Synthesis of low-cost multi-element Pt-based alloy nanoparticles as catalysts for the oxygen reduction reaction.

Due to their high catalytic activity, stability, and economic benefits, Pt-based multi-element alloyed nanoparticles (NPs) are considered promising electrodes for oxygen reduction reactions. However, a synthesis method capable of controlling the reduction reaction of elements with different redox potentials to synthesize multimetallic alloy NPs is yet to be developed. In this study, monodisperse NiPtPd alloy NPs with varying compositions were synthesized using 1-heptanol as a reducing solvent. The selection of low-reducing noble metal precursors and complexing agents is done strategically to adjust the reduction time of metal ions. The spectroscopic results confirmed that olelylamine (OAm) preferentially coordinates with Pt ions, while trioctylphosphine (TOP) preferentially coordinates with Pd ions. Consequently, control of the elemental distribution within the particle is successfully achieved by adjusting the OAm/Pt and TOP/Pd molar ratios. Subsequently, Ni78Pt11Pd11 alloy NPs were designed, and their catalytic properties as electrodes in the oxygen reduction reaction (ORR) were examined. Despite a low noble metal content of 22%, the catalytic performance and stability were superior to and comparable to those of commercial Pt NPs, respectively.

Speciation of chromium aqua and chloro complexes in hydrochloric acid solutions at 298 K.

The distribution of metal aqua and chloro complexes is fundamental information for analysis of a chemical reaction involving these complexes. The present study investigated the speciation and structures of chromium aqua and chloro complexes using the thermodynamic model fitting analysis of UV-vis/X-ray absorption spectra. The existence of a negatively charged species was examined by adsorbability of chromium species on a strong base anion exchanger. In the results, a planar square [CrIII(H2O)4]3+, a planar square or distorted tetrahedral [CrIIICl(H2O)3]2+, a trigonal bipyramidal [CrIIICl3(H2O)2]0, and a distorted octahedral [CrIIICl4(H2O)2]- were confirmed and the thermodynamic parameters of complexation reactions were quantitatively determined. Investigation of the evolution of speciation of chromium aqua and chloro complexes in a pH 1 solution suggested the existence of [CrIIICl2(H2O) m ]+ (m = 2 or 3) during the hydration process, which diminished in the equilibrium state. The kinetic analysis deserves further investigation to understand the speciation process quantitatively.

Synthesis of Electromagnetic Wave-Absorbing Co-Ni Alloys and Co-Ni Core-Shell Structured Nanoparticles.

Co-Ni alloy nanoparticles, a potential candidate for microwave absorption material, were successfully synthesized by tuning the reduction timing of Co and Ni ions by introducing oleylamine as a complexing agent and 1-heptanol as a reducing solvent. The formation mechanism elucidated using time-resolved sampling and in situ X-ray absorption spectroscopy (XAS) and ultraviolet-visible (UV-vis) spectrophotometry measurements suggested that the delay in the reduction of Co ions via complexation with oleylamine facilitated the co-reduction of Co with Ni ions and led to the formation of Co-Ni alloys. The successful synthesis of Co-Ni alloys experimentally confirmed the differences in magnetic properties between alloy and core-shell structured Co50Ni50 particles. Further, the syntheses of Co-Ni alloys with different compositions were also possible using the above technique. In addition, the microwave absorption properties were measured using the free-space method utilizing a vector network analyzer of Co50Ni50─polyethylene composite with different sheet thicknesses. A reflection loss (RL) value of -25.7 dB at 13.6 GHz for the alloy structure was more significant than the core-shell counterpart. The above values are high compared to results reported in the past. The validity of the measurements was confirmed by utilizing the parameter retrieval method to extract permittivity and permeability from the scattering parameter (S) and recalculation of the RL as a function of frequency.

Theoretical and Experimental Evaluation of the Reduction Potential of Straight-Chain Alcohols for the Designed Synthesis of Bimetallic Nanostructures.

Recently, the development of bimetallic nanoparticles with functional properties has been attempted extensively but with limited control over their morphological and structural properties. The reason was the inability to control the kinetics of the reduction reaction in most liquid-phase syntheses. However, the alcohol reduction technique has demonstrated the possibility of controlling the reduction reaction and facilitating the incorporation of other phenomena such as diffusion, etching, and galvanic replacement during nanostructure synthesis. In this study, the reduction potential of straight-chain alcohols has been investigated using molecular orbital calculations and experimentally verified by reducing transition metals. The alcohols with a longer chain exhibited higher reduction potential, and 1-octanol was found to be the strongest among alcohols considered. Furthermore, the experimental evaluation carried out via the synthesis of metallic Cu, Ni, and Co particles was consistent with the theoretical predictions. The reaction mechanism of metallic particle formation was also studied in detail in the Ni-1-octanol system, and the metal ions were confirmed to be reduced via the formation of nickel alkoxide. The results of this investigation were successfully implemented to synthesize Cu-Ni bimetallic nanostructures (core-shell, wire, and tube) via the incorporation of diffusion and etching besides the reduction reaction. These results suggest that the designed synthesis of a wide range of bimetallic nanostructures with more refined control has become possible.

Evaluation of quality of life among patients with ischemic heart disease who practiced self-care activities at home after elective percutaneous coronary intervention.

The present study compares health-related QOL between patients who practiced self-care activities comprising exercise and diet at home for at least 6 months (SA group; n = 84) after elective PCI and those who did not (NA group; n = 54). Health-related (HR) QOL was measured using the SF-36 questionnaire. Scores for two mental and three physical parameters of the HRQOL were increased in the SA, but not in the NA group. These findings indicated that the QOL was far superior among patients who exercised and consumed an appropriate diet at home for at least 6 months after elective PCI compared with those who did not.

The fate of arsenic in a river acidified by volcanic activity and an acid thermal water and sedimentation mechanism.

The Shozu-gawa river, located in the Aomori Prefecture, northern Japan, is affected by volcanic activities and acid thermal waters. The river is unique because both solid arsenic (As; as orpiment, As2S3) and dissolved As are supplied to the river from the uppermost caldera lake (Usori-ko Lake) and thermal ponds. The watershed is an excellent site for investigating the fate of different As species in a fluvial system. Upstream sediments near the caldera lake and geothermal ponds are highly contaminated by orpiment. This solid phase is transported as far as the mouth of the river. On the other hand, dissolved As is removed from the river system by hydrous ferric oxides (HFOs); however, HFO formation and removal of dissolved As do not occur in the uppermost area of the watershed, resulting in further downstream transport of dissolved As. Consequently, upstream river sediments are enriched in orpiment, whereas As(v), which is associated with HFOs in river sediments, increases downstream. Furthermore, orpiment particles are larger, and possibly heavier, than those of HFO with sorbed As. Fractionation between different chemical states of As during transport in the Shozu-gawa river is facilitated not only by chemical processes (i.e., sorption of dissolved As by HFOs), but also by physical factors (i.e., gravity). In contrast to acid mine drainage (AMD), in some areas of the Shozu-gawa river, both solid forms of As (as sulfide minerals) and dissolved As are introduced into the aquatic system. Considering that the stabilities of sulfide minerals are rather different from those of oxides and hydroxides, river sediments contacted with thermal waters possibly act as sources of As under both aerobic and anaerobic conditions.

Tetravalent dysprosium in a perovskite-type oxide.

The existence of tetravalent dysprosium in perovskite-type oxide barium zirconate is confirmed in this work. This discovery will stimulate many researchers in diverse fields such as catalysts, solid state ionics, sensors, and fluorescent materials.

Effects of cultivation conditions on the uptake of arsenite and arsenic chemical species accumulated by Pteris vittata in hydroponics.

The physiological responses of the arsenic-hyperaccumulator, Pteris vittata, such as arsenic uptake and chemical transformation in the fern, have been investigated. However, a few questions remain regarding arsenic treatment in hydroponics. Incubation conditions such as aeration, arsenic concentration, and incubation period might affect those responses of P. vittata in hydroponics. Arsenite uptake was low under anaerobic conditions, as previously reported. However, in an arsenite uptake experiment, phosphorous (P) starvation-dependent uptake of arsenate was observed under aerobic conditions. Time course-dependent analysis of arsenite oxidation showed that arsenite was gradually oxidized to arsenate during incubation. Arsenite oxidation was not observed in any of the control conditions, such as exposure to a nutrient solution or to culture medium only, or with the use of dried root; arsenite oxidation was only observed when live root was used. This result suggests that sufficient aeration allows the rhizosphere system to oxidize arsenite and enables the fern to efficiently take up arsenite as arsenate. X-ray absorption near edge structure (XANES) analyses showed that long-duration exposure to arsenic using a hydroponic system led to the accumulation of arsenate as the dominant species in the root tips, but not in the whole roots, partly because up-regulation of arsenate uptake by P starvation of the fern was caused and retained by long-time incubation. Analysis of concentration-dependent arsenate uptake by P. vittata showed that the uptake switched from a high-affinity transport system to a low-affinity system at high arsenate concentrations, which partially explains the increased arsenate abundance in the whole root.

GAS-PHASE FLAME SYNTHESIS AND PROPERTIES OF MAGNETIC IRON OXIDE NANOPARTICLES WITH REDUCED OXIDATION STATE.

Iron oxide nanoparticles of reduced oxidation state, mainly in the form of magnetite, have been synthesized utilizing a new continuous, gas-phase, nonpremixed flame method using hydrocarbon fuels. This method takes advantage of the characteristics of the inverse flame, which is produced by injection of oxidizer into a surrounding flow of fuel. Unlike traditional flame methods, this configuration allows for the iron particle formation to be maintained in a more reducing environment. The effects of flame temperature, oxygen-enrichment and fuel dilution (i.e. the stoichiometric mixture fraction), and fuel composition on particle size, Fe oxidation state, and magnetic properties are evaluated and discussed. The crystallite size, Fe(II) fraction, and saturation magnetization were all found to increase with flame temperature. Flames of methane and ethylene were used, and the use of ethylene resulted in particles containing metallic Fe(0), in addition to magnetite, while no Fe(0) was present in samples synthesized using methane.

pH-dependence of selenate removal from liquid phase by reductive Fe(II)-Fe(III) hydroxysulfate compound, green rust.

Removal of selenate ion from the liquid phase by hydroxysulfate green rust (GR(SO4)) was investigated in the pH range from 7.5 to 10.0. Batch tests showed that the total selenium concentration decreased more rapidly with increasing pH. However, the amount of selenium removed from the liquid phase increased as the pH decreased. X-ray absorption spectrometric analysis demonstrated that the Se(VI) in the selenate ion was reduced to elemental selenium Se(0) at pH 9.0, whereas the existence of small amount of intermediate Se(IV) was detected at pH 7.5. Comparing the mass balance of the amount of consumed ferrous iron in GR(SO4), [DeltaFe(II)], and the amount of Se(VI) removed from the liquid phase, [DeltaSe(VI)], [DeltaFe(II)] is approximately six times larger than [DeltaSe(VI)] in mol units. This is also indirect but convincing evidence that the oxidation of Fe(II) in GR(SO4) leads to the simultaneous reduction of Se(VI) to Se(0). Powder X-ray diffraction analysis showed that the end product of GR(SO4) depends on the pH: magnetite for pH>9.0, goethite for pH<8.0, and their mixture at pH 8.5. These results indicate that the solution pH has a significant effect on the reaction path of selenate removal by GR(SO4).

Ultra-stable nanoparticles of CdSe revealed from mass spectrometry.

Nanoparticles under a few nanometres in size have structures and material functions that differ from the bulk because of their distinct geometrical shapes and strong quantum confinement. These qualities could lead to unique device applications. Our mass spectral analysis of CdSe nanoparticles reveals that (CdSe)(33) and (CdSe)(34) are extremely stable: with a simple solution method, they grow in preference to any other chemical compositions to produce macroscopic quantities. First-principles calculations predict that these are puckered (CdSe)(28)-cages, with four- and six-membered rings based on the highly symmetric octahedral analogues of fullerenes, accommodating either (CdSe)(5) or (CdSe)(6) inside to form a three-dimensional network with essentially heteropolar sp(3)-bonding. This is in accordance with our X-ray and optical analyses. We have found similar mass spectra and atomic structures in CdS, CdTe, ZnS and ZnSe, demonstrating that mass-specified and macroscopically produced nanoparticles, which have been practically limited so far to elemental carbon, can now be extended to a vast variety of compound systems.