Atomically precise thiolate-protected gold nanoclusters: current advances in solar-powered photoredox catalysis

Liang, H.; Chen, Qing; Mo, Qiao‐Ling; Wu, Yue; Xiao, Fang‐Xing

doi:10.1039/d3ta01154b

Cited by 17 publications

(15 citation statements)

References 139 publications

(215 reference statements)

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“…Fine-size metal nanoclusters are particularly attractive in catalysis in terms of their maximized atom efficiency and superior reactivity. − Traditionally, the zeolite support featured with micropores below 2 nm was used to prepare metallic nanoclusters inside through pore confinement, which not only restricted particle overgrowth but also rendered the formed small nanoclusters therein with excellent thermal stability. , However, in another regard, the narrow pore window of the zeolite support inevitably hampered mass transfer kinetics and the reactants were commonly impeded to contact the active metal sites . It is widely accepted that the preparation of thermally stable and uniform metal nanoclusters within the more open mesoporous support is undoubtedly a better choice to attain high catalytic efficiency. − However, the mesopore-encapsulated metal nanoclusters were movable because of the lack of pore restriction and prone to transfer over the mesopore channels to aggregate, especially at high reaction temperatures, thus significantly degrading their catalytic properties …”

Section: Introductionmentioning

confidence: 99%

Stabilizing Active Metal Nanoclusters within Mesopores via an Inner Surface-Confinement Strategy

Liang

Liu

et al. 2023

Chem. Mater.

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Mesoporous support-encapsulated fine-size metal nanoclusters hold great potential for catalytic applications by virtue of their high reactivity and fast mass transport kinetics but suffer greatly from particle aggregation and/or sintering, especially under high reaction temperatures. Here, we report an inner surface-confinement strategy to stabilize a variety of ultrafine metal nanoclusters (M = Pt, Pd, Ni, and Ag) inside mesoporous silica supports. The strategy is based on the selective N functionalization of the inner surface of mesopores, which not only assures the direct growth of ultrafine metal nanoclusters therein but also endows the active metal nanoclusters with excellent thermal stability via N-metal coordination. Remarkably, the mesopore-encapsulated N-coordinated Pt nanoclusters are particularly selective for making α,β-unsaturated alcohol, benefiting from their energetically favored reaction pathway for end-on binding α,β-unsaturated aldehyde reactants and heterolytic dissociation of hydrogen. The synthetic methodology is expected to provide new guidelines to improve the thermal stability of mesopore-encapsulated metal nanoclusters for superb catalysis.

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Section: Introductionmentioning

confidence: 99%

Stabilizing Active Metal Nanoclusters within Mesopores via an Inner Surface-Confinement Strategy

Liang

Liu

et al. 2023

Chem. Mater.

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“…In the past few decades, metal nanoparticles (NPs) have ranked an important status among nanomaterials and have been widely used in various catalysis . When the size of metal NPs is reduced to a few or hundreds of atoms with a diameter of less than 2 nm, they are defined as atomically precise metal nanoclusters (NCs) that are completely different from traditional metal NPs in terms of their physicochemical properties and electronic structure. , More specifically, atomically precise metal NCs demonstrate discrete energy band structures, which endows them with a molecular-like highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) gap, featuring potential light harvesting antennas. − Moreover, peculiar atomic stacking fashion, quantum confinement effect, and enriched active sites of metal NCs make them applicable alternatives for multifarious photoredox catalysis. , However, photoinduced oxidative agglomeration of metal NCs results in the poor stability, considerably reducing the photosensitization effect of metal NCs and hinders their emerging applications in photoredox catalysis. − Therefore, how to rationally maneuver the instability of metal NCs is crucial to develop robust and durable metal NC photosystems.…”

Section: Introductionmentioning

confidence: 99%

Atomically Precise Metal Nanocluster Photosystem: Electron Relay Boosts Photocatalytic Organic Transformation

Chen,

Ge,

et al. 2023

Inorg. Chem.

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Atomically precise metal nanoclusters (NCs) demonstrate emerging potential as a new generation of photosensitizers in photoredox catalysis. However, metal NCs suffer from intrinsic poor instability, which leads to the loss of photosensitization effect and hampers their widespread applications in heterogeneous photocatalysis. Herein, we corroborate the design of a spatially directional charge transfer pathway over transition metal chalcogenide (TMC)based heterostructures by way of a facile and efficient electrostatic self-assembly approach. Positively charged solid-state nonconjugated insulating polymer of poly(allylamine hydrochloride) (PAH) and negatively charged glutathione (GSH) capped metal NCs [Ag 9 @(GSH) 6 ] as building blocks were controllably and highly ordered anchored on the TMC substrate. It was unveiled that owing to the appropriate energy level alignment and interface configuration, photogenerated electrons over metal NCs can directionally flow to the TMC substrate with the aid of PAH, which functions as an interfacial charge transfer mediator, and simultaneously holes migrate in the opposite direction, thereby collaboratively contributing to substantially boosted charge separation and prolonged charge lifetime. Benefiting from these merits, the thus self-assembled TMCs/PAH/metal NC heterostructure unfolds conspicuously enhanced photoactivity toward anaerobic selective photocatalytic reduction of nitroaromatics to amino derivatives under visible light irradiation. This work would significantly reinforce our fundamental understanding of the charge transfer characteristic of atomically precise metal NCs and the charge-withdrawing capability of solid insulating polymers for solar energy conversion.

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“…This provides an ideal model photosystem to make a critical comparison on the essential roles of alloy NCs and alloy NYs in boosting the interfacial carrier transport in photoelectrochemical (PEC) reaction, which is judiciously enabled by thermal-induced self-transformation of alloy NCs to alloy NYs. 5,29 In this way, the difference of these two metal materials consisting of the same metal atoms yet distinct dimensionality in solar-driven charge-transport behaviors can be finely tailored. In this work, atomically precise gold−silver alloy NCs (Ag x Au 1−x @GSH) are self-assembled on the TiO 2 substrate to fabricate the TiO 2 −Ag x Au 1−x NCs heterostructured photoanode for PEC water oxidation.…”

Section: Introductionmentioning

confidence: 99%

Self-Transformation of Atomically Precise Alloy Nanoclusters to Plasmonic Alloy Nanocrystals: Evaluating Photosensitization in Solar Water Oxidation

Li,

Chen,

Zhu

et al. 2023

Inorg. Chem.

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Atomically precise alloy nanoclusters (NCs) inherit the advantages of homometal NC counterparts such as atomic stacking fashion, quantum confinement effect, and enriched catalytic active sites and simultaneously possess the advantageous physicochemical properties such as significantly enhanced photostability, ideal photosensitization efficiency, and favorable energy band structure. Nevertheless, elucidation of the roles of alloy NCs and alloy nanocrystals (NYs) in boosting solar water oxidation has so far not yet been reported owing to the deficiency of applicable alloy NC photosystems. Herein, utilizing the generic thermal-induced self-transformation of alloy NCs to alloy NYs, we comprehensively explore the photosensitization properties of glutathione (GSH)-capped alloy NCs (Ag x Au 1−x @GSH and Cu x Au 1−x @GSH) and the corresponding alloy NY (AgAu and CuAu) counterparts in solar water oxidation reaction. The results imply that photoelectrons of alloy NCs surpass the hot electrons over plasmonic alloy NYs in stimulating the PEC water oxidation reaction. The photoelectrons of alloy NCs demonstrate lower interfacial charge-transfer resistance, longer carrier lifetime, and a more enhanced photosensitization effect with respect to the plasmonic alloy NYs, contributing to the significantly boosted photoelectrochemical water oxidation activities. Moreover, we found that our result is universal.

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Atomically precise thiolate-protected gold nanoclusters: current advances in solar-powered photoredox catalysis

Abstract: Photocatalysis has been regarded as an emerging technology to convert renewable solar energy to chemical fuels, providing unprecedented opportunities for solving the deteriorating energy crisis and environmental issues in the...

Cited by 17 publications

References 139 publications

Stabilizing Active Metal Nanoclusters within Mesopores via an Inner Surface-Confinement Strategy

Stabilizing Active Metal Nanoclusters within Mesopores via an Inner Surface-Confinement Strategy

Atomically Precise Metal Nanocluster Photosystem: Electron Relay Boosts Photocatalytic Organic Transformation

Self-Transformation of Atomically Precise Alloy Nanoclusters to Plasmonic Alloy Nanocrystals: Evaluating Photosensitization in Solar Water Oxidation

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