Preparation of novel silver-gold bimetallic nanostructures by seeding with silver nanoplates and application in surface-enhanced Raman scattering

Novel silver-gold bimetallic nanostructures were prepared by seeding with silver nanoplates in the absence of any surfactants. During the synthesis process, it was found that the frameworks of silver nanoplates were normally kept though the basal plane of silver nanoplates became rugged. The real morphology of these nanostructures depended on the molar ratio of gold ions to the seed particles. When the molar ratio of gold ions to silver atoms increased from 0.5 to 4, porous or branched silver-gold bimetallic nanostructures could be made. The growth mechanism was qualitatively discussed based on template-engaged replacement reactions and seed-mediated deposition reactions. Due to the unusual structures, they exhibited interesting optical properties. Moreover, they were shown to be an active substrate for surface-enhanced Raman scattering measurements.

Rapid synthesis of hexagon-shaped gold nanoplates by microwave assistant method

The microwave (MW)-based thermal process was applied to the preparation of hexagon-shaped gold nanoplates. The fort-nation of gold nanoplates occurs rapidly in a single step, carried out by directly heating a reaction mixture of HAuCl4 with sodium citrate in an MW reactor. And the gold nanoplates were characterized by UV-visible spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The experimental results indicated that the sizes and morphologies of the gold nanomaterials strongly depend both on the heating methods and molar ratio of HAuCl4 to sodium citrate in the initial reaction mixture. At the molar ratio 5 : 4 (HAuCl4 to sodium citrate), hexagonal nanoplates with large Au (111) crystallographic facet were preferentially synthesized by the MW assistant method.

Synthesis of gold nanoplates by aspartate reduction of gold chloride

Single crystal nanoplates with thickness less than 30 nm, characterized by hexagonal and truncated triangular shapes bounded mainly by {111} facets, were obtained in large quantities by aspartate reduction of gold chloride.

Surface-enhanced Raman scattering studies on aggregated silver nanoplates in aqueous solution

Four different sizes of citrate-protected silver nanoplates with the corresponding in-plane dipole resonance band at 530, 619, 778, and 858 nm, respectively, are synthesized for surface-enhanced Raman scattering (SERS) study. Their aggregation behaviors are monitored by use of UV-vis spectroscopy. During the aggregation process, a marked red shift of the in-plane dipole resonance of silver nanoplates is observed, whereas other resonance modes of them only have small alterations in the site or intensity. Aggregated silver nanoplates can serve as active SERS substrates with an enhancement factor of about 4.5 x 10(5) using 2-aminothiophenol as a probing molecule. The SERS performance of silver nanoplates is even superior to the commonly used Lee-Meisel silver colloid, making them very attractive for SERS applications.

Glycyl glycine templating synthesis of single-crystal silver nanoplates

We describe the small-biomolecule ( glycyl glycine)-directed synthesis of single-crystalline silver nanoplates, and different experimental conditions have been explored for a more thorough understanding of the growth mechanism. The yield of silver nanoplates relative to the total number of nanoparticles formed was as high as similar to 80%. It was found that the ratio of glycyl glycine to AgNO3 was the key to forming Ag nanoplates.

Biological Routes to Gold Nanoplates

Much effort has been devoted to the synthesis of gold nanoparticles with different shapes, including the zero-dimensional nanospheres, one dimensional nanorods, and two-dimensional nanoplates. Compared to zero or one dimensional nanostructures, the synthesis of two-dimensional nanostructures in high yield has always been more involved, often requiring complex and time-consuming steps such as morphology transformation from the nanospheres, or the seeded growth process. Herein we report a high yield method for gold nanoplate synthesis using the extract of unicellular green alga Chlorella vulgaris, which can be carried out under ambient conditions. More than 90% of the total nanoparticle population is of the platelet morphology, surpassing the previously reported value of 45%. The control of the anisotropic growth of different planes; as well as the lateral size, has also been partially optimized.

Kinetic effects of halide ions on the morphological evolution of silver nanoplates

Time-resolved extinction spectroscopy is employed to study the reaction kinetics in the shape-conversion reaction involving halide ions (including Cl-, Br- and I-) etching (sculpturing) silver nanoplates. A series of time-resolved extinction spectra are obtained during the in situ etching process and the evolution of surface plasmon resonance (SPR) of the silver nanoparticles is analyzed. Spectral analysis indicates that the conversion of nanoprisms starts simultaneously with the emergence of nanodisks when the halide ions are added. The etching rate of different halide ions is evaluated through the in-plane dipole resonance peak intensity of silver nanoplates vs. the reaction time (dI/dt). The relationship between the etching rate and the halide ion concentration shows that the halide ion etching reaction can be considered as a pseudo-first-order reaction. The effect of different halide ions on the shape-conversion of silver nanoplates is compared in detail. The activation energy of the etching reaction is calculated, which indicates that the etching ability of different halide ions is on the order of Cl - < I- < Br-.

Synthesis and characterization of hexagonal and truncated hexagonal shaped MoO3 nanoplates

Hexagonal and truncated hexagonal shaped MoO₃ nanoplates (MoO₃ HNP) were synthesized through a simple vapor-deposition method in Ar atmosphere under ambient pressure without the assistant of any catalysts. The structure and morphology of MoO₃ HNP were investigated by XRD, EDX, SEM, TEM, and HRTEM. The results reveal that the HNP are α-MoO₃ and have a large area surface. The Raman spectrum shows a significant size effect on the vibrational property of MoO₃ HNP. The photoluminescence (PL) spectrum was carried out, and two peaks at 351 and 410 nm were observed in the spectrum. In addition, a possible growth mechanism proposed as VS is discussed in detail.

Shape evolution of silver nanoplates through heating and photoinduction

Shape conversions of silver nanoplates were realized by heating and subsequent light irradiation. The initial silver nanoprisms were transformed into silver nanodisks gradually in the process of heating, which was possibly achieved through dissolving and readsorption of silver atoms on the surface of silver nanoplates. Subsequently, under light irradiation, the heating induced silver nanodisks were reversed to silver nanoprisms in the same solution. The dissolved oxygen was found to play a pivotal role in the shape conversion from nanoprism to nanodisk. In addition to heating, deionized water could induce the shape conversion of silver nanoplates when it was added to precipitate of the initial silver nanoprisms after centrifugation. Citrate in solution is essential to the photoinduced shape conversion process. Transmission electron microscopy (TEM) and extinction spectroscopy results demonstrated that localized surface plasmon resonance (LSPR) properties of silver nanoplates were effectively tuned through shape conversion.

Preparation of size-selective Mn3O4 hexagonal nanoplates with superior electrochemical properties for pseudocapacitors

Porous Mn3O4 hexagonal nanoplates were synthesized through annealing the hydrohausmannite precursor obtained by a one-pot hydrothermal process and by precisely controlling the concentrations of potassium hydroxide and glucose. The effect of potassium hydroxide and glucose on the growth of hexagonal nanoplates was investigated, and a growth mechanism was also proposed. Due to its abundant pores, the pure Mn3O4-based electrode exhibits excellent cycling stability with 100% capacity retention after 5000 cycles. The asymmetric supercapacitor exhibited high performance with an energy density of 17.276 W h kg^-1 at a power density of 207.3 W kg^-1 in a wide potential window of 1.5 V.

Photolumiscent Properties of Nanorods and Nanoplates Y2O3:Eu3+

Nanorods and nanoplates of Y2O3:Eu3+ powders were synthesized through the thermal decomposition of the Y(OH)(3) precursors using a microwave-hydrothermal method in a very short reaction time. These powders were analyzed by X-ray diffraction, field emission scanning electron microscopy, Fourrier transform Raman, as well as photoluminescence measurements. Based on these results, these materials presented nanoplates and nanorods morphologies. The broad emission band between 300 and 440 nm ascribed to the photoluminescence of Y2O3 matrix shifts as the procedure used in the microwave-hydrothermal assisted method changes in the Y2O3:Eu3+ samples. The presence of Eu3+ and the hydrothermal treatment time are responsible for the band shifts in Y2O3:Eu3+ powders, since in the pure Y2O3 matrix this behavior was not observed. Y2O3:Eu3+ powders also show the characteristic Eu3+ emission lines at 580, 591, 610, 651 and 695 nm, when excited at 393 nm. The most intense band at 610 nm is responsible for the Eu3+ red emission in these materials, and the Eu3+ lifetime for this transition presented a slight increase as the time used in the microwave-hydrothermal assisted method increases.

Cost-effective and eco-friendly synthesis of novel and stable N-doped ZnO/g-C3N4 core-shell nanoplates with excellent visible-light responsive photocatalysis

N-doped ZnO/g-C3N4 hybrid core–shell nanoplates have been successfully prepared via a facile, cost-effective and eco-friendly ultrasonic dispersion method for the first time. HRTEM studies confirm the formation of the N-doped ZnO/g-C3N4 hybrid core–shell nanoplates with an average diameter of 50 nm and the g-C3N4 shell thickness can be tuned by varying the content of loaded g-C3N4. The direct contact of the N-doped ZnO surface and g-C3N4 shell without any adhesive interlayer introduced a new carbon energy level in the N-doped ZnO band gap and thereby effectively lowered the band gap energy. Consequently, the as-prepared hybrid core–shell nanoplates showed a greatly enhanced visible-light photocatalysis for the degradation of Rhodamine B compare to that of pure N-doped ZnO surface and g-C3N4. Based on the experimental results, a proposed mechanism for the N-doped ZnO/g-C3N4 photocatalyst was discussed. Interestingly, the hybrid core–shell nanoplates possess high photostability. The improved photocatalytic performance is due to a synergistic effect at the interface of the N-doped ZnO and g-C3N4 including large surface-exposure area, energy band structure and enhanced charge-separation properties. Significantly, the enhanced performance also demonstrates the importance of evaluating new core–shell composite photocatalysts with g-C3N4 as shell material.

Facet-controlled Self-assembly of ZnO Nanocrystals by Non-Hydrolytic Aminolysis and their Photodegradation Activities

We report a method for controlling the exposed facets and hence the dimensionality and shape of ZnO nanocrystals using a non-hydrolytic aminolysis synthesis route. The effects of changes to reaction conditions on ZnO formation were investigated and possible self-assembly mechanisms proposed. The crystal facet growth and hence morphologies of the ZnO nanocrystals were controlled by varying reaction temperature and the reactant ratio. Four distinct ZnO nanocrystal types were produced (nanocones, nanobullets, nanorods and nanoplates). The relative photocatalytic activities of the exposed facets of these ZnO nanostructures were also examined, which showed the activities obviously depended on the reactivity of exposed crystal facets in the order: {1011}>>{0001}, {1010}.

Hybrid polymer/metal nanoparticles with surface enhanced raman tracking for potential use in nanomedicine

This project was a preliminary step towards the development of novel methods for early stage cancer diagnosis and treatment. Diagnostic imaging agents with high Raman signal enhancement were developed based on tailored assemblies of gold nanoparticles, which demonstrated potential for non-invasive detection from deep under the skin surface. Specifically designed polymers were employed to assemble gold nanoparticles into controlled morphologies including dimers, nanochains, nanoplates, globular and core-satellite nanostructures. Our findings suggest that the Raman enhancement is strongly dependent on assembly morphology and can be tuned to adapt to the requirements of the diagnostic agent.

Hybrid CuTCNQ/AgTCNQ metal-organic charge transfer complexes via galvanic replacement vs. corrosion recrystallization

This study reports a hybrid of two metal-organic semiconductors that are based on organic charge transfer complexes of 7,7,8,8-tetracyanoquinodimethane (TCNQ). It is shown that the spontaneous reaction between semiconducting microrods of CuTCNQ with Ag+ ions leads to the formation of a CuTCNQ/AgTCNQ hybrid, both in aqueous solution and acetonitrile, albeit with completely different reaction mechanisms. In an aqueous environment, the reaction proceeds by a complex galvanic replacement (GR) mechanism, wherein in addition to AgTCNQ nanowires, Ag0 nanoparticles and Cu(OH)2 crystals decorate the surface of CuTCNQ microrods. Conversely, in acetonitrile, a GR mechanism is found to be thermodynamically unfavorable and instead a corrosion-recrystallization mechanism leads to the decoration of CuTCNQ microrods with AgTCNQ nanoplates, resulting in a pure CuTCNQ/AgTCNQ hybrid metal-organic charge transfer complex. While hybrids of two different inorganic semiconductors are regularly reported, this report pioneers the formation of a hybrid involving two metal-organic semiconductors that will expand the scope of TCNQ-based charge transfer complexes for improved catalysis, sensing, electronics and biological applications.