Here we report a facile synthesis of Pt-on-Pd bimetallic nanodendrites with a Pd interior and dendritic Pt exterior. The developed route rationally utilizes the spontaneous separation of the depositions of Pd and Pt, which endows direct formation of Pt-on-Pd nanodendrites. This is a truly simple and unique process that is quite different from the traditional seed-mediated growth strategy. Fine-tuning of the Pt and Pd ratios afforded Pt-on-Pd nanodendrites with superior electrocatalytic activity in comparison with commercial Pt electrocatalysts.
Au@Pt nanocolloids with nanostructured dendritic Pt shells are successfully synthesized by chemically reducing both H 2 PtCl 6 and HAuCl 4 species in the presence of a low-concentration surfactant solution. By applying an ultrasonic treatment, the particle size of the Au@Pt nanocolloids is dramatically decreased and their size distribution becomes very narrow. The difference in reduction potentials of the two soluble metal salts (Au(III) and Pt(IV) species) plays a key role in the one-step synthesis of the core-shell structure. Because of the different reduction potentials, the reduction of Au ions preferentially occurs over a short time to form the Au seeds. It is followed by overgrowth of Pt nanodendritic nanowires on the Au seeds, which is confirmed by ultraviolet-visible light absorption spectroscopy and transmission electron microscopy. Interestingly, the Pt shell thicknesses on Au cores can be easily tuned by controlling the Pt/Au molar ratios in the starting precursor solutions. Through the optimization of the Pt shell thicknesses, the Au@Pt nanocolloids can exhibit enhanced activity as an electrocatalyst for a methanol oxidation reaction, which will be important to improve the utilization efficiency of Pt catalysts in the future.
Mesoporous Pt-Au binary alloys were electrochemically synthesized from lyotropic liquid crystals (LLCs) containing corresponding metal species. Two-dimensional exagonally ordered LLC templates were prepared on conductive substrates from diluted surfactant solutions including water, a nonionic surfactant, ethanol, and metal species by drop-coating. Electrochemical synthesis using such LLC templates enabled the preparation of ordered mesoporous Pt-Au binary alloys without phase segregation. The framework composition in the mesoporous Pt-Au alloy was controlled simply by changing the compositional ratios in the precursor solution. Mesoporous Pt-Au alloys with low Au content exhibited well-ordered 2D hexagonal mesostructures, reflecting those of the original templates. With increasing Au content, however, the mesostructural order gradually decreased, thereby reducing the electrochemically active surface area. Wide-angle X-ray diffraction profiles, X-ray photoelectron spectra, and elemental mapping showed that both Pt and Au were atomically distributed in the frameworks. The electrochemical stability of mesoporous Pt-Au alloys toward methanol oxidation was highly improved relative to that of nonporous Pt and mesoporous Pt films, suggesting that mesoporous Pt-Au alloy films are potentially applicable as electrocatalysts for direct methanol fuel cells. Also, mesoporous Pt-Au alloy electrodes showed a highly sensitive amperometric response for glucose molecules, which will be useful in next-generation enzyme-free glucose sensors.
Platinum (Pt) is widely used as battery electrodes, catalysts
for
chemicals, and catalysts for exhaust gas decomposition in industries.
Increasing need and very limited supply of rare Pt is a serious problem
in the world. Here, we propose new synthetic way for reducing the
use of Pt in a catalytic system by increasing the surface area and
modifying the Pt surface structure. Several types of mesoporous Pt
films with different pore sizes ranging from 5 to 30 nm are prepared
by electrochemical plating in aqueous surfactant solutions. The mesopore
walls are composed of connected Pt nanoparticles with around 3 nm
in diameter. The Pt atomic crystallinity is coherently extending across
over several Pt nanoparticles, showing a large number of atomic steps,
which can accelerate methanol oxidation reaction. As a result of a
high surface area and unique Pt surface, our mesoporous Pt film exhibits
high potentiality as a superior electrocatalyst.
Aggregation of gold nanoparticles (AuNPs) can be utilized in chemical and biomolecular sensing as a sensitive and easy-to-visualize process. However, interpretation of experimental results requires a clear understanding of physicochemical processes that take place upon multiple interactions between an analyte and AuNPs. In this article, interactions between citrate-stabilized AuNPs and organic compounds bearing various functional groups in an aqueous medium were experimentally and theoretically studied using spectrophotometry of the localized surface plasmon resonance (LSPR), transmission electron microscopy (TEM), conductometry, zeta potential measurements, and finite-difference time-domain (FDTD) modeling. As a result, it has been found that organic compounds containing both thiol and amine groups strongly promote the aggregation of AuNPs due to their cooperative functionalities. FDTD modeling has enabled consideration of the light extinction (i.e., LSPR response) properties of nanoparticle aggregates involving single, chain-like, and globular structures. Taking one billion distributions of differently structured aggregates into account, the theoretical light extinction was fitted to that of the experimental result with a root-mean-square deviation of 7%.
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