Structure Of Nanoclusters Research Articles

Core-Packing-Related Vibrational Properties of Thiol-Protected Gold Nanoclusters and Their Excited-State Behavior.

Thiolate-protected gold nanoclusters, with unique nuclearity- and structure-dependent properties, have been extensively used in energy conversion and catalysis; however, the mystery between kernel structures and properties remains to be revealed. Here, the influence of core packing on the electronic structure, vibrational properties, and excited-state dynamics of four gold nanoclusters with various kernel structures is explored using density functional theory combined with time-domain nonadiabatic molecular dynamics simulations. We elucidate the correlation between the geometrical structure and excited-state dynamics of gold nanoclusters. The distinct carrier lifetimes of the four nanoclusters are attributed to various electron-phonon couplings arising from the different vibrational properties caused by core packing. We have identified specific phonon modes that participate in the electron-hole recombination dynamics, which are related to the gold core of nanoclusters. This study paints a physical picture from the geometric configuration, electronic structure, vibrational properties, and carrier lifetime of these nanoclusters, thereby facilitating their potential application in optoelectronic materials.

Morphology and Phase Compositions of FePt and CoPt Nanoparticles Enriched with Noble Metal

The article reveals for the first time the features of nanoparticle morphology, phase compositions, and their changes when heating FePt and CoPt nanoalloys. Nanoparticles were obtained by co-reduction of precursor solution mixtures with hydrazine hydrate. The features were found by a complex of methods of X-ray diffraction (in situ XRD and X-ray scattering), TEM HR, and cyclic voltammetry. In addition, adsorbometry results were obtained, and the stability of different nanocluster structures was calculated by the molecular dynamics method. There were only FCC solid solutions in the X-ray patterns of the FePt and CoPt nanoalloys. According to XRD, in the case of nanoparticle synthesis with Fe and Co content less than 10 at. %, the composition of solid solutions was close to or practically equal to the composition of the as-synthesized nanoparticles quantified by inductively coupled plasma optical emission spectrometry. For systems synthesis with Fe and Co content greater than the above, the solubility limits (SLs) of Fe and Co in Pt were set 11.4 ± 0.7 at. % and 17.5 ± 0.6 at. %, respectively. Therefore, there were non-registered XRD extra-phases (XRNDPh-1) in the systems when CFe,Co ≥ SL. This statement was supported by the results of TEM HR and X-ray scattering: the smallest nanocrystals (1–2 nm) and amorphous particles were found, which qualitatively agreed with the sorbometry and SAXS results. Molecular dynamics calculations of stability for FePt and CoPt alloys claimed the structures of the most stable phase corresponded to phase diagrams (A1 and L12). Specific peculiarities of the morphology and compositions of the solid solutions of nanoalloys were established: structural blockiness (domain) and composition heterogeneity, namely, platinum enrichment of internal (deep) layers and homogenization of the nanoalloy compositions at relatively low temperatures (130–200 °C). The suggested model of the formation of nanoalloys during the synthesis, qualitatively, was compliant with the results of electrochemical deposition of FePt films on the surface of various electrodes. When nanocrystals of solid solutions (C(Fe, Co) < SL) were heated above specific temperatures, there were phase transformations with the formation of two-phase regions, with solid solutions enriched with platinum or iron (non-registered XRD phase XRNDPh-2). The newly formed phase was most likely intermetallic compounds, FePt3, CoPt3. As a result of the study, the model was developed, taking into account the nanoscale of the particles: XRDPh (A1, FeaPt1−a) → XRDPh (A1, Fem×a−xPtm−m×a+x) + XRNDPh-2 (Fen×a+yPtn−n×a−y) (here, m + n = 1, m ≤ 1, n ≤ 1).

Simulation of noble metal nanocluster systems formation during deposition from a colloid solution

A model was proposed for the convective flow of the liquid phase of a colloidal solution of glycerol and noble metal nanoparticles (Ag, Au, Ag/Au) near the substrate. The diffusion approximation is used to describe the formation of nanocluster systems on a substrate. The diffusion-limited aggregation model was implemented by applying a cellular automaton in the Neumann neighborhood. A diverse structure of model systems of nanoclusters, which adequately describes the structural features of the experimental samples, was obtained by varying the aggregation probability parameter. The proposed models can be useful for calibrating the parameters of the experimental production of systems of noble metal nanoclusters, as well as describing in the first approximation the processes that have a decisive effect on nanocluster structures.

Coexistent, Competing Tunnelling, and Hopping Charge Transport in Compressed Metal Nanocluster Crystals.

Understanding charge transport among metal particles with sizes of approximately 1 nm poses a great challenge due to the ultrasmall nanosize, yet it holds great significance in the development of innovative materials as substitutes for traditional semiconductors, which are insulative and unstable in less than ∼10 nm thickness. Herein, atomically precise gold nanoclusters with well-defined compositions and structures were investigated to establish a mathematical relation between conductivity and interparticle distance. This was accomplished using high-pressure in situ resistance characterizations, synchrotron X-ray diffraction (XRD), and the Murnaghan equation of state. Based on this precise correlation, it was predicted that the conductivity of Au25(SNap)18 (SNap: 1-naphthalenethiolate) solid is comparable to that of bulk silver when the interparticle distance is reduced to approximately 3.6 Å. Furthermore, the study revealed the coexisting, competing tunneling, and incoherent hopping charge transport mechanisms, which differed from those previously reported. The introduction of conjugation-structured ligands, tuning of the structures of metal nanoclusters, and use of high-pressure techniques contributed to enhanced conductivity, and thus, the charge carrier types were determined using Hall measurements. Overall, this study provides valuable insight into the charge transport in gold nanocluster solids and represents an important advancement in metal nanocluster semiconductor research.

Metasurface Absorbers with Film-Coupled Au Nanoclusters to Achieve Broadband and Polarization-Independent Absorption of UV-Vis Light.

Metasurface absorbers (MAs) have attracted widespread interest in the recent study of subwavelength artificial optical metasurfaces, although most reported MAs suffer from the actualities of costly and time-consuming fabrications, narrow working bandwidth, polarization-dependent responses, etc., somewhat limiting their practical applications. Herein, we introduce a facile and low-cost method to fabricate MAs with excellent absorption performances via the self-assembly of synthesized Au nanoclusters (NCs) on a Au film spaced by a nanoscale-thick dielectric SiO2. Interestingly, the proposed MAs with well-designed Au film-coupled Au NCs (i.e., an appropriate surface coverage of Au NCs and the compatible thickness of the SiO2 spacer) exhibited a measured average absorbance above 90% within a broad UV-vis wavelength band (200-800 nm). In addition, owing to the MAs' topological symmetry, their UV-vis absorption behaviors presented polarization insensitivity with the incident light angles ranging from 20 to 50°. It has been demonstrated that the excited different surface plasmon resonance modes between Au NCs and the adjacent Au film were vital; in addition, the light-trapping effects from "V"-shaped structures of Au NCs were favorable for the designed MAs with enhanced light absorption. We believe that such MAs and the potential self-assembly fabrication strategy may facilitate scalable optical applications such as photothermalvoltaics, ultraviolet protection, optical storage, and sensing.

Structure, stability and electronic properties of zirconium nitride nanoclusters

Zirconium nitride (ZrN) is an industrial material having very high melting point, hardness and chemical stability. Compared to the bulk ZrN, its nanoclusters (NCs) are rarely explored. In this report, we generate a few ZrN NCs using ab initio molecular dynamics simulation. We investigate their electronic properties in terms of Bader charge, electron localization function and density of states. The obtained results are compared with their bulk counterpart. We also study the static and dynamical stability of the NCs with the help of binding energy, density of states and phonon dispersion spectra. The electron localization function of bulk ZrN is reported here for the first time to better understand its often confusing bonding behaviour.

Clarifying the Electronic Structure of Anion-Templated Silver Nanoclusters by Optical Absorption Spectroscopy and Theoretical Calculation.

Electronic structures of anion-templated silver nanoclusters (Ag NCs) are not well understood compared to conventional, template-free Ag NCs. In this study, we synthesized three new anion-templated Ag NCs, namely [S@Ag17(S-4CBM)15(PPh3)5]0, [S@Ag18(S-4CBM)16(PPh3)8]0, and [Cl@Ag18(S-4CBM)16(PPh3)8][PPh4], where S-4CBM = 4-chlorobenzene methanethiolate, and single-crystal X-ray crystallography revealed that they have S@Ag6, S@Ag10, and Cl@Ag10 cores, respectively. Investigation of their electronic structures by optical spectroscopy and theoretical calculations elucidated the following unique features: (1) their electronic structures are different from those of template-free Ag NCs described by the superatomic concept; (2) optical absorption in the range of 550-400 nm for S2--templated Ag NCs is attributed to the charge transitions from S2--templated Ag-cage orbitals to the s-shaped orbital in the S2- moiety; (3) the Cl--templated Ag NCs can be viewed as [Cl@Ag18(S-4CBM)16(PPh3)8]0[PPh4]0 rather than the ion pair [Cl@Ag18(S-4CBM)16(PPh3)8]-[PPh4]+; and (4) singlet-coupled singly occupied orbitals are involved in the optical absorption of the Cl--templated Ag NC.

Ag Nanocluster Production through DC Magnetron Sputtering and Inert Gas Condensation: A Study of Structural, Kelvin Probe Force Microscopy, and Optical Properties.

Silver nanoclusters are valuable for a variety of applications. A combination of direct current (DC) magnetron sputtering and inert gas condensation methods, employed within an ultra-high vacuum (UHV) system, was used to generate Ag nanoclusters with an average size of 4 nm. Various analytical techniques, including Scanning Probe Microscopy (SPM), X-ray Diffraction (XRD), Kelvin Probe Force Microscopy (KPFM), UV-visible absorption, and Photoluminescence, were employed to characterize the produced Ag nanoclusters. AFM topographic imaging revealed spherical nanoparticles with sizes ranging from 3 to 6 nm, corroborating data from a quadrupole mass filter (QMF). The XRD analysis verified the simple cubic structure of the Ag nanoclusters. The surface potential was assessed using KPFM, from which the work function was calculated with a reference highly ordered pyrolytic graphite (HOPG). The UV-visible absorption spectra displayed peaks within the 350-750 nm wavelength range, with a strong absorption feature at 475 nm. Additionally, lower excitation wavelengths resulted in a sharp peak emission at 370 nm, which became weaker and broader when higher excitation wavelengths were used.

Structural transformations in Cu, Ag, and Au metal nanoclusters.

Finite-temperature structures of Cu, Ag, and Au metal nanoclusters are calculated in the entire temperature range from 0K to melting using a computational methodology that we proposed recently [M. Settem et al., Nanoscale 14, 939 (2022)]. In this method, Harmonic Superposition Approximation (HSA) and Parallel Tempering Molecular Dynamics (PTMD) are combined in a complementary manner. HSA is accurate at low temperatures and fails at higher temperatures. PTMD, on the other hand, effectively samples the high temperature region and melts. This method is used to study the size- and system-dependent competition between various structural motifs of Cu, Ag, and Au nanoclusters in the size range 1-2nm. Results show that there are mainly three types of structural changes in metal nanoclusters, depending on whether a solid-solid transformation occurs. In the first type, the global minimum is the dominant motif in the entire temperature range. In contrast, when a solid-solid transformation occurs, the global minimum transforms either completely to a different motif or partially, resulting in the co-existence of multiple motifs. Finally, nanocluster structures are analyzed to highlight the system-specific differences across the three metals.

Theoretical predictions and electronic properties of thiolate-protected gold nanocluster: Au44(SR)32

Thiolate-protected gold nanoclusters have received extensive attention both experimentally and theoretically due to their excellent physical and chemical properties. However, comprehending the geometric structure of thiolate-protected gold nanoclusters remains a challenging task. Predicting the structural configuration of these ligand-protected gold nanoclusters can enhance our understanding of this class of materials. Due to the current lack of knowledge regarding the structure of Au44(SR)32, we employed the grand unified model (GUM) for gold core stacking and the ring model to describe interfacial interactions between gold cores and the protection motifs. Based on these models, we successfully predicted the geometric structure of Au44(SR)32 clusters and demonstrated partial reproducibility between the calculated absorption spectra and experimental results. Furthermore, by analyzing the energy levels and molecular orbitals, we have identified that the absorption spectra of Au44(SR)32 arise from d→d and d→sp transitions, with the low-energy state primarily resulting from Au44-to-core transitions and the high-energy state from Au44-to-ligand transitions. These findings not only enhance our understanding of Au44(SR)32 clusters but also validate the effectiveness and applicability of GUM and ring model in predicting stable structures of thiolate-protected gold nanoclusters.

Study on the Degradation of Methylene Blue by Cu-Doped SnSe.

Treatment of organic wastewater is still a difficult problem to solve. In this paper, Cu-doped SnSe powder was synthesized by a convenient and efficient hydrothermal method. Meanwhile, the degradation effect of different doping concentrations of SnSe on methylene blue was investigated. It was found that at low doping concentrations, the degradation effect on methylene blue was not obvious because Cu was dissolved in the lattice of the SnSe matrix at low concentrations. As the doping concentration increased, SnSe changed from a layered structure to a nanocluster structure with reduced particle size, and a mixed phase of SnSe and Cu2SnSe4 appeared. In fact, the degradation effect on methylene blue was significantly enhanced, and we found that the catalytic degradation effect on methylene blue was best at a doping concentration of 10 wt.%.

Filling the Gap: Atomically Precise Metal Nanoclusters‐Induced Z‐Scheme Photosystem toward Robust and Stable Solar Hydrogen Generation

AbstractAtomically precise metal nanoclusters (NCs) represent a promising generation of metal nanomaterial because of characteristic atomic stacking mode, abundant catalytic active sites, and molecular‐like discrete energy band structure. However, crafting metal NCs‐dominated photocatalytic systems with mediated charge transport pathways for photoredox catalysis is in the infant stage and their photocatalytic mechanisms remain elusive, which is largely hampered by the ultra‐short charge lifetime, generic instability, and complicated electronic structure of metal NCs. In this study, the smart construction of all‐solid‐state metal NCs‐transition metal chalcogenides quantum dots (TMCs QDs) Z‐scheme artificial photosystems for robust and stable solar‐to‐hydrogen conversion is demonstrated. The concurrent favorable photosensitization efficiency of metal NCs and TMCs QDs synergistically stimulate the unexpected Z‐scheme charge transport pathway, which significantly boosts the anisotropic spatial vectorial charge transport/separation, giving rise to considerably enhanced visible‐light‐responsive photocatalytic hydrogen generation performances along with favorable stability. This study would push forward the prosperity of exploring metal NCs‐based photosystems for solar‐to‐hydrogen conversion.

Neighboring Platinum Atomic Sites Activate Platinum-Cobalt Nanoclusters as High-Performance ORR/OER/HER Electrocatalysts.

The rational design of efficient and multifunctional electrocatalysts for energy conversion devices is one of the major challenges for clean and renewable energy transition. Herein, the local electronic structure of cobalt-platinum nanoclusters is regulated by adjacent platinum atomic site encapsulated in N-doped hollow carbon nanotubes (PtSA -PtCo NCs/N-CNTs) by pyrolysis of melamine-orientation-induced zeolite imidazole metal-organic frameworks (ZIF-67) with thimbleful platinum doping. The introduction of melamine can reactivate adjacent carbon atoms and initiate the oriented growth of nitrogen-doped carbon nanotubes. The systematic analysis suggests the significant role of thimbleful neighboring low-coordinated Pt─N2 in altering the localized electronic structure of PtCo nanoclusters. The optimized PtSA -PtCo NCs/N-CNTs-900 exhibit excellent hydrogen evolution reaction (HER)/oxygen evolution reaction (OER)/oxygen reduction reaction (ORR)/ catalytic performance reaching the current density of 10mA cm-2 in 1m KOH under the low 47 (HER) and 252mV (OER) overpotentials, and a high half-wave potential of 0.86 and 0.89V (ORR) in 0.1m KOH and 0.1m HClO4 , respectively. Remarkably, the PtSA -PtCo NC/N-CNT-900 also presents outstanding catalytic performances toward water splitting and rechargeable Zn-air batteries. The theoretical calculations reveal that optimal regulation of the electronic structure of PtCo nanoclusters by thimbleful neighboring Pt atomic reduces the reaction energy barrier in electrochemical process, facilitating the ORR/OER/HER performance.

Protein-Templated Metal Nanoclusters: Molecular-like Hybrids for Biosensing, Diagnostics and Pharmaceutics.

The use of proteins as biomolecular templates to synthesize atomically precise metal nanoclusters has been gaining traction due to their appealing properties such as photoluminescence, good colloidal- and photostability and biocompatibility. The synergistic effect of using a protein scaffold and metal nanoclusters makes it especially attractive for biomedical applications. Unlike other reviews, we focus on proteins in general as the protective ligand for various metal nanoclusters and highlight their applications in the biomedical field. We first introduce the approaches and underlined principles in synthesizing protein-templated metal nanoclusters and summarize some of the typical proteins that have been used thus far. Afterwards, we highlight the key physicochemical properties and the characterization techniques commonly used for the size, structure and optical properties of protein-templated metal nanoclusters. We feature two case studies to illustrate the importance of combining these characterization techniques to elucidate the formation process of protein-templated metal nanoclusters. Lastly, we highlight the promising applications of protein-templated metal nanoclusters in three areas-biosensing, diagnostics and therapeutics.

Dynamic Metal Nanoclusters: A Review on Accurate Crystal Structures.

Dynamic metal nanoclusters have garnered widespread attention due to their unique properties and potential applications in various fields. Researchers have been dedicated to developing new synthesis methods and strategies to control the morphologies, compositions, and structures of metal nanoclusters. Through optimized synthesis methods, it is possible to prepare clusters with precise sizes and shapes, providing a solid foundation for subsequent research. Accurate determination of their crystal structures is crucial for understanding their behavior and designing custom functional materials. Dynamic metal nanoclusters also demonstrate potential applications in catalysis and optoelectronics. By manipulating the sizes, compositions, and surface structures of the clusters, efficient catalysts and optoelectronic materials can be designed and synthesized for various chemical reactions and energy conversion processes. This review summarizes the research progress in the synthesis methods, crystal structure characterization, and potential applications of dynamic metal nanoclusters. Various nanoclusters composed of different metal elements are introduced, and their potential applications in catalysis, optics, electronics, and energy storage are discussed. Additionally, the important role of dynamic metal nanoclusters in materials science and nanotechnology is explored, along with an overview of the future directions and challenges in this field.

Real-space solution to the electronic structure problem for nearly a million electrons.

We report a Kohn-Sham density functional theory calculation of a system with more than 200 000 atoms and 800 000 electrons using a real-space high-order finite-difference method to investigate the electronic structure of large spherical silicon nanoclusters. Our system of choice was a 20nm large spherical nanocluster with 202 617 silicon atoms and 13 836 hydrogen atoms used to passivate the dangling surface bonds. To speed up the convergence of the eigenspace, we utilized Chebyshev-filtered subspace iteration, and for sparse matrix-vector multiplications, we used blockwise Hilbert space-filling curves, implemented in the PARSEC code. For this calculation, we also replaced our orthonormalization + Rayleigh-Ritz step with a generalized eigenvalue problem step. We utilized all of the 8192 nodes (458 752 processors) on the Frontera machine at the Texas Advanced Computing Center. We achieved two Chebyshev-filtered subspace iterations, yielding a good approximation of the electronic density of states. Our work pushes the limits on the capabilities of the current electronic structure solvers to nearly 106 electrons and demonstrates the potential of the real-space approach to efficiently parallelize large calculations on modern high-performance computing platforms.

UV Photoluminescence Microscopy of Individual ZnO Nanostructured Clusters

Ultraviolet (UV) photoluminescence (PL) spectra were acquired from individual nanostructured ZnO clusters less than 1 μm in size. The nanostructured clusters were formed by aggregation of a small number of nanoparticles. This analysis employed a microscopy apparatus specially designed for PL assessments of nanostructures at UV wavelengths with a spatial resolution of 0.395 μm. Atomic force microscopy was also employed to ascertain the sizes and morphologies of the nanostructured clusters. The ZnO samples were prepared by laser ablation in liquid (LAL) and comprised spherical, rhomboid, or gel-coated particles. PL emissions originating from free excitons (FX), FX phonon replicas, and defects were observed. The FX peak widths and positions were found to vary (with positions from 3.30 to 3.36 eV), suggesting that a range of particle sizes and morphologies was obtained from the LAL process. FX peaks at higher energies exhibited greater widths as a consequence of a quantum size effect originating from the crystallites comprising the nanostructured clusters. The rhomboid particles showed less-intense emissions related to defects compared with the other two types while also exhibiting the least intense emissions related to FX phonon replicas. This work also examined the mechanism by which nanoparticles were produced by LAL on the basis of the spectroscopic data. The information presented herein is expected to assist in the design and fabrication of semiconductor nanoparticles for future nanotechnology applications.

Solving the electronic structure problem for over 100 000 atoms in real space

Using a real-space high-order finite-difference approach, we investigate the electronic structure of large spherical silicon nanoclusters. Within Kohn-Sham density functional theory and using pseudopotentials, we report the self-consistent field convergence of a system with over 100 000 atoms: a ${\mathrm{Si}}_{107,641}{\mathrm{H}}_{9,084}$ nanocluster with a diameter of 16 nm. Our approach uses Chebyshev-filtered subspace iteration to speed up the convergence of the eigenspace, and blockwise Hilbert space-filling curves to speed up sparse matrix-vector multiplications, all of which are implemented in the parsec code. For the largest system, we utilized 2048 nodes (114 688 cores) on the Frontera machine in the Texas Advanced Computing Center. Our quantitative analysis of the electronic structure shows how it gradually approaches its bulk counterpart as a function of nanocluster size. The band gap is enlarged due to quantum confinement in nanoclusters, but decreases as the system size increases, as expected. Our work serves as a proof of concept for the capacity of the real-space approach in efficiently parallelizing very large calculations using high-performance computer platforms, which can straightforwardly be replicated in other systems with more than ${10}^{5}$ atoms.

Isolation and Structures of Polyarene Palladium Nanoclusters.

We report that surrounding coordination of neutral six-membered arene rings affords molecularly well-defined organotransition metal nanoclusters. With the use of [2.2]paracyclophane as the face-capping arene ligand, we have isolated two polyarene palladium nanoclusters, one consisting of a hexakis-arene ligand shell and a hexagonal close-packed Pd13 anticuboctahedron trichloride core, and the other consisting of an octakis-arene ligand shell and a non-close-packed Pd17 square gyrobicupola dichloride core, both with Pd-Pd direct bonding. The μ4-facial coordination mode of arene was discovered through the structural characterization of the Pd13 cluster. Their Pd13 and Pd17 cores, which are distinct from the previously identified face-centered-cubic Pd13 core surrounded by seven-membered cycloheptatrienyl, are explained by stereochemical and theoretical analyses.

Slice Visualization for Imaging Nanocluster Transformations.

Metal nanoclusters have served as an emerging class of modular nanomaterials. Several efficient strategies have been proposed for transforming cluster precursors into new nanoclusters with customized structures and enhanced performance. However, such nanocluster transformations have still been in a "blind box" state, meaning that the existing intermediates were hard to track with atomic precision. Herein, we present a "slice visualization" approach for in-depth imaging of the nanocluster transformation from Au1Ag24(SR)18 to Au1Ag30(SR)20. With this approach, two cluster intermediates, namely, Au1Ag26(SR)19 and Au1Ag28(SR)20, were monitored with atomic precision. The four nanoclusters constituted a correlated Au1Ag24+2n (n = 0, 1, 2, and 3) cluster series with comparable structural features─the same Au1Ag12 icosahedral kernel but evolutionary peripheral motif structures. The mechanism of nanocluster structure growth was mapped in detail─insertion of Ag2(SR)1 or Ag-induced assembly of surface subunits. The presented "slice visualization" approach not only contributes an ideal cluster platform for in-depth investigations of structure-property correlations but also hopefully acts as a powerful means for obtaining clear information on nanocluster structure evolution.