Shaping the Optical Properties of Silver Clusters Inside Zeolite A via Guest–Host–Guest Interactions

Baekelant, Wouter; Aghakhani, Saleh; Coutiño-González, Eduardo; Kennes, Koen; d’Acapito, Francesco; Grandjean, D.; Auweraer, Mark Van der; Lievens, Peter; Roeffaers, Maarten B. J.; Hofkens, Johan; Steele, Julian A.

doi:10.1021/acs.jpclett.8b01890

Cited by 34 publications

(55 citation statements)

References 44 publications

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“…[63] Without organic templates, silver NCs confined in the rigid micropores of zeolites exhibited similar dual fluorescence-phosphorescence emission, in which higher energy emission band possessed a short lifetime (ns scale) and lower one possessed a long lifetime (µs scale). The emission properties can be tuned by the solvent [68], thermal annealing treatment [77] and cations [19,78,79], etc. which was highly related to the hydration state of silver NCs [20,80], and the emission was unambiguously attributed to the behavior of structural water molecules (SWs) confined in nanoscale interface and/or space [67][68][69][70][71].…”

Section: Resultsmentioning

confidence: 99%

Origin of the Bright Photoluminescence of Thiolate-protected Gold Nanoclusters: Confined Structural Water Molecules as Real Emitters

Peng

Zhang

2021

Preprint

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The availability of a range of excited states has enriched zero-, one- and two- dimensional quantum nanomaterials with interesting luminescence properties, in particular for noble metal nanoclusters (NCs) as typical examples. But, the elucidation and origin of optoelectronic properties remains elusive. In this report, using widely used Au(I)-alkanethiolate complex (Au(I)-SRs, R = -(CH2)12H) with AIE characteristics as a model system, by judiciously manipulating the delicate surface ligand interactions at the nanoscale interface, together with a careful spectral investigations and an isotope diagnostic experiment of heavy water (D2O), we evidenced that the structural water molecules (SWs) confined in the nanoscale interface or space are real emitter centers for photoluminescence (PL) of metal NCs and the aggregate of Au(I)-SRs complexes, instead of well-organized metal core dominated by quantum confinement mechanics. Interestingly, the aggregation of Au(I)-SRs generated dual fluorescence-phosphorescence emission and the photoluminescence intensity was independent on the degree of aggregation but showed strong dependency on the content and state of structural water molecules (SWs) confined in the aggregates. SWs are different from traditional hydrogen bonded water molecules, wherein, due to interfacial adsorption or spatial confinement, the p orbitals of two O atoms in SWs can form a weak electron interaction through spatial overlapping, which concomitantly constructs a group of interfacial states with π bond characteristics, consequently providing some alternative channels (or pathways) to the radiation and/or non-radiation relaxation of electrons. Our results provide completely new insights to understand the fascinating properties (including photoluminescence, catalysis and chirality, etc.) of other low-dimension quantum dots and even for aggregation-induced emission luminophores (AIEgens). This also answers the century old debate on whether and how water molecules emit bright color.

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Section: Resultsmentioning

confidence: 99%

Origin of the Bright Photoluminescence of Thiolate-protected Gold Nanoclusters: Confined Structural Water Molecules as Real Emitters

Peng

Zhang

2021

Preprint

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“…These changes were connected to shrinkage of the framework unit cell, induced by the different cations, similarly to the role enacted by Li + in Ag-LTA. [35] Through unit cell refinement, linear growth of the unit cell parameter was found going from Li + to Cs + . Furthermore, they suggested that the emission from Ag-NCs originated from both ligand-to-metal and metalto-metal charge transfer.…”

Section: Role Of Water Molecules and Counter-balancing Cations As Optical Modulators Of Ag-ncsmentioning

confidence: 98%

“…The knowledge gained by studying Li + -Ag-nanocluster interactions suggested that an additional degree of control could be introduced by carefully controlling the lithium content. In 2018 Steele and co-workers [35] not only sought to understand the concept of guest-host-guest interaction within this multicomponent system but control it. Here, silver-exchanged Li/Na-LTA zeolites were reported with luminescence colors spanning the whole visible range and PLQYs reached ≈50% by adjusting the Li/Na ratio in LTA zeolites (Figure 4b).…”

Section: Addition Of Counter-balancing Cations and Understanding Guest-host Interactionsmentioning

confidence: 99%

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Tunable Luminescence from Stable Silver Nanoclusters Confined in Microporous Zeolites

Romolini

Steele

Hofkens

et al. 2021

Advanced Optical Materials

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properties associated with nanoclusters' molecule-like structure and energetics. Most notably, metal nanoclusters rose to research prominence in connection to the discovery of outstanding optoelectronic properties and have found practical application within catalysis, bioimaging, lighting and molecular sensing. [1][2][3][4][5][6] However, nanocluster' stabilization remains a significant impediment owing to their tendency to merge and form ever-larger aggregates at the loss of their interesting properties. Therefore, research efforts have been devoted to developing novel synthetic strategies to stabilize isolated metal nanoclusters; [7] popular approaches have often taken the form of using organic scaffolds such as DNA/RNA, proteins, and polymers. [8][9][10][11][12][13][14][15][16] The use of organic molecules gives rise to high synthesis yields, good luminescence performance, and strong compatibility with living organism, making them excellent candidates as fluorophores. Unfortunately, a main drawback is their poor long-term stability, especially in solid form, hindering their application, e.g., within lighting devices. On the other hand, template-mediated strategies based on the self-organization of the metal nanocluster within a confined volume (so-called "ship-in-a-bottle" approach) provide a promising alternative, one where the size and shape of the final metal nanocluster are dictated by the spatial restrictions imposed by the rigid host nanostructure. [17] To date, common templating structures have included glass matrices, [18] metal-organic frameworks, [19] and porous aluminosilicate zeolite crystals. [20] Here, we will shine light on zeolites as a promising scaffold for the assembly of highly luminescent and functional silver nanoclusters (Ag-NCs) within their (nano)porous interior (Figure 1a-c). As a host framework, zeolites possess molecular-sized channels and cages which enable them to confine molecules or metal (oxide) clusters inside their crystalline interior in a controlled fashion. Moreover, the framework is negatively charged, requiring counter-balancing extra-framework cations, which can be easily replaced through simple exchange methods. As shown in Figure 1d, forming the caged Ag-NCs involves a scalable bottom-up approach, whereby Ag + ions are made to self-assemble into nanoclusters via energy-driven activation (thermal treatment, photoactivation, or X-rays irradiation). Once the cluster is assembled, its optical response can be further tuned by the intentional exchange of additional guest

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“…Zeolites are microporous crystalline solids constituted by a regular 3-dimensional arrangement of TO 4 groups (T=Si, Al) that form cages and channels with a size lower than 2 nm. The zeolite materials offer unique possibility to tailor the properties of photoactive guest chemical species, [1][2][3][4] organo-metallic complexes, [5,6] metal clusters and nanoparticles [7,8] by confining them inside the pores and aligning along their 3D architecture. [9,10] Metal-containing zeolites are notably investigated for photocatalysis [11][12][13] and one attractive route of development consists coupling of zeolites with plasmonic nanostructure to enhance their photocatalytic activity.…”

Section: Introductionmentioning

confidence: 99%

Hot‐Electron Photodynamics in Silver‐Containing BEA‐Type Nanozeolite Studied by Femtosecond Transient Absorption Spectroscopy

et al. 2020

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Silver cations were introduced in nanosized BEA‐type zeolite containing organic template by ion‐exchange followed by chemical reduction towards preparation of photoactive materials (Ag0‐BEA). The stabilization of highly dispersed Ag0 nanoparticles with a size of 1–2 nm in the BEA zeolite was revealed. The transient optical response of the Ag‐BEA samples upon photoexcitation at 400 nm was studied by femtosecond absorption. The photodynamic of the hot electrons was found to depend on the sample preparation. The lifetime of the hot electrons in the Ag−BEA samples containing small Ag nanoparticles (1–2 nm) is significantly shortened in comparison to bear Ag nanoparticles with a size of 10 nm. While for the larger Ag nanoparticles, the energy absorbed in the conduction band is decaying by electron‐phonon coupling into the metal lattice, the high surface‐to‐volume ratio of the small Ag nanoparticles favors the dissipation of the energy of the hot electrons from the metal nanoparticles (Ag0) towards the zeolitic micro‐environment. This finding is encouraging for further applications of Ag‐containing zeolites in photocatalysis and plasmonic chemistry.

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Shaping the Optical Properties of Silver Clusters Inside Zeolite A via Guest–Host–Guest Interactions

Cited by 34 publications

References 44 publications

Origin of the Bright Photoluminescence of Thiolate-protected Gold Nanoclusters: Confined Structural Water Molecules as Real Emitters

Origin of the Bright Photoluminescence of Thiolate-protected Gold Nanoclusters: Confined Structural Water Molecules as Real Emitters

Tunable Luminescence from Stable Silver Nanoclusters Confined in Microporous Zeolites

Hot‐Electron Photodynamics in Silver‐Containing BEA‐Type Nanozeolite Studied by Femtosecond Transient Absorption Spectroscopy

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