Search Results (227)

Molybdenum blue dispersions were synthesized via an ion-exchange approach using hydroquinone and glucose as reducing agents to clarify the influence of reductant chemistry on redox evolution and colloidal stability. Electrolyte-free conditions enabled controlled self-assembly of reduced polyoxomolybdate clusters. UV–Vis spectroscopy revealed characteristic absorption bands at ~750 and ~1100 nm associated with intervalence charge transfer in mixed-valence Mo⁵⁺/Mo⁶⁺ clusters, with hydroquinone stabilizing more deeply reduced clusters, while glucose-derived systems demonstrated a higher degree of reduction with a higher ratio of reducing agent to metal. Time dependence of oxidation–reduction potential and optical density measurements demonstrated prolonged redox equilibration and gradual self-organization over several weeks. Dynamic light scattering confirmed the formation of nanoclusters with comparable hydrodynamic diameters of approximately 3.5 nm for both reducing agents. Raman and FT-IR spectroscopy indicated structurally similar polyoxomolybdate frameworks. In contrast, electrokinetic measurements revealed pronounced differences in surface chemistry and stability: hydroquinone-derived dispersions exhibited robust, pH-independent electrostatic stabilization, whereas glucose-derived systems showed weaker, pH-dependent stabilization and rapid electrolyte-induced aggregation. These results demonstrate that the nature of the reducing agent has an impact on the synthesis and colloidal behavior of molybdenum blue dispersions synthesized by the ion-exchange route. Full article

Recent studies have demonstrated the relative stability of undercoordinated hexanuclear cobalt sulfide nanoclusters (NCs) with different charge states. Considering that these small metal NCs have atomically precise structures and high reactivity due to the open shell of the transition metals, and provide selectivity toward ligand loss, they are a vital model for catalysis. In this paper, the electronic structures of these NCs are investigated. These NCs are then used as the reference state to analyze the catalytic properties with respect to hydrogen evolution reaction (HER) and CO₂ reduction (CO₂R). Further, to understand the effect of heteroatom incorporation, the geometry and reactivity of ten different metal dopants are analyzed. This work shows that the type of metal incorporation greatly affects the electronic structure and formation energies for ligand binding and catalysis. Particularly, the d-orbital occupancy in the cobalt atoms remains largely unchanged, while the heteroatom greatly influences the reactivity of the undercoordinated NCs. Most notably, this work highlights that transition metals in [Co₅MS₈(PEt₃)₅]¹⁺ NCs would competitively prefer electrochemical adsorption of H over COOH, while the main group metals prefer COOH adsorption. Full article

Hydrogen peroxide (H₂O₂) plays a vital role as an eco-friendly oxidizer, extensively used in environmental cleanup, energy transformation, and organic production. Nonetheless, the conventional method of creating anthraquinones is intricate, resulting in significant energy and ecological costs, which calls for the development of more eco-friendly and efficient substitute technologies. The article methodically examines the reaction processes and methods for improving efficiency in photocatalytic H₂O₂ generation in the past few years. This review summarizes the design principles and key structural features of various novel catalytic materials, focusing on light absorption, charge separation and migration, surface redox reactions, and enhanced mass transfer. Approaches such as expanding the range of bandgap absorption, building conjugated structures, and incorporating metal nanoclusters can significantly enhance the efficiency of light absorption. In the charge separation process, constructing built-in electric fields at the interfaces of heterojunctions, homojunctions, and Schottky junctions is crucial for improving reaction efficiency. Additionally, defect engineering may encourage targeted carrier movement and minimize recombination. The review highlights the latest advancements in enhancing selectivity and reducing H₂O₂ breakdown in surface redox reactions, achieved by regulating active sites, introducing new functional groups, and developing dual-channel reaction pathways. Furthermore, constructing three-phase interfaces, regulating asymmetric wettability, and designing cyclic/flow reactors provide innovative engineering solutions to address the challenges of insufficient oxygen supply and large-scale continuous production. Ultimately, the potential for producing H₂O₂ in photocatalytic systems is detailed. Full article

Low-temperature methanation technology offers a promising pathway for carbon recycling and sustainable energy storage by enabling near-equilibrium CO₂ conversion under atmospheric pressure. However, efficiently activating CO₂ at low temperatures remains a significant challenge due to the kinetic limitations of hydrogenation intermediates. We construct a composite oxide–metal interface structure by anchoring highly dispersed CeCrO_x nanoclusters onto metallic nickel via an ion-exchange method. This catalyst exhibits superior activity compared to conventional Ni/oxide catalysts with identical composition. Under atmospheric pressure at 220 °C, it achieves nearly 80% CO₂ conversion with over 99% methane selectivity and maintains excellent catalytic performance and structural stability during a 240-h continuous test. Systematic characterizations, including high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, CO₂ temperature-programmed desorption, and in situ DRIFTS reflectance infrared Fourier-transform spectroscopy, reveal that the synergistic modification by CeO₂ and Cr₂O₃ not only optimizes the electronic structure of Ni to promote CO₂ adsorption and activation, but also enhances H₂ dissociation and intermediate conversion by regulating oxygen vacancy concentration and alkaline site distribution. Mechanistic studies indicate that the reaction follows a synergistic mechanism dominated by the formate pathway and assisted by the CO pathway. Moreover, the interfacial structure effectively stabilizes active sites and inhibits carbon deposition from CH₄ decomposition. This study provides a universal and effective strategy for designing Ni-based CO₂ conversion catalysts suited for mild reaction conditions and characterized by high energy efficiency. Full article

The adsorption and activation of CO₂ on Cu_xSc_y nanoclusters with x + y equal to 4 were analyzed using DFT and PDOS and TDOS signatures. The geometries of Cu₃Sc, Cu₂Sc₂, and CuSc₃ were optimized in the gas phase, and the minima were verified by frequencies in ORCA using M06-2X/def2-TZVP. Multiplicities 1, 3, and 5, temperatures between 298 and 400 K, and four CO₂ coordination modes R1 to R4 were evaluated. Naked and complex cluster comparison panels were constructed, and two energy windows, −18 to −10 eV and −8 to 6 eV around the Fermi level, were analyzed, complemented by frontier orbitals and charge maps. Thermodynamics indicated that mode and multiplicity control the adsorption energy, with ANOVA p-values of 0.002 and 0.008, while temperature was not significant (p = 0.682). In Cu₃Sc–C₂v(1), the R1 singlet at 298 K showed E_ads −33.43 kcal·mol⁻¹ with spin contamination, while alternative modes in the singlet were unfavorable. In PDOS and TDOS, the bare cluster exhibits a Cu d band at −11 to −10 eV and a valley around −5 eV. The exergonic complexes show CO₂ signals near the Fermi level, superimposed on Cu and Sc states, with state filling and broadening. Transferable indicators based on CO₂ intensity in the −8 to 6 eV range and metal–adsorbate overlap are proposed as predictors of exergonic adsorption. Full article

Fluorescent metal nanoclusters show great promise in heavy metal ion sensing. Herein, a bimetallic nanocluster (GSH-Au/Ag NCs) with orange fluorescence was synthesized through a facile one-pot method. The synthesized GSH-Au/Ag NCs displayed optimal excitation and emission peaks at 275 and 610 nm, respectively. The incorporation of silver can enhance the fluorescence of metal nanoclusters. The fluorescence of as-synthesized GSH-Au/Ag NCs can be significantly quenched by Hg²⁺ and Cu²⁺, and a “on–off” fluorescent probe was designed. The detection conditions, including pH and the concentration of the probe, were optimized. The respective detection limits for Hg²⁺ and Cu²⁺ ions under optimal detection conditions are estimated to be 40 nM and 33 nM, over the linear range of 100–1200 nM. Furthermore, a ratiometric fluorescent probe was prepared by mixing quinine sulfate and as-synthesized GSH-Au/Ag NCs. Hg²⁺ and Cu²⁺ can effectively quench the red fluorescence of GSH-Au/Ag NCs, whereas the blue fluorescence of quinine sulfate remains invariant. This leads to measurable changes in the RGB values of the resulting fluorescence images. The ratio (R/B) exhibits a linear relationship with the concentration of Hg²⁺ and Cu²⁺, enabling the determination of its concentration by analyzing RGB values in fluorescence images. This visual detection method significantly reduces both assay time and cost, making it suitable for on-site detection of heavy metal ions in water samples. Full article

In this work, we demonstrate a functional and previously insufficiently explored route for converting cyclic olefin copolymer (COC) TOPAS^® thin films into antibacterial hybrid materials through a combination of solvent casting, plasma activation, noble-metal sputtering, and subsequent thermal or laser treatment. While COC is already well-known as a transparent, chemically resistant material for pharmaceutical and optical applications, its coupling with post-treated noble-metal nanostructures for antibacterial functionality has not been systematically described. The main contribution of this study lies in showing that COC can serve not only as a passive packaging substrate, but also as an active platform for the formation of biologically relevant surface nanostructures. Compared with previously reported metal/polymer systems, the present work provides clear evidence that noble-metal layers on COC undergo substantial structural evolution after thermal and excimer-laser treatment, resulting in regular nanoclustered morphologies. A particularly important finding is the detection of Au particle implantation below the COC surface during sputtering, as revealed by Rutherford backscattering spectrometry, which distinguishes this system from conventional surface-only metal coatings. Furthermore, we show that laser and thermal processing do not merely reshape the deposited layer, but significantly influence the final biological response of the material. Ag-based structures showed strong bactericidal behavior against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus. The prepared samples were comprehensively characterized by AFM, DSC, RBS, SEM, and TGA, and their roughness and wettability were also evaluated, enabling direct correlation between physicochemical changes and antibacterial performance. These results introduce a new strategy for upgrading conventionally used pharmaceutical COC materials into multifunctional surfaces with added antibacterial value. Full article

Biocompatible nanocomposite hydrogels are emerging as versatile platforms in nanomedicine, particularly when natural proteins are used as both structural and chemical components. In this work, we report a green, simple, and rapid in situ synthesis of ultrasmall silver nanoparticles (uAgNPs) within a bovine serum albumin (BSA) hydrogel, in which albumin simultaneously acts as the reducing agent and three-dimensional scaffold. The confined reaction environment generated uniformly dispersed Ag nanostructures with diameters in the 4–40 nm range, as confirmed by DLS and TEM. High-resolution TEM revealed clear Face-Centered Cubic (FCC, 111) lattice fringes, demonstrating the crystalline nature of the embedded uAgNPs. Quantitative image analysis showed narrow size distributions and high circularities, consistent with cluster stabilization through protein–metal interactions. Rheological measurements further indicated that the incorporation of uAgNPs enhanced hydrogel stiffness and delayed yielding, reflecting a reinforcement effect mediated by the nanoparticles acting as additional cross-linking points. Moreover, when very small embedded uAgNPs are formed, the presence of emissive silver nanoclusters was found using fluorescence emission spectroscopy. Overall, our results show that BSA hydrogels provide an effective matrix for directing green uAgNP nucleation, ensuring high stability, controlled growth in less than 2 min, and improved mechanical properties. The resulting protein–nanoparticle composite constitutes a promising soft material for imaging, sensing, and other biomedical applications requiring stable, biocompatible nanoscale architectures. Full article

This study reports the precise synthesis of red-emitting gold–silver bimetallic nanoclusters (Au-AgNCs) via a one-pot hydrothermal method using thiolactic acid as both the ligand and reducing agent. The Au-AgNCs possess an average diameter of 1.85 nm and exhibit strong fluorescence emission at 687 nm. Furthermore, they display notable assembly-induced emission enhancement (AIEE) properties. Upon assembly with bovine serum albumin (BSA), their fluorescence quantum yield significantly increases from 2.50% to 7.78%. Then Au-AgNCs@BSA assembly was employed as a ratiometric fluorescence sensor for the detection of chlortetracycline (CTC). In the presence of CTC, the original red emission of the assembly at 687 nm remained stable, while a new blue emission emerged at 420 nm and intensified progressively with CTC concentration. The ratio of the two emission intensities (I₄₂₀/I₆₈₇) exhibited an excellent linear correlation with CTC concentration over the range of 0.10 to 15 μM, with a limit of detection (LOD) of 20 nM. Notably, the sensor demonstrated exceptional selectivity for CTC, showing negligible response to common interfering substances such as metal ions, anions, amino acids, and crucially, other tetracycline antibiotics (tetracycline, oxytetracycline, and doxycycline). The practical applicability of the sensor was validated through the determination of spiked CTC in real water samples, achieving satisfactory recovery rates. In conclusion, this work accomplishes two key objectives: the development of novel AIEE-active Au-Ag bimetallic nanoclusters and the design of an efficient ratiometric sensing strategy. This approach enables the highly selective and sensitive detection of CTC, offering a promising tool for environmental monitoring. Full article

The electronic stability and global reactivity of Cu_xSc_γ (x + y = 4) bimetallic nanoclusters were investigated within the framework of rational design of functional materials and active catalytic phases. M06-2X/def2-TZVP DFT was used for geometric optimization and electronic characterization, and global descriptors were calculated, including ΔE_gap, chemical toughness, chemical potential, and electrophilicity. The orbital contribution was analyzed using DOS/PDOS with Multiwfn; PCA and ANOVA were applied to quantify descriptor–structure relationships. The results show that adding Sc changes the cluster’s electron density and stiffness in a consistent manner, enabling distinction between more stable and more reactive configurations. In particular, Cu₃Sc is the most electronically stable, exhibiting the highest ΔE_gap, while Cu₂Sc₂ shows a more tunable electronic response, consistent with scenarios requiring greater reactivity. Multivariate analysis shows that ΔE_gap accounts for most of the electronic variability in the dataset, making it the primary descriptor for selection and design. Taken together, these results open a descriptor-guided path to designing active Cu–Sc phases for supported catalysis and to their assembly into tunable metal nanocomposites. Full article

In recent years, metal nanoclusters (NCs) with atomic-scale precision have emerged as novel photosensitizers for light energy conversion in metal cluster-sensitized semiconductor (MCSS) systems. However, conventional NCs often suffer from photodegradation after binding with semiconductors, limiting their long-term catalytic stability. Modifying NCs via single-atom doping provides an effective strategy to tailor their interfacial charge transfer behavior. In this study, PtAg₂₈ NCs were synthesized by doping Pt single atoms into Ag₂₉ NCs and subsequently loaded onto TiO₂ via electrostatic adsorption to construct composite photocatalysts. Systematic investigations revealed that Pt doping significantly enhances light absorption and promotes the formation of a direct Z-scheme heterojunction. The optimized PtAg₂₈/TiO₂ composite exhibits effective suppression of charge recombination. This enhanced charge separation efficiency, driven by pronounced band bending at the interface, leads to a remarkable hydrogen evolution rate of 14,564 μmol g⁻¹ h⁻¹. This work demonstrates the critical role of single-atom doping in regulating the photophysical properties of metal NCs and offers a feasible approach for designing highly efficient and stable metal-cluster-based photocatalytic systems. Full article

In this work, highly water-soluble silk fibroin (SF) is first prepared by recrystallizing degummed silkworm cocoon fibers in concentrated CaCl₂ solution (replacing the conventional Ajisawa’s reagent), and then used as both stabilizing and reducing agents to synthesize copper nanoclusters (Cu@SF NCs) at pH = 11. Due to the existence of unreacted Cu²⁺ ions, the resulting SF-templated Cu NCs form slight aggregates, yielding a purple-colored solution with blue fluorescence. Interestingly, upon adding the pesticide 2,4-dichlorophenoxyacetic acid (2,4-D), the Cu NCs aggregates disassemble and the fluorescence is significantly enhanced, creating a “fluorescence-on” sensor for 2,4-D with a detection limit of 0.65 μM. In contrast, the pollutant p-nitrophenol (p-NP) quenches the fluorescence of Cu NCs via a fluorescence resonance energy transfer mechanism (with a detection limit as low as 1.35 nM), which is attributed to the large overlap between absorption spectrum of p-NP and excitation spectrum of Cu NCs. Other tested analytes (i.e., pyrifenox, carbofuran and melamine) produce negligible fluorescence changes. The distinct sensing mechanisms are elucidated with experimental evidence and density functional theory (DFT) calculations. The evolutions of fluorescence as a function of incubation time and analyte concentration are systematically investigated, demonstrating a versatile platform for sensitive and selective detection of target analytes. These findings provide an effective strategy for optimizing the optical properties of metal nanoclusters and improving their performance in environmental applications. Full article

Herein, we propose a simple and cost-effective method for fabricating moderate-sensitivity surface-enhanced Raman scattering (SERS) substrates using Cu-plasma polymer fluorocarbon (Cu-PPFC) nanocomposite films fabricated through RF sputtering. The use of a composite target composed of carbon nanotube (CNT), Cu, and polytetrafluoroethylene (PTFE) powders (5:60–80:35–15 wt%) offers the advantage of the simple fabrication of moderate-sensitivity SERS substrates with a single cathode compared to co-sputtering. X-ray photoelectron spectroscopy (XPS) revealed that the film surface was partially composed of metallic Cu with Cu-F bonds and Cu–O bonds, confirming the coexistence of the conducting and plasmon-active domains. UV-VIS spectroscopy revealed a distinct absorption peak at approximately 680 nm, indicating the excitation of localized surface plasmon resonances in the Cu nanoclusters embedded in the plasma polymer fluorocarbon (PPFC) matrix. Atomic force microscopy and grazing incidence small-angle X-ray scattering analyses confirmed that the Cu nanoparticles were uniformly distributed with interparticle distances of 20–35 nm. The Cu-PPFC nanocomposite film with the highest Cu content (80 wt%) exhibited a Raman enhancement factor of 2.18 × 10⁴ for rhodamine 6G, demonstrating its potential as a moderate-sensitivity SERS substrate. Finite-difference time-domain (FDTD) simulations confirmed the strong electromagnetic field localization at the Cu-Cu nanogaps separated by the PPFC matrix, corroborating the experimentally observed SERS enhancement. These results suggest that a Cu-PPFC nanocomposite film, easily fabricated using a composite target, provides an efficient and scalable route for fabricating reproducible, inexpensive, and moderate-sensitivity SERS substrates suitable for practical sensing applications. Full article

Ruthenium-based catalysts supported on TiO₂, SnO₂, and WO₃ were synthesized via a microwave-assisted rapid reduction method and evaluated for the hydrogen evolution reaction (HER) in acidic media. The Ru species existed as highly dispersed nanoclusters, as confirmed by XRD and TEM, and the catalytic activity was strongly dependent on the oxide support. Ru/TiO₂ exhibited the best HER performance, achieving an overpotential of 187 mV at 10 mA·cm⁻² and a Tafel slope of 97.56 mV·dec⁻¹. While particle size differences (1.8–3.7 nm) did not account for the activity trend, XPS revealed distinct metal–support interactions that modulated the electronic state of Ru. Ru/TiO₂ showed an intermediate electron depletion that optimizes the Ru-H binding strength, explaining its superior kinetics. Regulation of Ru loading further identified Ru/15TiO₂ as the optimal catalyst, exhibiting low charge transfer resistance and excellent stability over 17 h. This study highlights the critical role of support-induced electronic modulation and loading engineering in designing efficient Ru-based electrocatalysts for acidic HER. Full article

Since Pt cocatalysts play an important role in photocatalytic H₂ evolution, it is necessary to track Pt over Pt/g-C₃N₄ catalysts during the evolution process to understand the associated photocatalytic deactivation behavior. In this study, bulk g-C₃N₄ (CN) and oxidized g-C₃N₄ (OCN) catalysts containing a Pt cocatalyst were prepared to investigate photocatalytic deactivation behavior through tracking changes in the catalytic properties of the Pt cocatalyst and g-C₃N₄ surface during photocatalytic H₂ evolution. While CN catalysts show a lower photocatalytic activity than OCN catalysts, the former exhibit high resistance to catalytic deactivation with a lower deactivation rate than the latter. The high photocatalytic activity of OCN catalysts is caused by the highly dispersed Pt species on chemically oxidized g-C₃N₄ with abundant O-containing functional groups, relating to the excellent separation efficiency of photogenerated electron/hole pairs. During the evolution process, highly dispersed Pt species over fresh OCN are easily and rapidly agglomerated into large Pt nanoclusters due to its exfoliated thin-layered g-C₃N₄ structure, whereas the three-dimensional multi-layered g-C₃N₄ structure of CN catalysts hinders the agglomeration of Pt over the CN catalyst. In addition, during the photocatalytic H₂ evolution, the O-containing functional groups on the OCN catalyst significantly disappear, which causes a weak metal/support interaction and, eventually, fast photocatalytic deactivation due to the agglomeration of Pt. Full article