Kinetics of Spontaneous Bimetallization between Silver and Noble Metal Nanoparticles.

A physical mixture of polymer-protected Ag nanoparticles and Rh, Pd, or Pt nanoparticles spontaneously forms Ag-core bimetallic nanoparticles. The formed nanoparticles were smaller than the parent Ag nanoparticles. In the initial process of this reaction, the surface plasmon absorption of Ag nanoparticles diminished and then almost ceased within one hour. Within several minutes, the decrease in Ag surface plasmon absorption could be analyzed by second-order reaction. This reaction was accelerated with an increase of temperature and the energy gap in the Fermi level between Ag and the other metals. The activation energy (Ea ) of this reaction could be determined. An electron transfer reaction from Ag to other metal nanoparticles was proposed as the initial interaction between these metal nanoparticles because the Fermi level of Ag is relatively high, and the electron transfer is possible in terms of energy. The Marcus plot between the rate constant and the driving force, roughly estimated from the work function of metals, and the observed Ea values reasonably explained the proposed electron transfer mechanism.

Thermostability of Hybrid Thermoelectric Materials Consisting of Poly(Ni-ethenetetrathiolate), Polyimide and Carbon Nanotubes.

Three-component organic/inorganic hybrid films were fabricated by drop-casting the mixed dispersion of nanodispersed-poly(nickel 1,1,2,2-ethenetetrathiolate) (nano-PETT), polyimide (PI) and super growth carbon nanotubes (SG-CNTs) in N-methylpyrrolidone (NMP) at the designed ratio on a substrate. The dried nano-PETT/PI/SG-CNT hybrid films were prepared by the stepwise cleaning of NMP and methanol, and were dried once more. The thermoelectric properties of Seebeck coefficient S and electrical conductivity σ were measured by a thin-film thermoelectric measurement system ADVANCE RIKO ZEM-3M8 at 330-380 K. The electrical conductivity of nano-PETT/PI/SG-CNT hybrid films increased by 1.9 times for solvent treatment by clearing insulated of polymer. In addition, the density of nano-PETT/PI/SG-CNT hybrid films decreased 1.31 to 0.85 g·cm-3 with a decrease in thermal conductivity from 0.18 to 0.12 W·m-1·K-1. To evaluate the thermostability of nano-PETT/PI/SG-CNT hybrid films, the samples were kept at high temperature and the temporal change of thermoelectric properties was measured. The nano-PETT/PI/SG-CNT hybrid films were rather stable at 353 K and kept their power factor even after 4 weeks.

Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters.

Understanding of the "structure-activity" relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au(3+) ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size.

Novel hybrid organic thermoelectric materials:three-component hybrid films consisting of a nanoparticle polymer complex, carbon nanotubes, and vinyl polymer.

A novel class of hybrid organic thermoelectric materials is demonstrated for the first time for constructing flexible thermoelectric devices on polyimide substrates with high output power by using nanotechnology instead of conducting polymers such as poly(3,4-ethylenedioxythiophene). The hybrid organic thermoelectric materials are composed of nanoparticles of a polymer complex, carbon nanotubes, and poly(vinyl chloride), and show high performance (dimensionless thermoelectric figure-of-merit, ZT ≈ 0.3, based on the thermal conductivity through the film).

Synthesis and catalytic activity of crown jewel-structured (IrPd)/Au trimetallic nanoclusters.

Crown-jewel-structured (IrPd)/Au trimetallic nanoclusters are prepared by a galvanic replacement reaction using Ir/Pd nanoclusters with a structure of Ir rich in the core and Pd rich in the shell as mother clusters. The catalytic activity of the top Au atoms for aerobic glucose oxidation of the trimetallic nanoclusters is the highest ever reported among all supported and colloidal catalysts.

Zirconia nanocolloids having a nanospace of poly(cyclodextrin): preparation and application to liquid crystal devices.

Poly(gamma-cyclodextrin) (PgammaCyD)-protected ZrO2 nanocolloids were prepared by using a microwave reactor equipped with ultrasonic nozzle mixing at 240 degrees C for 30 min in a tetraethylene glycol solution of zirconium (IV) ethoxide in the presence of poly(gamma-cyclodextrin). Particles in PgammaCyD-protected ZrO2 nanocolloids have an average diameter of 7.2 nm and mainly distribute within the range of about 3 to 10 nm. The nanocolloids were dispersed in 4'-pentylbiphenyl-4-carbonitrile (5CB) and practical liquid crystal to construct novel twisted nematic liquid crystal devices (TN-LCDs). The response time of this TN-LCDs in the presence of PgammaCyD-protected ZrO2 nanocolloids was faster than that in the absence. The threshold voltage of TN-LCDs by doping PgammaCyD-protected ZrO2 nanocolloids decreased. The decrease of threshold voltage can reduce power consumption, which may meet the demands of future power-saving LCDs.

Novel formation of Ag/Au bimetallic nanoparticles by physical mixture of monometallic nanoparticles in dispersions and their application to catalysts for aerobic glucose oxidation.

Ag/Au bimetallic nanoparticles (BNPs) with a size less than 2 nm were prepared by physical mixture of colloidal dispersions of Ag and Au nanoparticles (NPs). This provides an example of fabrication of BNPs with self-organization by the reaction between metal NPs. Although Ag/Au BNPs having different structures and compositions are one of the most widely studied bimetallic systems in the literature due to their wide range of uses such as in catalysis, electronics, plasmonics, optical sensing, and surface-enhanced Raman scattering, we first prepared such BNPs by physical mixture and characterized them by UV-vis spectroscopy, SERS, XPS, TEM, and EDS in HR-STEM. The present fabrication method has the advantage of avoiding the unfavorable formation of AgCl precipitates in the reaction process which are always produced when Ag(+) ions are used as a starting material in combination with a HAuCl4 precursor. These Ag/Au BNPs showed high catalytic activities for aerobic glucose oxidation, and the highest activity of 11,510 mol of glucose·h(-1)·mol of metal(-1) was observed for the BNPs with a Ag/Au atomic ratio of 1/4; the activity value is about 2 times higher than that of Au NPs with nearly the same particle size. XPS and DFT calculation results show that the negatively charged Au atoms due to the electron charge transfer effects from neighboring Ag atoms and poly(N-vinyl-2-pyrrolidone) act as catalytically active sites and play an important role in the aerobic glucose oxidation.

Crown jewel-structured Au/Pd nanoclusters as novel catalysts for aerobic glucose oxidation.

Low-coordination Au sites have been proved to play a key role in defining the catalytic activity of Au nanoclusters (NCs). At the present time, it is still of great interest and challenge to design and synthesize catalysts containing the desired amount of low-coordinated Au atoms by a simple, easy, and large-scale method. In this study, PVP-protected 'crown jewel'-structured Au/Pd (CJ-Au/Pd) catalyst containing an abundance of top Au atoms were prepared by redox replacement reaction between Pd NCs and Au3+ ions. The catalytic activity of the CJ-Au/Pd NCs for aerobic glucose oxidation is about 3 times higher than that of the Au/Pd alloy NCs prepared by alcohol reduction method, although all of these NCs possess almost the same particle size.

Synthesis of Au/Pt bimetallic nanoparticles with a Pt-rich shell and their high catalytic activities for aerobic glucose oxidation.

Integration of 'green chemistry' principles into nanotechnology is one of the key issues in nanoscience research today. In this work, three series of Au/Pt bimetallic nanoparticles (BNPs) with a structure of Au-rich core/Pt-rich shell were prepared using simultaneous reduction with rapid injection of NaBH(4), simultaneous reduction with dropwise addition of NaBH(4), and simultaneous alcohol reduction. The effects of particle size, electronic structure and composition upon the catalytic activities for aerobic glucose oxidation of the BNPs were also investigated. Catalytically highly active PVP-protected Au/Pt BNPs of about 1.5 nm in diameter were synthesized using simultaneous reduction with rapid injection of NaBH(4). The prepared colloidal Au/Pt BNPs catalysts possessed a high and durable catalytic activity for aerobic glucose oxidation, which were stably kept for more than 2 months under ambient conditions. The maximum activities normalized with Au content of the BNPs with Au/Pt atomic ratio of 4/6 were nearly 10 times higher than that of Au nanoparticles (NPs) with nearly the same particle size. The higher catalytic activity of the prepared Au/Pt BNPs than the Au NPs can be ascribed to the following two factors; (1) the small average diameter, usually about 1.5 nm, and (2) the presence of negatively charged Au and Pt atoms due to electron donation from protecting polymer (PVP: poly(N-vinyl-2-pyrrolidone)) by electronic charge transfer effects upon catalytically active sites. In contrast, the Au/Pt BNPs, synthesized by alcohol reduction and dropwise addition of NaBH(4) into the starting solution and having the large mean particle sizes, showed a low catalytic activity.

Construction and electro-optic properties of liquid-crystal display doped by rhodium nanoparticles.

We prepared 4'-pentylbiphenyl-4-carbonitrile (5CB)-stabilized rhodium (5CB-Rh) nanoparticles and poly(cyclodextrin) (PCyD)-stabilized rhodium (PCyD-Rh) nanoparticles. The average diameter of Rh nanoparticles stabilized by 5CB, PalphaCyD, PbetaCyD, and PgammaCyD are 1.2, 5.4, 6.8, and 5.2 nm, respectively. The nanoparticles were dispersed in liquid crystal 5CB to construct novel twisted nematic liquid crystal device (TN-LCD). Voltage holding ratio was measured for TN-LCD fabricated by doping PbetaCyD-Rh nanoparticles. The decrement of the voltage was very much reduced for that doped with PbetaCyD-Rh. The response time of this TN-LCD in the presence of PbetaCyD-Rh nanoparticles was faster than that in the absence.

Liquid crystal sol containing oleophilic Pd nanoparticles for liquid crystal device.

We have succeeded in preparation of liquid crystal sol containing oleophilic Pd nanoparticles (NPs) stabilized by multidentate copolymer and fabrication of the twisted nematic liquid crystal devices (TN-LCDs) by using Pd NP-containing liquid crystal sol. Oleophilic Pd NPs were prepared by refluxing Pd acetate solution in toluene/ethanol containing poly(N-vinyl-2-pyroridone-co-styrene). Oleophilic Pd NPs showed better solubility in liquid crystal medium than poly(N-vinyl-2-pyrrolidone)-stabilized NPs. The TN-LCDs were fabricated by using two kinds of practical liquid crystal materials doped with oleophilic Pd NPs. The NP-doped LCD showed 22% faster response than non-doped one at -20 degrees C without a chiral dopant. However, LCDs fabricated by liquid crystal materials with a chiral dopant were not affected by NPs. These results suggest that the effect of NPs on the electro-optic performance of LCD is incompatible with that of a chiral dopant.

Catalytically highly active top gold atom on palladium nanocluster.

Catalysis using gold is emerging as an important field of research in connection with 'green' chemistry. Several hypotheses have been presented to explain the markedly high activities of Au catalysts. So far, the origin of the catalytic activities of supported Au catalysts can be assigned to the perimeter interfaces between Au nanoclusters and the support. However, the genesis of the catalytic activities of colloidal Au-based bimetallic nanoclusters is unclear. Moreover, it is still a challenge to synthesize Au-based colloidal catalysts with high activity. Here we now present the 'crown-jewel' concept (Supplementary Fig. S1) for preparation of catalytically highly Au-based colloidal catalysts. Au-Pd colloidal catalysts containing an abundance of top (vertex or corner) Au atoms were synthesized according to the strategy on a large scale. Our results indicate that the genesis of the high activity of the catalysts could be ascribed to the presence of negatively charged top Au atoms.

One-pot synthesis of Ag-Au bimetallic nanoparticles with Au shell and their high catalytic activity for aerobic glucose oxidation.

PVP-protected Ag(core)/Au(shell) bimetallic nanoparticles of enough small size, i.e., 1.4nm in diameter were synthesized in one-vessel using simultaneous reduction of the corresponding ions with rapid injection of NaBH(4), and characterized by HR-TEM. The Ag(core)/Au(shell) bimetallic nanoparticles show a high and durable catalytic activity for the aerobic glucose oxidation, and the catalyst can be stably kept for more than 2months under ambient conditions. The highest activity (16,890mol-glucoseh(-1)mol-metal(-1)) was observed for the bimetallic nanoparticles with Ag/Au atomic ratio of 2/8, the TOF value of which is several times higher than that of Au nanoparticles with nearly the same particle size. The higher catalytic activity of the prepared bimetallic nanoparticles than the usual Au nanoparticles can be ascribed to: (1) the small average diameter, usually less than 2.0nm, and (2) the electronic charge transfer effect from adjacent Ag atoms and protecting PVP to Au active sites. In contrast, the Ag-Au alloy nanoparticles, synthesized by dropwise addition of NaBH(4) into the starting solution and having the large mean particle size, showed a low catalytic activity.

Novel ferromagnetic materials of SmCo5 nanoparticles in single-nanometer size: chemical syntheses and characterizations.

We first succeeded in preparing ferromagnetic materials of SmCo(5) nanoparticles in sizes of single nanometers by a chemical route using a polyol process. In order to produce ferromagnetic SmCo(5) nanoparticles with a CaCu(5)-type structure, the chemical preparation was conducted under a molar ratio of 1:1.3 of Sm:Co as compositions of metallic precursors when tetraethylene glycol (TEG), and oleic acid and oleylamine were used as a reductant and protectant, respectively. However, XRD profiles of the products showed the presence of oxides and other by-products besides the CaCu(5)-type structured nanoparticles. The best metallic precursors and protective reagent to prevent oxidization under reaction were SmCl(3) and Co(acac)(3), and 1-adamantanecarboxylic acid (ACA) and poly(N-vinyl-2-pyrrolidone) (PVP), respectively when TEG was used as the reducing reagent. We found that oxides and other by-products were not detected and pure SmCo(5) nanoparticles with the CaCu(5)-type structure were prepared under the chemical condition. The SmCo(5) nanoparticles coated by ACA and PVP were 6.2 nm in diameter and showed a coercivity of 1500 Oe at 300 K.

Direct synthesis and characterizations of fct-structured FePt nanoparticles using poly(N-vinyl-2-pyrrolidone) as a protecting agent.

FePt alloy in a bulk state is well known as a magnetic material. FePt nanoparticles, which are protected by poly(N-vinyl-2-pyrrolidone) (PVP) and have a face-centered tetragonal (fct) structure at a size of a few nanometers in diameter, have been directly synthesized by a polyol process in high-boiling point tetraethylene glycol used as a reducing reagent for the reduction of Fe(III) acetylacetonate and Pt(II) acetylacetonate. Their magnetic properties (coercivity and saturation magnetization) were dependent on the size and made progress as their diameters increased. The size in diameter was easily controlled by altering the content of PVP, the time for refluxing, and reaction temperature. FePt nanoparticles showed diameter-dependent coercivities at room temperature and they abruptly increased at over 4 nm in diameter. Ferromagnetic FePt nanoparticles with an fct structure were also synthesized at relatively low reaction temperature without refluxing. Likewise, as-synthesized FePt nanoparticles prepared by refluxing at 251 degrees C for 3 h displayed the fct structure and clearly indicated the ferromagnetism at room temperature. Reaction kinetics such as long refluxing time and slow temperature elevation rate were found to be important key factors to synthesize the ferromagnetic FePt nanoparticles although the reaction temperature was very critical as well.

Calorimetric study on interaction of water-soluble copolymers with ionic surfactant.

Using isothermal titration microcalorimetry (ITC), we examined the aggregation behavior of water-soluble copolymers, poly(methoxypolyethylene glycol methacrylate-co-ethyl acrylate)s (PME-EA)s, with ionic surfactant, sodium dodecyl sulfate (SDS). From ITC measurements the values of critical aggregation concentration (cac) and saturation concentration (C(2)), the concentration at which the aggregation of the copolymers starts to form and reaches saturation, respectively, were determined. Thermodynamic parameters such as DeltaG(0)(agg), DeltaH(agg), and TDeltaS(0)(agg) of the aggregation were deduced. Results indicate that cac of the PME-EA remained constant with increase in the concentration of the copolymers, while C(2) increased linearly. On the other hand, the effect of the weight ratio of the EA unit in the copolymer was such that cac of the PME400-EA decreased, while C(2) increased with increase in the weight ratio. The results suggested that the EA units are the main binding sites of the copolymer with SDS.

Platinum nanoparticle is a useful scavenger of superoxide anion and hydrogen peroxide.

Bimetallic nanoparticles consisting of gold and platinum were prepared by a citrate reduction method and complementarily stabilized with pectin (CP-Au/Pt). The percent mole ratio of platinum was varied from 0 to 100%. The CP-Au/Pt were alloy-structured. They were well dispersed in water. The average diameter of platinum nanoparticles (CP-Pt) was 4.7 +/- 1.5 nm. Hydrogen peroxide (H(2)O(2)) was quenched by CP-Au/Pt consisting of more than 50% platinum whereas superoxide anion radical (O(2)(-)) was quenched by any CP-Au/Pt. The CP-Au/Pt quenched these two reactive oxygen species in dose-dependent manners. The CP-Pt is the strongest quencher. The CP-Pt decomposed H(2)O(2) and consequently generated O(2) like catalase. The CP-Pt actually quenched O(2)(-) which was verified by a superoxide dismutase (SOD) assay kit. This quenching activity against O(2)(-) persisted like SOD. Taken together, CP-Pt may be a SOD/catalase mimetic which is useful for medical treatment of oxidative stress diseases.

Direct synthesis of fct-structured FePt nanoparticles at low temperature with assistance of poly(N-vinyl-2-pyrrolidone).

Direct synthesis of fct-structured FePt nanoparticles was successfully achieved by using poly(N-vinyl-2-pyrrolidone) as a protective reagent at lower temperature than the case using low molecular weight ligands as a protective reagent. Experimental data suggest that a transformation of FePt nanoparticles from face-centered cubic to face-centered tetragonal (fct) structure takes place at reaction temperature of 261 degrees C. The results of XRD and the magnetic properties exhibit that the FePt nanoparticles synthesized at 261 degrees C have partially ordered fct-structure and a ferromagnetic behavior at room temperature.

Aggregated structure analysis of polymer-protected platinum/ruthenium colloidal dispersions using EXAFS, HRTEM, and electron diffraction measurements.

Polymer-protected platinum/ruthenium colloidal dispersions were prepared by refluxing mixed solutions of hexachloroplatinic(IV) acid and ruthenium(III) chloride in a mixture of ethanol/water (1/1 v/v) in the presence of poly(N-vinyl-2-pyrrolidone). The electronic spectra and transmission electron micrographs suggested that the colloidal dispersions are almost composed of the mixture of the small monometallic Pt and Ru clusters over all the ratio of Pt/Ru compositions. Extended X-ray absorption fine structure analyses and high resolution electron microprobe analyses indicated that no Pt/Ru alloy clusters exist in the dispersions, and the aggregation occurs between small monometallic Pt clusters (diameter ca. 15 A) and partially oxidized Ru microclusters (diameter less than 10 A). Electron diffraction measurements also suggested that the diffraction pattern of aggregated Pt/Ru cluster particles prepared by the simultaneous reduction of Pt and Ru ions is the same as that of the physical mixture of the small monometallic Pt and Ru clusters separately prepared. Therefore, it can be concluded that the aggregated Pt/Ru cluster particles, with 10 to 60 A in diameter, are built up by small monometallic Pt clusters and partially oxidized Ru microclusters, and that Pt/Ru alloy clusters are not formed.

Spontaneous formation of core/shell bimetallic nanoparticles: a calorimetric study.

We showed recently that low entropy core/shell structured nanoparticles form spontaneously from the physical mixture of a dispersion of Ag nanoparticles and that of another noble metal (Rh, Pd, or Pt) at room temperature. Here we use isothermal titration calorimetry (ITC) and show that the initial step of such a spontaneous process is strongly exothermic. When the alcohol dispersion of poly(N-vinyl-2-pyrrolidone) (PVP)-protected Rh nanoparticles (average diameter 2.3 nm) was titrated into the alcoholic dispersion of PVP-protected Ag nanoparticles, a strong exothermic enthalpy change, DeltaH, was observed: DeltaH = -908 kJ/mol for Ag(S) nanoparticle (average diameter 10.8 nm) and -963 kJ/mol for Ag(L) nanoparticles (average diameter 22.5 nm). The strength of interaction increases in the order of Rh/Ag > Pd/Ag > Pt/Ag. This strong exothermic interaction is considered as a driving force to from low entropy bimetallic nanoparticles by simple mixing of two kinds of monometallic nanoparticles. We show also that exothermic interactions occur between a pair of noble metal nanoparticles themselves by using ITC.