Small Au Research Articles

Silicon Nanowire Arrays Coated with Ag and Au Dendrites for Surface-Enhanced Raman Scattering

Silicon nanowires (SiNWs) were comprehensively characterized in dependence on conditions of their formation via metal (Ag) -assisted chemical etching (MACE) of monocrystalline Si. The Ag structures remained on/between SiNWs based on both n- and p-Si were found to promote surface enhancement of Raman scattering (SERS) from organic molecules adsorbed on their surface. The Ag structures on/between the SiNWs/p-Si facilitated two times higher SERS-signal from 10-6 M rhodamine 6G than those in the SiNWs/n-Si. The activity of the SERS-substrates based on p-Si was improved by modification with small Au dendrites, which provided rich family of hot spots and prevented degradation of the SERS-activity observed for pure Ag dendrites due to formation of Ag2S during one week of storage in air. The SERS-substrates based on the Au/Ag dendrites on SiNWs/p-Si allowed to achieve nanomolar detection limit of rhodamine 6G and 5,5′-dithiobis (2-nitrobenzoic acid).

Electron-Rich Gold Clusters Stabilized by Poly(vinylpyridines) as Robust and Active Oxidation Catalysts.

In this report, we introduced poly(n-vinylpyridine) (PnVP, n = 2, 4) as an electron-donating stabilizer for small (<2 nm) Au clusters and elucidated how coordinating pyridines affect the physical, optical, chemical, and catalytic properties of Au clusters. Spectroscopic measurements and theoretical calculation suggested the high electron-donating ability of PnVP. PnVP-stabilized Au clusters improved robustness in aerobic oxidation of alcohols compared to poly(N-vinyl-2-pyrrolidone)-stabilized ones, while retaining catalytic activities.

Direct Gas-Phase Oxidation of Propylene to Acetone in the Presence of H2 and O2 over Au/TS-1 Catalyst.

A novel process for the preparation of acetone is reported by gas-phase oxidation of propylene in the presence of H2 and O2 with Au supported TS-1 catalyst (Au/TS-1). By elevating the reaction temperature to 280°C, Au/TS-1 catalyzes 11.6% propylene generating acetone with 70.6% selectivity, and 8.2% acetone in onepass yield. Acetone is originated from propylene oxide isomerization, which is mainly attributed to the surface of the Lewis base and high reaction temperature. Furthermore, small Au nanoparticle size promotes the reaction.

Size Transformation of the Au22(SG)18 Nanocluster and Its Surface-Sensitive Kinetics.

For many applications of well-defined gold nanoclusters, it is desirable to understand their structural evolution behavior under working conditions with molecular precision. Here we report the first systematic investigation of the size transformation products of the Au22(SG)18 nanocluster under representative working conditions and highlight the surface effect on the transformation kinetics. Under thermal and aerobic conditions, the consecutive and pH-dependent transformation from Au22 to both well-defined clusters and small Au(I)SR species was identified by ESI-MS and UV-vis spectroscopy. By introducing a perturbation onto the Au22 surface, significant changes in the activation parameters were determined from the kinetic study of the Au22 transformation. This indicates the sensitivity of the nanocluster transformation pathway to the cluster surface. The systematic study of cluster transformation and the sensitivity of cluster transformation to the surface revealed herein has significant implications for future attempts to design gold nanoparticles with adaptation to the working environment and the regeneration of active nanoparticles.

Seedless Hydrothermal Growth of ZnO Nanorods as a Promising Route for Flexible Tactile Sensors.

Hydrothermal growth of ZnO nanorods has been widely used for the development of tactile sensors, with the aid of ZnO seed layers, favoring the growth of dense and vertically aligned nanorods. However, seed layers represent an additional fabrication step in the sensor design. In this study, a seedless hydrothermal growth of ZnO nanorods was carried out on Au-coated Si and polyimide substrates. The effects of both the Au morphology and the growth temperature on the characteristics of the nanorods were investigated, finding that smaller Au grains produced tilted rods, while larger grains provided vertical rods. Highly dense and high-aspect-ratio nanorods with hexagonal prismatic shape were obtained at 75 °C and 85 °C, while pyramid-like rods were grown when the temperature was set to 95 °C. Finite-element simulations demonstrated that prismatic rods produce higher voltage responses than the pyramid-shaped ones. A tactile sensor, with an active area of 1 cm2, was fabricated on flexible polyimide substrate and embedding the nanorods forest in a polydimethylsiloxane matrix as a separation layer between the bottom and the top Au electrodes. The prototype showed clear responses upon applied loads of 2–4 N and vibrations over frequencies in the range of 20–800 Hz.

Efficient Hot Electron Transfer from Small Au Nanoparticles.

Many important chemical transformations enabled by plasmonic hot carrier photocatalysis have been reported, although their efficiencies are often too low for practical applications. We examine how the efficiency of plasmon-induced hot electron transfer depends on the Au particle size in Au-tipped CdS nanorods. We show that with decreasing Au size, the plasmon width increases due to enhanced surface damping contributions. The excitation of Au nanoparticles leads to an instrument response time-limited ultrafast hot electron transfer process to CdS (≪140 fs). The quantum efficiency of this process increases from ∼1% to ∼18% as the particle size decreases from 5.5 ± 1.1 to 1.6 ± 0.5 nm due to both enhanced hot electron generation and transfer efficiencies in small Au particles. Our finding suggests that decreasing plasmonic particle size is an effective approach for improving plasmon-induced hot carrier transfer efficiency and provides important insight for the rational improvement of plasmonic hot carrier-based devices.

2D/3D graphene on h-BN interlayer-silicon solar cell with ZnO:Al buffer layer and enormous light captivation using Au/Ag NPs

In this paper, systematic design and analysis of thin-film graphene-silicon solar cells with the addition of an anti-reflection coating (ARC), hexagonal boron nitride (h-BN) interlayer and decorated with Au/Ag NPs infused in rear ZnO:Al buffer layer is reported. The 3D NPs are located on the top and rear side of the solar cell. Initially, we simulated a reference 2D graphene-silicon solar cell with highest simulated short circuit current density (Jsc) 30mA/ cm2 and power conversion efficiency (PCE) of 10.65%. Using 2D and 3D full vectorial finite element method (FVFEM) simulations, we significantly improved the Jsc by 6.2mA/ cm2 from 30mA/cm2 to 36.21mA/cm2 and PCE from 10.93% to 12.03%. We utilized a patterned graphene sheet with small nanoholes to increase surface and optical conductivity. Plasmonic NPs embedded in a graphene-silicon solar cell to increase plasmonic resonance effects is investigated. The 3D position of the patterned graphene, rear buffer layer stack, size, shape, and periodicity of NPs were well-controlled and analyzed under certain parametric variation conditions. Ag NPs located inside textured ZnO:Al detached to metal contact and small periodic Au NPs decorated beneath a h-BN interlayer lead to highly efficient light confinement and increase photon current generation. The proposed device exhibits 12.03% PCE, maximum light absorption over 80% and high overall quantum efficiency (QE). Furthermore, this structure offers major light trapping advantages, including significant EM light propagation throughout the solar cell structure.

Boosting the catalysis of gold by O2 activation at Au-SiO2 interface

Supported gold (Au) nanocatalysts have attracted extensive interests in the past decades because of their unique catalytic properties for a number of key chemical reactions, especially in (selective) oxidations. The activation of O2 on Au nanocatalysts is crucial and remains a challenge because only small Au nanoparticles (NPs) can effectively activate O2. This severely limits their practical application because Au NPs inevitably sinter into larger ones during reaction due to their low Taman temperature. Here we construct a Au-SiO2 interface by depositing thin SiO2 layer onto Au/TiO2 and calcination at high temperatures and demonstrate that the interface can be not only highly sintering resistant but also extremely active for O2 activation. This work provides insights into the catalysis of Au nanocatalysts and paves a way for the design and development of highly active supported Au catalysts with excellent thermal stability.

From spherical to bone-shaped gold nanoparticles-Time factor in the formation of Au NPs, their optical and photothermal properties.

Using the same synthesis method, which was stopped at different time intervals, gold nanoparticles (Au NPs) with different shapes, from spherical to bone-shaped, were obtained. The physical properties of the synthesized Au NPs were investigated using transmission electron microscopy (TEM) combined with selected area electron diffraction patterns (SAED) and ultraviolet-visible spectroscopy (UV-vis). The TEM images showed, that stopping the synthesis after one minute lead to the formation of small spherical Au NPs, which evolved to the cubic shape, rods and bone-shaped Au NPs after 15 min, 30 min, 2 h, respectively. SAED patterns showed, that all the obtained Au NPs were crystalline. UV-vis spectra revealed, that the light absorbance depends on the shape of the Au NPs. Moreover, the effects of the time factor in the formation of Au NPs on the effective conversion of electromagnetic energy into thermal energy, was studied. Furthermore, simulated photothermal therapy (PTT) in combination with the obtained NPs, was done for two cancer cell lines SW480 and SW620. The mortality of cells after using the differently shaped Au NPs as photosensitizers is between 18 % and 52 % and increases with the decrease of the synthesis time.

Facile Sonochemical Preparation of Au-ZrO2 Nanocatalyst for the Catalytic Reduction of 4-Nitrophenol

High-intensity ultrasonic waves have great potential for the green synthesis of various nanomaterials under mild conditions and offer an excellent alternative for hazardous chemical methods. Herein a facile approach for the eco-friendly synthesis of Au-ZrO2 nanocatalyst with a high catalytic activity using a facile ultrasonic method is presented. Gold (Au) in the nanosize regime was successfully deposited on the surface of solvothermally synthesized monodispersed ZrO2 nanoparticles (ZrO2 NPs) in a very short period of time (5 min) at room temperature. Spherical shape small size Au nanoparticles that are uniformly dispersed on the surface of ZrO2 nanoparticles were obtained. Notably, in the absence of ZrO2 nanoparticles, HAuCl4 could not be reduced, indicating that nano-sized ZrO2 not only acted as support but also helped to reduce the gold precursor at the surface. The as-prepared Au-ZrO2 nanocatalyst was characterized by various techniques. The Au-ZrO2 nanocatalyst served as a highly efficient reducing catalyst for the reduction of 4-nitrophenol. The reaction time decreased with increasing the amount of catalyst.

The influence of oxygen vacancy and Ce3+ ion positions on the properties of small gold clusters supported on CeO2−x(111)

We studied the influence of oxygen vacancies on small Au clusters supported on CeO2 using dispersion-corrected density functional theory (DFT-D3).

Gold(i)-silver(i)-calix[8]arene complexes, precursors of bimetallic alloyed Au-Ag nanoparticles.

In this paper, we report the first synthesis and characterisations of bimetallic gold(i)–silver(i) calix[8]arene complexes. We show that the radiolytic reduction of these complexes leads to the formation of small bimetallic nanoparticles with an alloyed structure, as evidenced by XPS, HR-TEM and STEM/HAADF-EDX measurements.

Decoration of plasmonic Mg nanoparticles by partial galvanic replacement.

Plasmonic structures have attracted much interest in science and engineering disciplines, exploring a myriad of potential applications owing to their strong light-matter interactions. Recently, the plasmonic concentration of energy in subwavelength volumes has been used to initiate chemical reactions, for instance by combining plasmonic materials with catalytic metals. In this work, we demonstrate that plasmonic nanoparticles of earth-abundant Mg can undergo galvanic replacement in a nonaqueous solvent to produce decorated structures. This method yields bimetallic architectures where partially oxidized 200-300 nm Mg nanoplates and nanorods support many smaller Au, Ag, Pd, or Fe nanoparticles, with potential for a stepwise process introducing multiple decoration compositions on a single Mg particle. We investigated this mechanism by electron-beam imaging and local composition mapping with energy-dispersive X-ray spectroscopy as well as, at the ensemble level, by inductively coupled plasma mass spectrometry. High-resolution scanning transmission electron microscopy further supported the bimetallic nature of the particles and provided details of the interface geometry, which includes a Mg oxide separation layer between Mg and the other metal. Depending on the composition of the metallic decorations, strong plasmonic optical signals characteristic of plasmon resonances were observed in the bulk with ultraviolet-visible spectrometry and at the single particle level with darkfield scattering. These novel bimetallic and multimetallic designs open up an exciting array of applications where one or multiple plasmonic structures could interact in the near-field of earth-abundant Mg and couple with catalytic nanoparticles for applications in sensing and plasmon-assisted catalysis.

Conversion of glycerol to dihydroxyacetone over Au catalysts on various supports

AbstractBACKGROUNDGlycerol, which is a coproduct of biodiesel production, has been identified as a key platform compound for producing various valuable chemicals. The selective catalytic oxidation of glycerol to dihydroxyacetone is very attractive.RESULTSA series of Au catalysts supported on metallic oxides, i.e. ZnO, CuO, Al2O3, Fe2O3 and NiO, were studied for selective catalytic oxidation of glycerol to dihydroxyacetone under base‐free conditions. Among the catalysts, Au/CuO showed the best catalytic activity (glycerol conversion of 89% and dihydroxyacetone selectivity of 82.6% at 80 °C under 10 bar of O2), followed by Au/ZnO ≫ Au/NiO &gt; Au/Al2O3 ≈ Au/CuO‐SD ≈ Au/Fe2O3. The catalytic behaviors of these supported Au catalysts varied depending on the Au particle size, Au oxidation state, Au–support interactions and lattice oxygen reducibility.CONCLUSIONThe main reasons for the high catalytic activity of Au/CuO are as follows. Firstly, the catalyst has small metallic Au particles, which are more active in cleavage of the secondary CH bond in glycerol molecules. Secondly, the interactions between Au and CuO facilitate lattice oxygen reduction, and this increases oxygen mobility, which may promote regeneration of Au–support perimeter active sites by gaseous oxygen. © 2019 Society of Chemical Industry

Electron beam-induced changes in tips of multi-walled carbon nanotubes with/without Au nanoparticles

Tips of multi-walled carbon nanotube of dissimilar shapes with/without gold nanoparticles are irradiated under electron beam. The tips become meta-stable and cause reduction in lengths of tubes under a high intense uniform electron beam by their smaller radius of curvature when the diffusion and evaporation of carbon atoms are activated. Meanwhile, normal-tube-tips and volcano-tube-tips with/without gold nanoparticles present dissimilar changes in their diameters. The gold nanoparticles with size ≥ 3 nm not only slow down length reduction process in the normal-tube-tips and increase tips diameters but also increase their size on the normal-tube-tip by the interaction and growth, while gold nanoparticles with size ≤ 1.5 nm retard the length reduction process in volcano-tube-tips without any change in the tips diameters. Furthermore, they also activate formation of carbon shells over their surface and keep their positions fixed on the volcano-tube-tip. This abnormal interaction of gold nanoparticles with the unstable tips is elucidated in terms of irradiation-induced activation of the graphitic layers, diffusion of Au atoms and bonding between adjacent large (≥ 3 nm) Au NPs, and catalytic effects of small (≤ 1.5 nm) Au NPs. The method can be employed to modify nanotubes with almost atomic precision and to create a predefined pattern of metal nanoparticles on tube tips and surface.

In Situ Observation of Dynamic Galvanic Replacement Reactions in Twinned Metallic Nanowires by Liquid Cell Transmission Electron Microscopy

AbstractGalvanic replacement is a versatile approach to prepare hollow nanostructures with controllable morphology and elemental composition. The primary issue is to identify its fundamental mechanism. In this study, in situ liquid cell transmission electron microscopy was employed to monitor the dynamic reaction process and to explore the mechanism of galvanic replacement. The detailed reaction process was revealed based on in situ experiments in which small Au particles first appeared around Ag nanowires; they coalesced, grew, and adhered to Ag nanowires. After that, small pits grew from the edge of Ag nanowires to form tubular structures, and then extended along the Ag nanowires to obtain hollowed structures. All of our experimental observations from the viewpoint of electron microscopy, combined with DFT calculations, contribute towards an in‐depth understanding of the galvanic replacement reaction process and the design of new materials with hollow structures.

Pressure-Induced Transformations of Three-Component Heterostructural Nanocrystals with CdS–Au2S Janus Nanoparticles as Hosts and Small Au Nanoparticles as Satellites

Heterostructural nanocrystals (HNCs) have drawn enormous attention because of the combined and synergistic properties inherited from their individual components and interactions. Here we design a t...

Enhancing Au/TiO2 Catalyst Thermostability and Coking Resistance with Alkyl Phosphonic-Acid Self-Assembled Monolayers.

Metal oxide-supported Au catalysts, particularly those with small Au nanoparticles, catalyze a variety of reactions including low-temperature CO oxidation and selective hydrogenation of alkynes. However, the facile nature of Au particle growth at even moderate temperatures poses significant challenges to maintaining catalyst activity under reaction conditions. Here, we present a method to reduce the rate of sintering and coke formation in TiO2-supported Au catalysts via the deposition of alkyl-phosphonic acid (PA) self-assembled monolayers. After surface modification with PAs, the resultant catalysts exhibited significantly improved resistance to Au sintering. PA deposition strongly suppressed CO oxidation rates, consistent with poisoning of active sites. In contrast, modification with PAs significantly improved the rate of C2H2 hydrogenation on Au/TiO2. The enhanced activity was accompanied by a dramatically improved resistance to accumulation of surface carbonaceous species.

Controlled Electrochemical Synthesis of Ag Nanoparticles and Their Morphology-Dependent Performances on Catalysing Hydrogen Evolution Reactions

Hydrogen evolution reaction (HER) is one of the most critical reactions in fuel chemistry to produce clean and sustainable hydrogen gas as a renewable energy source. Nowadays, HER has always been catalysed with costly Pt or Pd metal1. To reduce the cost but still maintain a satisfactory performance, studies on Pt/Pd free catalysts for HER have never ceased. In the present work, we explore the electrodeposition of three morphologies (polyhedral, dendritic, and spherical) of Ag nanoparticles on boron-doped diamond electrodes (BDDEs) in various electrochemical conditions including deposition potential and deposition time. Specifically, by varying the deposition potentials of the single-stepped electrochemical deposition, a morphological change from polyhedral to homogeneous dendritic Ag was observed. The high deposition potential would drive the formation of dendritic Ag, which is a thermodynamically unfavourable structure with high surface energy. On the other hand, a two-stepped deposition mechanism was performed to synthesize spherical Ag nanoparticles. This two-stepped mechanism, which was used in synthesising small Au nanoparticles with high coverage by F. Bottari et al., contains a nucleation step at a more negative potential, and a growth step at a less negative potential.2 The sizes of each type of Ag nanoparticles were confirmed by Scanning Electron Microscopy (SEM), and the surface compositions were verified by X-Ray Photoelectron Spectroscopy (XPS). The current densities for HER catalysis were investigated using Linear Sweep Voltammetry (LSV), and a connection between morphologies and catalytic activities was drawn. All three types of Ag modified BDDEs showed better catalytic performance compared to that of drop-coated colloidal Ag-BDDE with comparable coverage and bare BDDE. Notably, spherical Ag-NP modified BDDE with an average particle diameter of 75nm has the highest percentage of pure elemental silver and showed the best performance as well as high stability in HER catalysis, which can be a less expensive yet efficient alternative for Pt/Pd containing catalysts.

Facile fabrication of Au/Fe3O4 nanocomposites as excellent nanocatalyst for ultrafast recyclable reduction of 4-nitropheol

A highly efficient Au/Fe3O4 nanocatalyst is fabricated by using a seed deposition method, and is characterized by XRD, TEM, EDS, XPS, UV–vis and VSM, respectively. TEM image shows that small Au nanoparticles are immobilized onto Fe3O4 surface uniformly and densely. After immersion treatment by NaBH4, the Au/Fe3O4 nanocatalyst exhibits high catalytic efficiency in reducing 4-nitrophenol to 4-aminophenol. The 4-nitrophenol could be fully degraded in less than one minute. The Au/Fe3O4 nanocatalyst demonstrate good magnetic recoverability and high conversion in 1 min (>98%) after 8 successive cycles. The reaction rate constant k of the catalyst with volume Au sol/mass Fe3O4 microspheres ratio 3 (Au/FeO-3) is 13.8 min−1, which is 4.7 times larger than that of Au/FeO-1. The catalytic mechanisms were discussed. This work provides a simple and environmentally friendly method for preparing magnetic noble nanocatalyst used for 4-nitrophenol reduction.