterparts, which attributed differentiated binding free energies, supported density-functional theory (DFT) calculations. This thought first report approach stabilization with

Язык: Английский

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Engineering Single-Atom Sites into Pore-Confined Nanospaces of Porphyrinic Metal–Organic Frameworks for the Highly Efficient Photocatalytic Hydrogen Evolution Reaction

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(49), С. 22747 - 22758

Опубликована: Ноя. 25, 2022

As a type of heterogeneous catalyst expected for the maximum atom efficiency, series single-atom catalysts (SACs) containing spatially isolated metal single atoms (M-SAs) have been successfully prepared by confining M-SAs in pore-nanospaces porphyrinic metal–organic frameworks (MOFs). The MOF composites M-SAs@Pd-PCN-222-NH2 (M = Pt, Ir, Au, and Ru) display exceptionally high persistent efficiency photocatalytic hydrogen evolution reaction with turnover number (TON) up to 21713 32 h beginning/lasting frequency (TOF) larger than 1200/600 h–1 based on under visible light irradiation (λ ≥ 420 nm). photo-/electrochemical property studies density functional theory calculations disclose that close proximity catalytically active Pt-SAs Pd–porphyrin photosensitizers confinement stabilization effect chemical binding could accelerate electron–hole separation charge transfer pore-nanospaces, thus promoting catalytic H2 lasting effectiveness.

Язык: Английский

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