Metal nanomaterials have been extensively investigated owing to their unique properties in contrast to bulk counterparts. Gold nanoparticles (e. g., 3-100â nm) show quasi-continuous energy bands, while gold nanoclusters (<3â nm) and complexes exhibit discrete energy levels and display entirely different photophysical properties than regular nanoparticles. This review summarizes the electronic dynamics of these three types of gold materials studied by ultrafast spectroscopy. Briefly, for gold nanoparticles, their electronic relaxation is dominated by heat dissipation between the electrons and the lattice. In contrast, gold nanoclusters exhibit single-electron transitions and relatively long excited-state lifetimes being analogous to molecules. In gold complexes, the excited-state dynamics is dominated by intersystem crossing and phosphorescence. A detailed understanding of the photophysical properties of gold nanocluster materials is still missing and thus calls for future efforts. The fundamental insights into the discrete electronic structure and the size-induced evolution in quantum-sized nanoclusters will promote the exploration of their applications in various fields.
The synthesis of atomically precise gold nanoclusters with high photoluminescence quantum yield (PLQY) in the near-infrared (NIR) region and understanding their photoluminescence mechanism are crucial for both fundamental science and practical applications. Herein, we report a highly luminescent, molecularly pure Au39(PET)29 (PET = 2-phenylethanethiolate) nanocluster with PLQY of 19% in the NIR range (915 nm). Steady state and time-resolved PL analyses, as well as temperature-dependent PL measurements reveal the emission nature of Au39(PET)29, which consists of prompt fluorescence (weak), thermally activated delayed fluorescence (TADF), and phosphorescence (predominant). Furthermore, strong dipole-dipole interaction in the solid-state (e.g., Au39(PET)29 nanoclusters embedded in a polystyrene thin-film) is found to narrow the energy gap between the S1 and T1 states, which results in faster intersystem crossing and reverse intersystem crossing; thus, the ratio of TADF to phosphorescence varies and the total PLQY is increased to 32%. This highly luminescent nanocluster holds promise in imaging, sensing and optoelectronic applications.
Increasing energy demands and environmental problems require carbon-free and renewable energy generation systems. For this purpose, we have synthesized efficient photocatalysts (i.e., g-C3N4, Cu@g-C3N4, Ce@g-C3N4 and Cu/Ce@g-C3N4) for H2 evolution from water splitting. Their optical, structural and electrochemical properties were investigated by UV-Vis-DRS, PL, XRD, FTIR, Raman and EIS methods. Their surface morphologies were evaluated by AFM and SEM analyses. Their chemical characteristics, compositions and stability were assessed using XPS, EDX and TGA techniques. Photoreactions were performed in a quartz reactor (150 mL/Velp-UK), whereas hydrogen generation activities were monitored using a GC-TCD (Shimadzu-2014/Japan). The results depicted that Cu/Ce@g-C3N4 catalysts are the most active catalysts that deliver 23.94 mmol g-1 h-1 of H2. The higher rate of H2 evolution was attributed to the active synergism between Ce and Cu metals and the impact of surface plasmon electrons (SPEs) of Cu that were produced during the photoreaction. The rate of H2 production was optimized by controlling various factors, including the catalyst amount, light intensity, pH, and temperature of the reaction mixture. It has been concluded that the current study holds promise to replace the conventional and costly catalysts used for hydrogen generation technologies.
Atomically precise control over anisotropic nanoclusters constitutes a grand challenge in nanoscience. In this work, we report our success in achieving a periodic series of atomically precise gold quantum rods (abbrev. Au QRs) with unusual excitonic properties. These QRs possess hexagonal close-packed kernels with a constant three-atom diameter but increasing aspect ratios (ARs) from 6.3 to 18.7, all being protected by the same thiolate (SR) ligand. The kernels of the QRs are in a Au1-(Au3)n-Au1 configuration (where n is the number of Au3 layers) and follow a periodic elongation with a uniform Au18(SR)12 increment consisting of four Au3 layers. These Au QRs possess distinct HOMO-LUMO gaps (Eg = 0.6 to 1.3 eV) and exhibit strongly polarized excitonic transition along the longitudinal direction, resulting in very intense absorption in the near-infrared (800 to 1,700 nm). While excitons in gapped systems and plasmons in gapless systems are distinctly different types of excitations, the strongly polarized excitons in Au QRs surprisingly exhibit plasmon-like behaviors manifested in the shape-induced polarization, very intense absorption (~106 M-1 cm-1), and linear scaling relations with the AR, all of which resemble the behaviors of conventional metallic-state Au nanorods (i.e., gapless systems), but the QRs possess distinct gaps and very long excited-state lifetimes (10 to 2,122 ns), which hold promise in applications such as near-infrared solar energy utilization, hot carrier generation and transfer. The observation of plasmon-like behaviors from single-electron transitions in Au QRs elegantly bridges the distinct realms of single-electron and collective-electron excitations and may stimulate more research on excitonics and plasmonics.
Atomically precise gold nanoclusters (NCs) have emerged as a new class of precision materials and attracted wide interest in recent years. One of the unique properties of such nanoclusters pertains to their photoluminescence (PL), for it can widely span visible to near-infrared-I and -II wavelengths (NIR-I/II), and even beyond 1700 nm by manipulating the size, structure, and composition. The current research efforts focus on the structure-PL correlation and the development of strategies for raising the PL quantum yields, which is nontrivial when moving from the visible to the near-infrared wavelengths, especially in the NIR-II regions. This review summarizes the recent progress in the field, including i) the types of PL observed in gold NCs such as fluorescence, phosphorescence, and thermally activated delayed fluorescence, as well as dual emission; ii) some effective strategies that are devised to improve the PL quantum yield (QY) of gold NCs, such as heterometal doping, surface rigidification, and core phonon engineering, with double-digit QYs for the NIR PL on the horizons; and iii) the applications of luminescent gold NCs in bioimaging, photosensitization, and optoelectronics. Finally, the remaining challenges and opportunities for future research are highlighted.
Nanoparticles (NPs) may behave like atoms or molecules in the self-assembly into artificial solids with stimuli-responsive properties. However, the functionality engineering of nanoparticle-assembled solids is still far behind the aesthetic approaches for molecules, with a major problem arising from the lack of atomic-precision in the NPs, which leads to incoherence in superlattices. Here we exploit coherent superlattices (or supercrystals) that are assembled from atomically precise Au103S2(SR)41 NPs (core dia. = 1.6 nm, SR = thiolate) for controlling the charge transport properties with atomic-level structural insights. The resolved interparticle ligand packing in Au103S2(SR)41-assembled solids reveals the mechanism behind the thermally-induced sharp transition in charge transport through the macroscopic crystal. Specifically, the response to temperature induces the conformational change to the R groups of surface ligands, as revealed by variable temperature X-ray crystallography with atomic resolution. Overall, this approach leads to an atomic-level correlation between the interparticle structure and a bi-stability functionality of self-assembled supercrystals, and the strategy may enable control over such materials with other novel functionalities.
One of the important factors that determine the photoluminescence (PL) properties of gold nanoclusters pertain to the surface. In this study, four Au52(SR)32 nanoclusters that feature a series of aromatic thiolate ligands (-SR) with different bulkiness at the para-position are synthesized and investigated. The near-infrared (NIR) photoluminescence (peaks at 900-940 nm) quantum yield (QY) is largely enhanced with a decrease in the ligand's para-bulkiness. Specifically, the Au52(SR)32 capped with the least bulky p-methylbenzenethiolate (p-MBT) exhibits the highest PLQY (18.3% at room temperature in non-degassed dichloromethane), while Au52 with the bulkiest tert-butylbenzenethiolate (TBBT) only gives 3.8%. The large enhancement of QY with fewer methyl groups on the ligands implies a nonradiative decay via the multiphonon process mediated by C-H bonds. Furthermore, single-crystal X-ray diffraction (SCXRD) comparison of Au52(p-MBT)32 and Au52(TBBT)32 reveals that fewer methyl groups at the para-position lead to a stronger interligand π···π stacking on the Au52 core, thus restricting ligand vibrations and rotations. The emission nature is identified to be phosphorescence and thermally activated delayed fluorescence (TADF) based on the PL lifetime, 3O2 quenching, and temperature-dependent PL and absorption studies. The 1O2 generation efficiencies for the four Au52(SR)32 NCs follow the same trend as the observed PL performance. Overall, the highly NIR-luminescent Au52(p-MBT)32 nanocluster and the revealed mechanisms are expected to find future applications.
More than a decade of research on the photoluminescence (PL) of classic Au25(SR)18 and its doped nanoclusters (NCs) still leaves many fundamental questions unanswered due to the complex electron dynamics. Here, we revisit the homogold Au25 (ligands omitted hereafter) and doped NCs, as well as the Ag25 and doped ones, for a comparative study to disentangle the influencing factors and elucidate the PL mechanism. We find that the strong electron-vibration coupling in Au25 leads to weak PL in the near-infrared region (â¼1000 nm, quantum yield QY = 1% in solution at room temperature). Heteroatom doping of Au25 with a single Cd or Hg atom strengthens the coupling of the exciton with staple vibrations but reduces the coupling with the core breathing and quadrupolar modes. The QYs of the three MAu24 NCs (M = Hg, Au, and Cd) follow a linear relation with their PL lifetimes, suggesting a mechanism of suppressed nonradiative decay in PL enhancement. In contrast, the weaker electron-vibration coupling in Ag25 leads to higher PL (QY = 3.5%), and single Au atom doping further leads to a 5× enhancement of the radiative rate and a suppression of nonradiative decay rate (i.e., twice the PL lifetime of Ag25) in AuAg24 (hence, QY 35%), but doping more Au atoms results in gold distribution to staple motifs and thus triggering of strong electron-vibration coupling as in the MAu24 NCs, hence, counteracting the radiative enhancement effect and giving rise to only 5% QY for AuxAg25-x (x = 3-10). The obtained insights will provide guidance for the design of metal NCs with high PL for lighting, sensing, and optoelectronic applications.
In this work, we report a synergism of Co/Na in Co@Na-BiVO4 microstructures to boost the photocatalytic performance of bismuth vanadate (BiVO4) catalysts. A co-precipitation method has been employed to synthesize blossom-like BiVO4 microstructures with incorporation of Co and Na metals, followed by calcination at 350 °C. The structure and morphology of the as-prepared photocatalysts are characterized by XRD, Raman, FTIR, SEM, EDX, AFM, UV-vis/DRS and PL techniques. Dye degradation activities are evaluated by UV-vis spectroscopy, in which methylene blue, Congo red and rhodamine B dyes are chosen for comparative study. The activities of bare BiVO4, Co-BiVO4, Na-BiVO4, and Co@Na-BiVO4 are compared. To evaluate the ideal conditions, various factors that affect degradation efficiencies have been investigated. The results of this study show that the Co@Na-BiVO4 photocatalysts exhibit higher activity than bare BiVO4, Co-BiVO4 or Na-BiVO4. The higher efficiencies were attributed to the synergistic role of Co and Na contents. This synergism assists in better charge separation and more electron transportation to the active sites during the photoreaction.
When plasmonic metal nanoparticles become smaller and smaller, a new class of nanomaterials-metal nanoclusters of atomic precision-comes to light and has become an attractive research topic in recent years. These ultrasmall nanoparticles (or nanoclusters) are unique in that they are molecularly uniform and pure, often possess a quantized electronic structure, and can grow into single crystals as do protein molecules. Exciting achievements have been made by correlating their properties with the precise structures at the atomic level, which has provided a profound understanding of some mysteries that could not be elucidated in the studies on conventional nanoparticles, such as the critical size at which plasmons are emergent. While most of the reported nanoclusters are spherical or quasi-spherical owing to the reduced surface energies (and hence stability), some anisotropic nanoclusters of high stability have also been obtained. Compared to the anisotropic plasmonic nanoparticles, the nanocluster counterparts such as rod-shaped nanoclusters can provide insights into the growth mechanisms of plasmonic nanoparticles at the early stage (i.e., nucleation), reveal the evolution of properties (e.g., optical), and offer new opportunities in catalysis, assembly, and other themes. In this Review, we highlight the anisotropic nanoclusters of atomic precision obtained so far, primarily gold, silver, and bimetallic ones. We focus on several aspects, including how such nanoclusters can be achieved by kinetic control, and how the anisotropy gives rise to new properties over the isotropic ones. The anisotropic nanoclusters are categorized into three types, (i) dimeric, (ii) rod-shaped, and (iii) oblate-shaped nanoclusters. For future research, we expect that anisotropic nanoclusters will provide exciting opportunities for tailoring the physicochemical properties and thus lead to new developments in applications.
Chirality has risen as an attractive topic in materials research in recent years, but the attainment of enantiopure materials remains a major challenge. Herein, we obtained homochiral nanoclusters by a recrystallization strategy, without any chiral factors (i.e., chiral ligands, counterions, etc.). Through the rapid flipping of configuration of silver nanoclusters in solution, the initial racemic Ag40 (triclinic) nanoclusters are converted to homochiral (orthorhombic) as revealed by X-ray crystallography. In the seeded crystallization, one homochiral Ag40 crystal is used as a seed to direct the growth of crystals with specific chirality. Furthermore, enantiopure Ag40 nanoclusters can be used as amplifiers for the detection of chiral carboxylic drugs. This work not only provides chiral conversion and amplification strategies to obtain homochiral nanoclusters but also explains the chirality origin of nanoclusters at the molecular level.
The emergence of ligand-protected, atomically precise gold nanoclusters (NCs) in recent years has attracted broad interest in catalysis due to their well-defined atomic structures and intriguing properties. Especially, the precise formulas of NCs provide an opportunity to study the size effects at the atomic level without complications by the polydispersity in conventional nanoparticles that obscures the relationship between the size/structure and properties. Herein, we summarize the catalytic size effects of atomically precise, thioate-protected gold NCs in the range of tens to hundreds of metal atoms. The catalytic reactions include electrochemical catalysis, photocatalysis, and thermocatalysis. With the precise sizes and structures, the fundamentals underlying the size effects are analyzed, such as the surface area, electronic properties, and active sites. In the catalytic reactions, one or more factors may exert catalytic effects simultaneously, hence leading to different catalytic-activity trends with the size change of NCs. The summary of literature work disentangles the underlying fundamental mechanisms and provides insights into the size effects. Future studies will lead to further understanding of the size effects and shed light on the catalytic active sites and ultimately promote catalyst design at the atomic level.
Photoluminescence of ultrasmall, atomically precise gold nanoclusters constitutes an area of significant interest in recent years for both fundamental research and biological applications. However, the exploration of near-infrared photoluminescence of gold nanoclusters is still in its infancy due to the limitations of synthetic methods and characterization techniques. Herein, the photoluminescence properties of an Au38(PET)26 (PET = 2-phenylethanethiolate) nanocluster are investigated in detail. The Au38(PET)26 exhibits an emission peak at 865 nm, which is revealed to be a mix of fluorescence, thermally activated delayed fluorescence, and phosphorescence via the combined analyses of time-resolved and temperature-dependent photoluminescence measurements. The quantum yield of Au38(PET)26 is determined to be 1.8% at room temperature under ambient conditions, which increases to above 90% by suppressing the non-radiative relaxation pathway at a cryogenic temperature (80 K). Overall, the results of this work discover the coexistence of three radiative processes in thiolate-protected Au nanoclusters and will pave the way for understanding the intriguing photoluminescence properties of gold nanoclusters in future studies.
The development of renewable energy technologies is critical for reducing global carbon emissions. Water splitting offers a promising renewable energy mechanism by converting water into H2 and O2 gas, which can directly power fuel cells or be utilized as chemical feedstocks. To increase the efficiency of water splitting, catalysts must be developed for the water reduction and water oxidation half-reactions. To promote rational catalyst design, atomically precise metal clusters (APMCs) with earth-abundant metals provide a framework for developing both structure-activity relationships and cost-effective catalysts. Previous reports on the water oxidation activity of nickel-thiolate clusters [Nin(SR)2n] have not developed a systematic description of a possible size-activity relationship. Utilizing recent advancements in preparative chromatography for isolating APMCs, we have synthesized a series of Nin(SR)2n (n = 4, 5, or 6) clusters as electrocatalysts for the oxygen evolution reaction. We discovered a clear size-activity and size-stability trend, with intrinsic activity and stability increasing with cluster size. Using density functional theory, we found that intrinsic activity is inversely correlated to intermediate binding energy, and by extension the oxidation potential of each cluster. Our work demonstrates the ability of APMCs to uncover previously unknown structure-activity relationships that can guide future catalyst design.
This work investigates the critical factors impacting electrochemical CO2 reduction reaction (CO2 RR) using atomically precise Au nanoclusters (NCs) as electrocatalysts. First, the influence of size on CO2 RR is studied by precisely controlling NC size in the 1-2.5â nm regime. We find that the electrocatalytic CO partial current density increases for smaller NCs, but the CO Faradaic efficiency (FE) is not directly associated with the NC size. This indicates that the surface-to-volume ratio, i.e. the population of active sites, is the dominant factor for determining the catalytic activity, but the selectivity is not directly impacted by size. Second, we compare the CO2 RR performance of Au38 isomers (Au38 Q and Au38 T) to reveal that structural rearrangement of identical size NCs can lead to significant changes in both CO2 RR activity and selectivity. Au38 Q shows higher activity and selectivity towards CO than Au38 T, and density functional theory (DFT) calculations reveal that the average formation energy of the key *COOH intermediate on the proposed active sites is significantly lower on Au38 Q than Au38 T. These results demonstrate how the structural isomerism can impact stabilization of reaction intermediates as well as the overall CO2 RR performance of identical size Au NCs. Overall, this work provides important structure-property relationships for tailoring the NCs for CO2 RR.
Understanding the electron-phonon interaction in Au nanoclusters (NCs) is essential for enhancing and tuning their photoluminescence (PL) properties. Among all the methods, ligand engineering is the most straightforward and facile one to design Au NCs with the desired PL properties. However, a systematic understanding of the ligand effects toward electron-phonon interactions in Au NCs is still missing. Herein, we synthesized four Au25(SR)18- NCs protected by different -SR ligands and carefully examined their temperature-dependent band-gap renormalization behavior. Data analysis by a Bose-Einstein two-oscillator model revealed a suppression of high-frequency optical phonons in aromatic-ligand-protected Au25 NCs. Meanwhile, a low-frequency breathing mode and a quadrupolar mode are attributed as the main contributors to the phonon-assisted nonradiative relaxation pathway in aromatic-ligand-protected Au25 NCs, which is in contrast with non-aromatic-ligand-protected Au25 NCs, in which tangential and radial modes play the key roles. The PL measurements of the four Au25 NCs showed that the suppression of optical phonons led to higher quantum yields in aromatic-ligand-protected Au25 NCs. Cryogenic PL measurements provide insights into the nonradiative energy relaxation, which should be further investigated for a full understanding of the PL mechanism in Au25 NCs.
This work presents the synthesis and intriguing photoluminescence of the Au42(PET)32 (PET = 2-phenylethanethiolate) nanocluster (NC). The Au42(PET)32 NC exhibits dual emission at 875 and 1040 nm, which are revealed to be fluorescence and phosphorescence, respectively. The emission quantum yield (QY) of Au42(PET)32 in dichloromethane is 11.9% at room temperature in air, which is quite rare for thiolate-protected Au NCs. When Au42(PET)32 NCs are embedded in polystyrene films (solid state), the fluorescence was dramatically suppressed while the phosphorescence was significantly enhanced. This divergent behavior is explained by dipolar interaction-induced enhancement of intersystem crossing from singlet to triplet excited state.
Methylene Chloride , Polystyrenes , Temperature , Spectrometry, Fluorescence
Metal nanoclusters are a unique class of synthetic material, as their crystal structures can be resolved using X-ray diffraction, and their chemical formula can be precisely determinated from mass spectroscopy. However, a complete structure characterization by these two techniques is often a challenging task. Here, we utilize small-angle neutron scattering (SANS) to directly quantify the key structure parameters of a series of silver and gold nanoclusters in solution. The results not only correlate well to their crystallographic structures, but also allow the quantification of the counterions layer surrounding charged nanoclusters in solution. Furthermore, when combining with X-ray scattering, it is possible to estimate the molecular weight of both the metal core and the ligand shell of nanoclusters. This work offers an alternative characterization tool for nanoclusters without the requirement of crystallization or gas phase ionization.
Metallic-state gold nanorods are well known to exhibit strong longitudinal plasmon excitations in the near-infrared region (NIR) suitable for photothermal conversion. However, when the size decreases below â¼2 nm, Au nanostructures become nonmetallic, and whether the longitudinal excitation in plasmonic nanorods can be inherited is unknown. Here, we report atomically precise rod-shaped Au42(SCH2Ph)32 with a hexagonal-close-packed Au20 kernel of aspect ratio as high as 6.2, which exhibits an intense absorption at 815 nm with a high molar absorption coefficient of 1.4 × 105 M-1 cm-1. Compared to other rod-shaped nanoclusters, Au42 possesses a much more effective photothermal conversion with a large temperature increase of â¼27 °C within 5 min (λex = 808 nm, 1 W cm-2) at an ultralow concentration of 50 µg mL-1 in toluene. Density functional theory calculations show that the NIR transition is mainly along the long axis of the Au20 kernel in Au42, i.e., a longitudinal excitonic oscillation, akin to the longitudinal plasmon in metallic-state nanorods. Transient absorption spectroscopy reveals that the fast decay in Au42 is similar to that of shorter-aspect-ratio nanorods but is followed by an additional slow decay with a long lifetime of 2400 ns for the Au42 nanorod. This work provides the first case that an intense longitudinal excitation is obtained in molecular-like nanorods, which can be used as photothermal converters and hold potential in biomedical therapy, photoacoustic imaging, and photocatalysis.
Nanostructures , Nanotubes , Gold/chemistry , Nanostructures/chemistry , Nanotubes/chemistry
