Ultrasmall Metal Research Articles

In situ confinement of ultra-small metal nanoparticles in redox-active zirconium MOFs for catalysis.

Herein, we successfully fabricated ultra-small metal nanoparticles into two stable Zr-based metal-organic frameworks via in situ redox reactions between triphenylamine and the corresponding metal ions to afford Pd NPs@1 and Pd NPs@2, which exhibit excellent activity and reusability for Suzuki coupling reactions as heterogeneous catalysts.

Quantitative Three-Dimensional Imaging Analysis of HfO2 Nanoparticles in Single Cells via Deep Learning Aided X-ray Nano-Computed Tomography.

It is crucial for understanding mechanisms of drug action to quantify the three-dimensional (3D) drug distribution within a single cell at nanoscale resolution. Yet it remains a great challenge due to limited lateral resolution, detection sensitivities, and reconstruction problems. The preferable method is using X-ray nano-computed tomography (Nano-CT) to observe and analyze drug distribution within cells, but it is time-consuming, requiring specialized expertise, and often subjective, particularly with ultrasmall metal nanoparticles (NPs). Furthermore, the accuracy of batch data analysis through conventional processing methods remains uncertain. In this study, we used radioenhancer ultrasmall HfO2 nanoparticles as a model to develop a modular and automated deep learning aided Nano-CT method for the localization quantitative analysis of ultrasmall metal NPs uptake in cancer cells. We have established an ultrasmall objects segmentation method for 3D Nano-CT images in single cells, which can highly sensitively analyze minute NPs and even ultrasmall NPs in single cells. We also constructed a localization quantitative analysis method, which may accurately segment the intracellularly bioavailable particles from those of the extracellular space and intracellular components and NPs. The high bioavailability of HfO2 NPs in tumor cells from deeper penetration in tumor tissue and higher tumor intracellular uptake provide mechanistic insight into HfO2 NPs as advanced radioenhancers in the combination of quantitative subcellular image analysis with the therapeutic effects of NPs on 3D tumor spheroids and breast cancer. Our findings unveil the substantial uptake rate and subcellular quantification of HfO2 NPs by the human breast cancer cell line (MCF-7). This revelation explicates the notable efficacy and safety profile of HfO2 NPs in tumor treatment. These findings demonstrate that this 3D imaging technique promoted by the deep learning algorithm has the potential to provide localization quantitative information about the 3D distributions of specific molecules at the nanoscale level. This study provides an approach for exploring the subcellular quantitative analysis of NPs in single cells, offering a valuable quantitative imaging tool for minute amounts or ultrasmall NPs.

Strategic Fabrication of Au4Cu2 NC/ZIF‐8 Composite Via In Situ Integration Technique for Enhanced Energy Storage Applications

AbstractMetal–organic frameworks (MOFs), known for their extensive porosity and versatile crystallinity, play a crucial role in the development of advanced energy storage materials. However, their application is limited by stability and conductivity issues. This study addresses these challenges by integrating ultrasmall metal nanoclusters, specifically Au4Cu2 NC, synthesized using a mixed ligand strategy combining 2, 4‐Dimethyl benzene thiol (2,4‐DMBTH) and 1,2‐bis(diphenylphosphino)ethane (dppe). The bimetallic Au4Cu2 NC, characterized by Single Crystal X‐Ray Diffraction (SCXRD), is applied to zeolitic imidazolate framework‐8 (ZIF‐8) using both in situ and ex situ methods to explore their electrochemical and physicochemical properties in energy storage. The in situ Au4Cu2 NC/ZIF‐8 composite demonstrated a specific capacitance that is almost two times higher than its ex situ counterpart, attributed to homogeneous dispersion and hence enhanced conductivity. This in situ integration of atomically precise bimetallic nanoclusters on MOFs significantly boosts supercapacitor performance, offering a more effective and reliable solution for energy storage. Further, in practical applications, this device demonstrated an energy density of 87.2 Wh kg−1 at a power density of 1474 W kg−1, highlighting its robustness and potential for high‐performance energy storage applications. This approach effectively combats the issue of nanocluster aggregation on substrates, marking a significant progression in supercapacitor technology.

Reversible metal cluster formation on Nitrogen-doped carbon controlling electrocatalyst particle size with subnanometer accuracy

Copper and nitrogen co-doped carbon catalysts exhibit a remarkable behavior during the electrocatalytic CO2 reduction (CO2RR), namely, the formation of metal nanoparticles from Cu single atoms, and their subsequent reversible redispersion. Here we show that the switchable nature of these species holds the key for the on-demand control over the distribution of CO2RR products, a lack of which has thus far hindered the wide-spread practical adoption of CO2RR. By intermitting pulses of a working cathodic potential with pulses of anodic potential, we were able to achieve a controlled fragmentation of the Cu particles and partial regeneration of single atom sites. By tuning the pulse durations, and by tracking the catalyst’s evolution using operando quick X-ray absorption spectroscopy, the speciation of the catalyst can be steered toward single atom sites, ultrasmall metal clusters or large metal nanoparticles, each exhibiting unique CO2RR functionalities.

Confinement and synergy effects of supported-confined bimetal catalysts with superior stability and catalytic activity

Bimetallic nanocrystals have attracted considerable attention because of their complicated systems, which are far superior to those of their individual constituents. A TiO2-confined PtMnP bimetallic catalyst (PtMnP@TiO2) was prepared using an ultrasonic-assisted coincident strategy, which demonstrated exceptional catalytic activity in the universal hydrogen evolution reaction (HER). Owing to the bimetallic synergistic effect and TiO2 confinement, PtMnP@TiOx showed ultrasmall metal nanoparticles (NPs), a higher active Pt0 content, adequate activation at the porous surface, and abundant acid sites. Simulations were performed to visualize the strain properties of Mn and Pt during the bending process and demonstrate the high activity of Pt. The Pt-Mn bimetallic catalysts were enriched with Pt NPs, convoyed by electron transfer from Mn to Pt. Briefly, PtMnP@TiO2 showed robust evolution reaction activities (an overpotential of 220 mV at a current density of 10 mA cm−2 and a Tafel slope of 186 mV dec−1) and the ability to contrast stated catalysts without ultrasonication-plasma. This protocol revealed that the geometrical and electronic effects of Pt and P surrounding the Mn species in PtMnP@TiO2 were crucial for increasing the catalytic activity (99%) and durability (over 20 cycles), which were far superior to those of other reported catalysts.

Solid-State Surface-Anchoring Strategy to Prepare Anti-Sintering Supported Metal Cluster Catalysts.

Due to the unique geometric and electronic structures, supported metal clusters with sizes below 3 nm have appealed to great interest in heterogeneous catalysis. However, these supported ultrasmall metal clusters would endure severe particle coalescences under high reaction temperatures. Herein, based on the technology of ball-milling processing, we propose a solid-state "surface-anchoring" strategy to synthesize thermally stabilized Al2O3-supported Ni nanoclusters. Interestingly, when the theoretical Ni loading weight was 1 wt %, highly dispersed Ni species were found where no Ni nanoparticles would be seen after 500 °C calcination. Until the Ni loading weight increased to 5 wt % and the calcination temperature increased to 750 °C, the Ni nanoparticles became significant but still with a size of only about 6.8 nm. With the small Ni nanoparticles, the final 5-Ni-Al2O3-OAm-750 sample worked well as methane dry reforming catalysts with excellent anticoking performance during a 500 h stability test.

Ultrasmall Metal TPZ Complexes with Deep Tumor Penetration for Enhancing Radiofrequency Ablation Therapy and Inducing Antitumor Immune Responses.

Radiofrequency ablation (RFA) is one of the most common minimally invasive techniques for the treatment of solid tumors, but residual malignant tissues or small satellite lesions after insufficient RFA (iRFA) are difficult to remove, often leading to metastasis and recurrence. Here, Fe-TPZ nanoparticles are designed by metal ion and (TPZ) ligand complexation for synergistic enhancement of RFA residual tumor therapy. Fe-TPZ nanoparticles are cleaved in the acidic microenvironment of the tumor to generate Fe2+ and TPZ. TPZ, an anoxia-dependent drug, is activated in residual tumors and generates free radicals to cause tumor cell death. Elevated Fe2+ undergoes a redox reaction with glutathione (GSH), inducing a strong Fenton effect and promoting the production of the highly toxic hydroxyl radical (•OH). In addition, the ROS/GSH imbalance induced by this treatment promotes immunogenic cell death (ICD), which triggers the release of damage-associated molecular patterns, macrophage polarization, and lymphocyte infiltration, thus triggering a systemic antitumor immune response and noteworthy prevention of tumor metastasis. Overall, this integrated treatment program driven by multiple microenvironment-dependent pathways overcomes the limitations of the RFA monotherapy approach and thus improves tumor prognosis. Furthermore, these findings aim to provide new research ideas for regulating the tumor immune microenvironment.

Strategic framework for harnessing luminescent metal nanocluster assemblies in biosensing applications.

The distinctive physicochemical attributes of ultra-small metal nanoclusters (MNCs) resembling those of molecules make them versatile constituents for self-assembled frameworks. This critical review scrutinizes the influence of assembly on the photoluminescence (PL) properties of MNCs and investigates their utility in biosensing applications. The investigation isinitiated with an assessment of the shift from individual MNCs to assemblies and its repercussions on PL efficacy. Subsequently, two distinct biosensing modalities are explored: assembly-driven detection mechanisms and detection predicated on structural modifications in assembled MNCs. Through meticulous examination, we underscore the potential of self-assembly methodologies in tailoring the PL behavior of MNCs for the detection of diverse biological analytes and diseases.

Fusion Growth and Extraordinary Distortion of Ultrasmall Metal Oxide Nanoparticles.

Ultrasmall metal oxide nanoparticles (<5 nm) potentially have new properties, different from conventional nanoparticles. The precise size control of ultrasmall nanoparticles remains difficult for metal oxide. In this study, the size of CeO2 nanoparticles was precisely controlled (1.3-9.4 nm) using a continuous-flow hydrothermal reactor, and the atomic distortion that occurs in ultrasmall metal oxides was explored for CeO2. The crystalline nanoparticles grow rapidly like droplets via coalescence, although they reach a critical particle size (∼3 to 4 nm), beyond which they grow slowly and change shape through ripening. In the initial growth stage, the ultrasmall nanoparticles exhibit disordered atomic configurations, including stacking faults. In ultrasmall CeO2 nanoparticles (<3 to 4 nm), unusual electron localization occurs on Ce 4f orbitals (Ce3+) as a result of O disordering, regardless of O vacancy concentration. This behavior differs from ordinary electron localization caused by the presence of O vacancies. The ultrasmall metal oxides have extraordinary distortion states, making them promising for use in nanotechnology applications. Furthermore, the proposed synthesis method can be applied to various other metal oxides and allows exploration of their properties.

Selective electrocatalytic oxidation of ammonia to nitrogen by using titanium dioxide nanorod array decorated with ultrasmall Ir nanoparticles and non-noble metal Fe nanoparticles

Electrochemical ammonia oxidation process through active chlorine has been proposed as a potentially effective method for ammonia removal. Currently, most of the anodes require to use high-stable TiO2 loaded with large particles of noble metal Ru or Ir, which have low activity and high cost. Herein, we prepare ultrasmall and uniform metal nanoparticles of Ir on TiO2 to remove ammonia. Moreover, we use non-noble metal Fe to replace noble metals. The ammonia removal efficiency of Fe/TiO2 under 2 VVS Ag / AgCl during 2 h is 100 % and 94 % of ammonia is converted to N2. The Fe/TiO2 anodes not only have higher catalytic activity but also show excellent stability and reusability. Fe/TiO2 anodes still exhibit excellence activity and selectivity after 1 year. As a common metal, Fe will have more application space than iridium in ammonia removal for its low cost and selectively high efficiency.

Ternary Photoanodes with AgAu Nanoclusters and CoNi-LDH for Enhanced Photoelectrochemical Water Oxidation.

Atomically precise metal nanoclusters (NCs) present new opportunities for creating innovative solar-powered photoanodes due to their extraordinary physicochemical properties. Nevertheless, ultrasmall metal NCs tend to aggregate and lack active sites under light irradiation, which severely limits their widespread application. We have developed a strategy to design efficient ternary photoanodes by successively modifying AgAu NCs and CoNi-LDH on BiVO4 substrates using versatile impregnation and electrodeposition. The electronic properties of AgAu NCs facilitate the rapid transfer of photogenerated carriers on BiVO4 and CoNi-LDH. Additionally, ultrathin CoNi-LDH acts as a hole-collecting layer, which quickly extracts holes to the electrode/electrolyte interface. The synergistic effect and the matched energy levels between the ternary heterostructures promote the OER process, which significantly improved the photoelectrochemical (PEC) water oxidation performance. This study presents a new idea for further exploration of metal nanocluster-based PEC systems.

Accelerating water dissociation at hierarchical nanostructured electrocatalyst for efficient hydrogen evolution

The sluggish kinetics of the water electrolysis reaction is a key issue for hydrogen production, so the rational design of a high-efficiency hydrogen evolution reaction (HER) electrocatalyst with various structures has attracted extensive attention. Herein, a coaxial hierarchical three-dimensional (3D) nanostructure, Pt@Mo–S–Ni-CNTs, was prepared. In this nanostructure, carbon nanotubes (CNTs) as the core, Mo–S–Ni ultrathin nanosheets as shells, and ultrasmall metal nanoparticles (NPs) were grown uniformly on the surface of Mo–S–Ni nanosheets (NSs). At a current density of 10 mA m−2, the catalyst under investigation has remarkable hydrogen evolution reaction (HER) activity under acidic conditions. The overpotential (η10) is measured to be 61.2 mV, while the Tafel slope is determined to be 40.2 mV dec−1. Meanwhile, in an alkaline medium, η10 is 80.5 mV and the Tafel slope is 52.3 mV dec−1. It also shows great mass activities of 1.32 A mg−1 and 1.86 A mg−1, which are higher than those of commercial Pt/C HER catalysts. Impressively, the excellent HER activity and durability of Pt@Mo–S–Ni-CNTs are mainly attributed to the close binding effects among Pt, MoS2, and NiS. Theoretical simulations show that the MoS2/NiS interfaces facilitate H2O dissociation and that Platinum (Pt) enhances the absorption of hydrogen atoms (H) and increases the charge transfer kinetics of the Mo–S–Ni, thus significantly improving the HER activity. This work highlights the importance of engineering interface nanosheets based on transition-metal dichalcogenides for enhanced HER performance.

Bottom-Up Construction of Metal-Organic Framework Loricae on Metal Nanoclusters with Consecutive Single Nonmetal Atom Tuning for Tailored Catalysis.

The introduction of single or multiple heterometal atoms into metal nanoparticles is a well-known strategy for altering their structures (compositions) and properties. However, surface single nonmetal atom doping is challenging and rarely reported. For the first time, we have developed synthetic methods, realizing "surgery"-like, successive surface single nonmetal atom doping, replacement, and addition for ultrasmall metal nanoparticles (metal nanoclusters, NCs), and successfully synthesized and characterized three novel bcc metal NCs Au38I(S-Adm)19, Au38S(S-Adm)20, and Au38IS(S-Adm)19 (S-Adm: 1-adamantanethiolate). The influences of single nonmetal atom replacement and addition on the NC structure and optical properties (including absorption and photoluminescence) were carefully investigated, providing insights into the structure (composition)-property correlation. Furthermore, a bottom-up method was employed to construct a metal-organic framework (MOF) on the NC surface, which did not essentially alter the metal NC structure but led to the partial release of surface ligands and stimulated metal NC activity for catalyzing p-nitrophenol reduction. Furthermore, surface MOF construction enhanced NC stability and water solubility, providing another dimension for tunning NC catalytic activity by modifying MOF functional groups.

Facile Synthesis of a Broad Range of Colloidal Nanocrystals by Membrane-Mediated pH Gradient under Ambient Conditions

We report a simple synthesis process for a wide variety of ultrasmall nanocrystals. Simply immersing a dialysis bag containing an aqueous solution of a metal salt mixed with citric acid in a NaOH solution reservoir for 10 min, nanocrystals measuring only a few nanometers in size are formed inside the dialysis bag. We demonstrated the synthesis of ultrasmall nanocrystals of Co, Ni, Cu, Ag, Au, Pd, Cu2O, FeO, and CeO2, and found that the gradual change in pH caused by the diffusion of OH− ions through the dialysis membrane played an essential role in the formation of these nanocrystals. This method can be readily adapted for almost all transition metal elements, providing researchers in the fields of catalysis and nanomedicine an easy access to a wide range of ultrasmall metal and oxide nanocrystals.

Ultrasmall metal alloy nanozymes mimicking neutrophil enzymatic cascades for tumor catalytic therapy

Developing strategies that emulate the killing mechanism of neutrophils, which involves the enzymatic cascade of superoxide dismutase (SOD) and myeloperoxidase (MPO), shows potential as a viable approach for cancer therapy. Nonetheless, utilizing natural enzymes as therapeutics is hindered by various challenges. While nanozymes have emerged for cancer treatment, developing SOD-MPO cascade in one nanozyme remains a challenge. Here, we develop nanozymes possessing both SOD- and MPO-like activities through alloying Au and Pd, which exhibits the highest cascade activity when the ratio of Au and Pd is 1:3, attributing to the high d-band center and adsorption energy for superoxide anions, as determined through theoretical calculations. The Au1Pd3 alloy nanozymes exhibit excellent tumor therapeutic performance and safety in female tumor-bearing mice, with safety attributed to their tumor-specific killing ability and renal clearance ability caused by ultrasmall size. Together, this work develops ultrasmall AuPd alloy nanozymes that mimic neutrophil enzymatic cascades for catalytic treatment of tumors.

Plasmon-enhanced multi-photon excited photoluminescence of Au, Ag, and Pt nanoclusters

In this work, we have studied the multi-photon excited photoluminescence from metal nanoclusters (NCs) of Au, Ag and Pt embedded in Al2O3 matrix by ion implantation. The thermal annealing process allows to obtain a system composed of larger plasmonic metal nanoparticles (NPs) surrounded by photoluminescent ultra-small metal NCs. By exciting at 1064 nm, visible emission, ranging from 450 to 800 nm, was detected. The second and fourth-order nature of the multiphoton process was verified in a power-dependent study measured for each sample below the damage threshold. Experiments show that Au and Ag NCs exhibit a four-fold enhanced multiphoton excited photoluminescence with respect to that observed for Pt NCs, which can be explained as a result of a plasmon-mediated near-field process that is of less intensity for Pt NPs. These findings provide new opportunities to combine plasmonic nanoparticles and photoluminescent nanoclusters inside a robust inorganic matrix to improve their optical properties. Plasmon-enhanced multiphoton excited photoluminescence from metal nanoclusters may find potential application as ultrasmall fluorophores in multiphoton sensing, and in the development of solar cells with highly efficient energy conversion modules.

Small-size and well-dispersed Fe nanoparticles embedded in carbon rods for efficient oxygen reduction reaction.

The preparation of ultra-small and well-dispersed metal nanoparticles (NPs) is of great importance for promoting oxygen reduction. Here, a metal (Fe and Zn) NP (7 nm) based catalyst derived from a Zn-based metal-organic framework was obtained by a vapor adsorption strategy, demonstrating a high half-wave potential (0.868 V) and power density (196 mW cm-2).

Possibilities and limitations of solution-state NMR spectroscopy to analyze the ligand shell of ultrasmall metal nanoparticles

Unlike larger plasmonic nanoparticles, ultrasmall nanoparticles with a diameter of 1–2 nm can be well analyzed by NMR spectroscopy. This gives deep insight into the nature of the organic ligand shell.

The size-dependent valence and conduction band-edge energies of Cu quantum dots.

Ultra-small metal particles having band gaps are regarded as a new class of functional materials. We investigated the size dependencies of the band-edge energies on Cu quantum-dots in the size range of 0.7-2.1 nm. The extremely high conduction band-edge energies owing to the strong quantum-size effects were observed for sizes below 1 nm.

Anti-galvanic reaction induced interfacial engineering to reconstruct ternary colloid satellite platform for exceptionally high-performance redox-responsive sensor

The anti-galvanic reaction (AGR), which is a classic galvanic reaction (GR) with an opposite effect, is a unique phenomenon associated with the quantum size effect. This reaction involves the interaction between metal ions and nanoclusters, offering opportunities to create well-defined nanomaterials and diverse reductive behavior. In hence, in our work, we utilize the AGR to generate gold (Au), silver (Ag), and copper (Cu) satellite nanoclusters which have superior electromagnetic properties for Surface-enhanced Raman spectroscopy (SERS) sensor. As the AGR process, weak oxidant Cu2+ is selected to etched matrix Au@Ag NPs, reduced to Cu(0) or Cu(1) and generated the ultrasmall metal nanoparticles (Ag). To facilitate the AGR, we introduce the nucleophilic thiol 4-mercaptopyridine (4-Mpy) to bridge the metal ions or ultrasmall metal nanoparticles to reconstruct the satellite nanoclusters. These experimental displays that the AGR based biosensors has highly sensitivity for reductive molecule glucose. The liner ranges from 1 mmol/L to 1 nmol/L and alongs with a correlation coefficient and detection limit (LOD) of 0.999 and 0.14 nmol/L. Moreover, the AGR based biosensors exhibits remarkable stability and high repeatability with RSD 1.3 %. The food samples are tested to further investigate the accuracy and reliability of the method, which provides a novel and effective SERS method for the reduction molecules detection.