Au Seeds Research Articles

Effects of Zinc Nitrate and HMTA on the Formation Mechanisms of ZnO Nanowires on Au Seed Layers

Effects of Zinc Nitrate and HMTA on the Formation Mechanisms of ZnO Nanowires on Au Seed Layers

Dual Function of 4-Aminothiophene in Surface-Enhanced Raman Scattering Application as an Internal Standard and Adsorbent for Controlling Au Nanocrystal Morphology.

The sensitivity and quantitative accuracy of surface-enhanced Raman scattering (SERS) are the main factors that restrict its application. Here, novel Au nanoscale convex polyhedrons (Au NCPs) were designed and fabricated to solve these problems via an embedded standard, including eight pods and six small protrusions. Spherical Au seeds regrew into different sizes of Au NCPs with a face-centered cubic structure. This morphology is due to the dual mechanism of the 4-aminothiophene (4-ATP) molecule that serves as an internal standard and a surface ligand regulator combined with the regulatory role of hexadecyl trimethyl ammonium chloride. The results show that Au NCPs were enclosed by high-index {12 9 1} facets, which greatly improved the local plasma resonance and reduced the lowest SERS detectable concentration of pyrene in standard seawater to 0.5 nM. An effective reference was produced by embedding 4-ATP with a relative standard deviation value less than 2.97% (in the same batch) and 3.92% (between different batches). Our research offers a new strategy for morphological regulation of metal nanocrystals, which is useful for the preparation of highly sensitive SERS substrates and trace analysis.

Lattice Mismatch-Induced Formation of Copper Nanoplates with Embedded Ultrasmall Platinum or Palladium Cores for Tunable Optical Properties.

Although noble metal nanocrystals have been studied extensively in the past decades, the shape-controlled synthesis of non-noble metal nanocrystals has remained challenging with limited success, which is a grand obstacle to their wide applications. Herein, a novel lattice mismatch-involved shape-control mechanism of Cu nanocrystals in a seed-mediated synthesis is reported, which can produce Cu nanoplates in high yield with tailored sizes (28-130nm), holding great potential in optical and catalytic applications. The lattice mismatch between Cu and the seed is found effective in inducing crystallographic defects for symmetry breaking toward anisotropic nanocrystals. While a too-large lattice mismatch (11.7% for Au seeds) leads to multiple twin defects to form quasi-spherical Cu nanocrystals, an appropriately large lattice mismatch (7.7% for Pt and 6.9% for Pd seeds) successfully induces planar defects for the formation of Cu nanoplates. The size of the Cu nanoplates is customizable by controlling the concentration of the seeds, leading to tunable optical properties. A prototype of a colorimetric indicator with Cu nanoplates, potentially applicable to the safety control of foods and drugs is demonstrated. This mechanism paves a new way for the shape-controlled synthesis of Cu and other metal nanocrystals for a broad range of applications.

Growth pathways of Cu shells on Au and AuCu seeds: interdiffusion, shape transformations, strained shells and patchy surfaces.

The growth of AuCu nanoparticles obtained by depositing Cu atoms on starting seeds of pure Au and on mixed AuCu seeds is studied by molecular dynamics simulations. Depending on the shape of the seed, its composition and the growth temperature, different growth pathways are observed, in which several types of structural transformations take place. The final growth structures comprise Au@Cu core@shell arrangements as well as Janus-like structures with patchy surfaces. The results of the growth simulations are rationalized in terms of the activation of different diffusion processes, both on the surface and inside the growing clusters. These diffusion processes regulate structural transitions between different motifs and the occurrence of dewetting phenomena. The simulation results show that depositon of Cu atoms on pure Au or mixed AuCu seed can be an effective tool for producing clusters with uncommon surface atom arrangements of potential interest for catalysis.

Au-Seeded CsPbI3 Nanowire Optoelectronics via Exothermic Nucleation.

Converting vapor precursors to solid nanostructures via a liquid noble-metal seed is a common vapor deposition principle. However, such a noble-metal-seeded process is excluded from the crystalline halide perovskite synthesis, mainly hindered by the growth mechanism shortness. Herein, powered by a spontaneous exothermic nucleation process (ΔH < 0), the Au-seeded CsPbI3 nanowires (NWs) growth is realized based on a vapor-liquid-solid (VLS) growth mode. It is energetically favored that the Au seeds are reacted with a Pb vapor precursor to form molten Au-Pb droplets at temperatures down to 212 °C, further triggering the low-temperature VLS growth of CsPbI3 NWs. More importantly, this Au-seeded process reduces in-bandgap trap states and consequently avoids Shockley-Read-Hall recombination, contributing to outstanding photodetector performances. Our work extends the powerful Au-seeded VLS growth mode to the emerging halide perovskites, which will facilitate their nanostructures with tailored material properties.

Silver‐Free Synthesis of Concave Au Nanocubes with Enhanced Activity Towards Electro‐Oxidation of Ethanol: Experimental and Theoretical Studies

AbstractWe report a silver‐free synthesis of gold (Au) concave nanocubes (CNCs) that involves the direct deposition of Au atoms over spherical Au seeds under well‐controlled reaction kinetics and surface capping. The elementally‐pure composition makes them ideal research candidate towards validating structural advantage of concave surface in electrocatalytic oxidation of ethanol. In particular, the as‐obtained Au CNCs exhibited an enhanced specific activity and reaction kinetics, but weakened long‐term stability, as compared to quasi‐spherical counterparts. Theoretical simulations suggest that the high‐index planes represent a high catalytic performance for ethanol oxidation. The current work offers an effective synthetic strategy that successfully excludes the necessary and wide use of Ag+ ions in controlled synthesis of pure Au nanocrystals with a concave cubic shape, shedding light on the rational design of fuel cell electrocatalyst from the perspective of crystal facet effect.

Facile and controllable synthesis of monodisperse gold nanoparticle bipyramid for electrochemical dopamine sensor

We demonstrated potential features of gold nanoparticle bipyramid (AuNB) for an electrochemical biosensor. The facile synthesis method and controllable shape and size of the AuNB are achieved through the optimization of cetyltrimethylammonium chloride (CTAC) surfactant over citric acid (CA) ratio determining the control of typically spherical Au seed size and its transition into a penta-twinned crystal structure. We observe that the optimized ratio of CTAC and CA facilitates flocculation control in which Au seeds with size as tiny as ∼14.8 nm could be attained and finally transformed into AuNB structures with an average length of ∼55 nm with high reproducibility. To improve the electrochemical sensing performance of a screen-printed carbon electrode, surface modification with AuNB via distinctive linking procedures effectively enhanced the electroactive surface area by 40%. Carried out for the detection of dopamine, a neurotransmitter frequently linked to the risk of Parkinson’s, Alzheimer’s, and Huntington’s diseases, the AuNB decorated-carbon electrode shows outstanding electrocatalytic activity that improves sensing performance, including high sensitivity, low detection limit, wide dynamic range, high selectivity against different analytes, such as ascorbic acid, uric acid and urea, and excellent reproducibility.

Tunable Reversal of Circular Dichroism in the Seed-Mediated Growth of Bichiral Plasmonic Nanoparticles.

Plasmonic nanoparticles with an intrinsic chiral structure have emerged as a promising chiral platform for applications in biosensing, medicine, catalysis, separation, and photonics. Quantitative understanding of the correlation between nanoparticle structure and optical chirality becomes increasingly important but still represents a significantly challenging task. Here we demonstrate that tunable signal reversal of circular dichroism in the seed-mediated chiral growth of plasmonic nanoparticles can be achieved through the hybridization of bichiral centers without inverting the geometric chirality. Both experimental and theoretical results demonstrated the opposite sign of circular dichroism of two different bichiral geometries. Chiral molecules were found to not only contribute to the chirality transfer from molecules to nanoparticles but also manipulate the structural evolution of nanoparticles that synergistically drive the formation of two different chiral centers. By deliberately adjusting the concentration of chiral molecules and other synthetic parameters, such as the reducing agent concentration, the capping surfactant concentration, and the amount of Au precursor, we have been able to fine-tune the circular dichroism reversal of bichiral Au nanoparticles. We further demonstrate that the structure of chiral molecules and the crystal structure of Au seeds play crucial roles in the formation of Au nanoparticles with bichiral centers. The insights gained from this work not only shed light on the underlying mechanisms dictating the intriguing geometric and chirality evolution of bichiral plasmonic nanoparticles but also provide an important knowledge framework that guides the rational design of bichiral plasmonic nanostructures toward chiroptical applications.

Atom Absorption Energy Directed Symmetry-Breaking Synthesis of Au-Ag Hierarchical Nanostructures and Their Efficient Photothermal Conversion.

Asymmetric plasmonic hierarchical nanostructures (HNs) are of great significance in optics, catalysis, and sensors, but the complex growth kinetics and lack of fine structure design limit their practical applications. Herein, a new atom absorption energy strategy is developed to achieve a series of Au-Ag HNs with the continuously tuned contact area in Janus and Ag island number/size on Au seeds. Different from the traditional passive growth mode, this strategy endows seed with a hand to capture the hetero atoms in a proactive manner, which is beyond the size, shape, and assembles of Au seed. Density functional theory reveals ththe adsorption of PDDA on Au surface leads to lower formation energy of Au-Ag bonds (-3.96eV) than FSDNA modified Au surface (-2.44eV). The competitive adsorption of two ligands on Au seed is the decisive factor for the formation of diverse Au-Ag HNs. In particular, the Au-Ag2 HNs exhibit outstanding photothermal conversion capability in the near-infrared window, and in vivo experiments verify them as superior photothermal therapy agents. This work highlights the importance of the atom absorption energy strategy in unlocking the diversity of HNs and may push the synthesis and application of superstructures to a higher level.

Seed-mediated growth of highly concentrated silver nanoparticles on a flexible substrate for applications in SERS-based trace detection

In this work, we demonstrate a seeded approach for in-situ growth of Ag nanostructures directly on filter paper. Multiple growth steps were used to increase the size of Ag NPs grown from Au seeds. Essentially, this procedure generated a high density of NPs on filter paper which in turn provided high enhancement of Raman signals. We have seen a marked increase in the SERS enhancement factor with each growth step. Moreover, the relative standard deviation (RSD) values decreased with each growth step, indicating the relatively uniform distribution of NPs on the substrate. With four growth steps, we were able to achieve an EF of 9.28 × 104 with RSD values of 14%. In particular, the detection limit of 10 nM for CV has been achieved by both solution drying and swabbing. Moreover, swab detection of explosive material ammonium nitrate down to 100 µM has also been demonstrated.

Anisotropic Ag@Au architectures through real-time surface-based strategy of synthesis: Large-area enhanced nanosensors

Here, we report an innovative facile polymer-templated synthesis of Ag/Au bimetallic nanoparticles (BNPs) on large surface for sensing. By controlling the reaction kinetics, the bimetallic nanoparticles have been successfully prepared with a variety of structures: heterostructures, eccentric core-shells, and physical mixtures of two metals. The amount and initial shape of the Au seeds determined the final architectures of bimetallic nanostructures. The underlying synthesis mechanism of BNPs was regulated by a seed-mediated growth (SMG) on the surface. The newly formed Ag atoms were directed to selectively nucleate and then epitaxially grow on specific facets of cubic/hexagonal Au seeds. Comprehensive results demonstrating an optical response of two metallic/poly (methyl methacrylate) (M+/PMMA) layers on opaque surfaces by micro-extinction measurements were obtained. Sensors based on anisotropic bimetallic substrates were ideal for sensitive 4,4′-bipyridine (4,4’-BP) detection. The polymer surface-induced accumulation of high electric fields on nanoscale sensing volumes of anisotropic core/shell BNPs allowed more analyte molecules to access their high-index facets. This sample possessed a high surface-enhanced Raman scattering (SERS) sensitivity despite only being validated on very small densities of surfaces; thanks to the synergistic effects between the two coupled metals. The present findings suggest that a surfactant-free synthesis can be used as a powerful mean of defining growth strategies based on silicon substrate platforms.

Dendrimer-based magneto-plasmonic nanosorbents for water quality monitoring using surface-enhanced Raman spectroscopy

In this work, we report the synthesis of magneto-plasmonic dendrimer-based nanosorbents containing Au nanostars and we demonstrate that they can be used as versatile optical sensors for the detection of pesticides in spiked water samples. The magnetic hybrid nanoparticles were obtained by conjugating silica-functionalized G5-NH2 PAMAM dendrimers to silica-coated magnetite cores. The resulting magnetic-PAMAM conjugates were then used to reduce and sequester Au seeds for the subsequent in situ growth of Au nanostars. The dendrimer-based magneto-plasmonic substrates containing the Au anisotropic nanophases were then investigated regarding their ability to monitor water quality through surface-enhanced Raman scattering (SERS) spectroscopy. As a proof-of-concept, the ensuing multifunctional materials were investigated as SERS probing systems to detect dithiocarbamate pesticides (ziram and thiram) dissolved in water samples. It was observed that the magneto-plasmonic hybrid materials enhance the Raman signal of these pesticides under variable operational conditions, suggesting the versatility of these systems for water quality monitoring. Moreover, a detailed analysis of the SERS data was accomplished to predict the adsorption profile of the dithiocarbamate pesticides to the Au surface.

Fabrication of Gold-Based "Sphere-on-Plate" Hybrid Nanostructures with Dual Plasmonic Absorptions Covering Visible and Near-Infrared II Windows via the Volmer-Weber Growth Mode.

We report a synthetic strategy to create gold(Au)-based "sphere-on-plate" hybrid nanostructures (SPHNSs). The surface doping of plate-like Au seeds with Pt/Ag atoms is found to be crucial to increase the lattice spacing, inducing island-like deposition of Au atoms via the Volmer-Weber growth mode. The resulting products are featured with the morphology that quasi-spherical nanoparticles are scattered over the nanoplates. Due to the presence of two distinctly dimensioned particles in one entity, the current Au-based SPHNSs exhibit unique dual plasmonic absorptions, where the visible absorbance centered at 546 nm is related to the size of the anchored particles. Arising from such a plasmonic advantage, the Au-based SPHNSs exhibit enhancement in photothermal conversion under laser irradiations at the wavelengths of both 808 and 1064 nm. The current work offers a feasible route to fabricate noble metal hybrid nanostructures involving zero-dimensional (0D) and two-dimensional (2D) structures, which could work as promising materials for photothermal conversion.

Fabrication of monodisperse gold-copper nanocubes and AuCu-cuprous sulfide heterodimers by a step-wise polyol reduction

Monodisperse gold-copper nanocubes and AuCu-cuprous sulfide (Cu1.96S) heterodimers were fabricated by a step-wise polyol reduction with the aid of oleylamine and 1-dodecanethiol. The geometric configuration was mediated by simply varying the Cu/Au atomic ratio: Au-Cu cubes with sizes of 6.4 and 4.3 nm were yielded at Cu/Au atomic ratios of 1/3 and 1/1, respectively; while AuCu-Cu1.96S heterodimer, consisting of a AuCu cube of 4.6 nm and a Cu1.96S sphere of 6.3 nm was obtained at Cu/Au atomic ratio of 3/1. Detailed structural analysis on the intermediate products, collected at different intervals during the synthesis, revealed that small-sized Au seeds formed at 423 K, followed by the growth of Cu and Cu1.96S crystals at 473 K. Oleylamine coordinated to Au3+ and Cu2+ and thus mediated the particle size; while 1-dodecanethiol bonded to Au3+ and directed the cubic morphology. Excessive Cu2+, at the Cu/Au atomic ratio of 3/1, interacted with 1-dodecanethiol and formed Cu1.96S spherical particle that epitaxially grew over the AuCu cube, resulting in a heterodimer structure. Due to the enriched surficial Cu atoms and their electronic interactions with Au atoms, Au-Cu nanocubes and AuCu-Cu1.96S heterodimers showed pronounced activities for the catalytic reduction of 4-nitrophenol to 4-aminophenol with NaBH4 at 298 K.

Seeded Growth of Gold-Copper Janus Nanostructures as a Tandem Catalyst for Efficient Electroreduction of CO2 to C2+ Products.

Gold-copper (Au-Cu) Janus nanostructures (Au-Cu Janus NSs) are successfully prepared using N-oleyl-1,3-propanediamine as capping agent and Cu(acac)2 as the precursor in a typical seeded growth strategy. By preferably depositing Cu atoms on one side of concave cubic Au seeds, the Cu part gradually grows larger as more Cu precursors are added, making the size tuning feasible in the range of 74-156nm. When employed as an electrocatalyst for electrochemical CO2 reduction (CO2 RR), the Au-Cu Janus NSs display superior performance to Au@Cu core-shell NSs and Cu NPs in terms of C2+ products selectivity (67%) and C2+ partial current density (-0.29Acm-2 ). Combined experimental verification and theoretical simulations reveal that CO spillover from Au sites to the nearby Cu counterparts would enhance CO coverage and thus promote C-C coupling, highlighting the unique structural advantages of the Au-Cu Janus NSs toward deep reduction of CO2 . The current work provides a facile strategy to fabricate tandem catalyst with a Janus structure and validates its structural advantages toward CO2 RR, which are of critical importance for the rational design of efficient CO2 RR catalyst.

The patchy growth mode: Modulation of the Au-Au interface via phenynyl ligands

Surface ligands play critical roles in nano-synthesis and thus it is of great importance in expanding the scope of suitable ligands. In this work, we explore phenynyl ligands in modulating the Au-Au interface when growing Au domains on Au seeds. A patchy growth mode is observed where the emerging islands are flat-laying with holes and branches. This growth mode is distinctively different from the conventional facet-controlled growth using weak ligands, and the non-wetting island growth using strong ligands. Through manipulating the molecular structure and the packing of the phenynyl ligands on the Au seeds, the overgrown Au domains are continuously tuned, from patches to islands, extending the plasmon absorption peak into the near-infrared spectral range. We believe that the new ligand with intermediate affinity and the unusual growth mode would expand the control in both synthesis and application.

Tuning the Shape of Gold‐Silver Nanocrystals by Separately Controlling the Metal‐Atom Concentration in a One‐Pot Synthesis

AbstractWe report a niche synthetic strategy to manipulate the shape of gold‐silver (AuAg) nanocrystals based on kinetics control. The success of current work relies on the use of two syringe pumps to add Au and Ag precursor solutions independently at distinct injection rates, which allows the separate control over the feeding rate of Au and Ag atoms, respectively. Such strategy is validated effective in both one‐pot reduction and seeded growth involving spherical and rod‐likes Au seeds. By conducting orthogonal experiments setting two injection rates at three levels, a set of morphologies are obtained. Interestingly, AuAg alloy nanocrystals in the form of multipod, hollow protruded particles, and branched hollow nanoplate, that are rare to obtain via conventional routes, are successfully screened out, exhibiting the unique advantage of this strategy. The current work provides a feasible approach to applying kinetics control over AuAg bimetallic nanocrystals, which could be extended to other noble metals or material combinations.

Light‐Induced Solid‐State Protrusion of Gold Nanowires and Their Derivatives for Sensing Applications

AbstractGold nanowires (AuNWs) have been one of the key components for nanoelectronics and optoelectronic devices but the fabrication has been poorly customized for this purpose even though diverse synthetic strategies bloomed over the last decades. Here, the concept of light‐induced protrusion of AuNWs directly from solid state substrate is demonstrated, which is highly compatible for on‐chip fabrication of functional nanodevices. This is realized by irradiating the Au ion‐doped titanium dioxide (TiO2) films with continuous wave laser. The blue laser triggers the reduction and nucleation of Au(0) which grows vertically into AuNW bundles with diffusion‐controlled supply of Au ions within the TiO2 matrix. Thus, the morphology of the AuNWs can be tuned with irradiation time/power as well as the ion concentration, which can derive into Au nanorings (NRs) and NR stacks in 1D photonic crystal with reduced plasmon linewidth. Such light‐induced protrusion can also generate nanopillars by introducing Au seeds before irradiation. The surface‐enhanced Raman scattering performance of the AuNW bundles is excellent with fm detection limit. Such laser‐directed solid‐state growth technique is facile, versatile, cost‐effective site‐selective, ligand‐free, and wafer‐scalable, which opens up many promising applications in (bio)chemical sensing, photovoltaics, photocatalysis, plasmonic displays, and integrated nanoelectronic/optoelectronic devices.

Trimetallic Au@RhCu Core‐Shell Nanodendrites as Efficient Bifunctional Electrocatalysts toward Hydrogen and Oxygen Evolution Reactions

AbstractDeveloping efficient and stable electrocatalysts for water splitting is highly desirable due to growing energy demands. Here, Au@RhCu nanodendrites with core‐shell nanostructure were facile generated via seed‐mediated method. Through composition optimization, the Au@Rh3Cu nanodendrites show excellent hydrogen evolution reaction (HER) activity with an overpotential of 83 mV at the current density of 10 mA cm−2, together with a small Tafel slope of 33.4 mV dec−1. Meanwhile, the Au@Rh3Cu nanocrystals are also a good oxygen evolution reaction (OER) catalyst with an overpotential of 415 mV (at 10 mA cm−2) and a Tafel slope of 127 mV dec−1. Additionally, the Au@Rh3Cu exhibits excellent stability for both HER and OER. Such attractive catalytic performance can be assigned to the large surface area produced by the unique core‐shell dendritic nanostructure, the synergistic effect between different metal elements and the positive influence of Au seeds. This work would offer a reliable pathway for the design of multimetallic core‐shell dendritic nanostructures as promising electrocatalysts toward water splitting.

Asymmetric seed passivation for regioselective overgrowth and formation of plasmonic nanobowls.

Plasmonic nanoparticles (NPs) have garnered excitement over the past several decades stemming from their unique optoelectronic properties, leading to their use in various sensing applications and theranostics. Symmetry dictates the properties of many nanomaterials, and nanostructures with low, but still defined symmetries, often display markedly different properties compared to their higher symmetry counterparts. While numerous methods are available to manipulate symmetry, surface protecting groups such as polymers are finding use due to their ability to achieve regioselective modification of NP seeds, which can be removed after overgrowth as shown here. Specifically, poly(styrene-b-polyacrylic acid) (PSPAA) is used to asymmetrically passivate cubic Au seeds through competition with hexadecyltrimethylammonium bromide (CTAB) ligands. The asymmetric passivation via collapsed PSPAA causes only select vertices and faces of the Au cubes to be available for deposition of new material (i.e., Au, Au-Ag alloy, and Au-Pd alloy) during seeded overgrowth. At low metal precursor concentrations, deposition follows observations from unpassivated seeds but with new material growing from only the exposed seed portions. At high metal precursor concentrations, nanobowl-like structures form from interaction between the depositing phase and the passivating PSPAA. Through experiment and simulation, the optoelectronic properties of these nanobowls were probed, finding that the interiors and exteriors of the nanobowls can be functionalized selectively as revealed by surface enhanced Raman spectroscopy (SERS).