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.

Kinetically Controlled Direct Synthesis of B2- and A1-Structured Cu-Pd Nanoparticles.

Atomic arrangement in Cu-Pd alloy nanoparticles (NPs) has been reported to influence the catalytic activity, but they have yet to be studied in detail. Unlike previous studies, where the B2 structure Cu-Pd NPs are obtained by heat treating the A1 structure, this study reports the one-pot direct syntheses of A1- and B2-structured Cu-Pd NPs using an alcohol reduction method. The alcohol reduction technique facilitates the kinetic control of the reduction reaction by selecting the appropriate alcohol type and complexing agent to delay the reduction of easily reducible metallic elements to realize control over the reduction kinetics for coreduction. Different formation mechanisms for A1- and B2-structured CuPd NPs were confirmed by in situ ultraviolet-visible (UV-vis) measurements and morphological and structural analyses of samples withdrawn during the reaction. Finally, the direct formation of single-phase B2-structured Cu-Pd NPs with an average diameter of 18.6 ± 7.6 nm was realized using tri-n-octyl phosphine as a complexing agent. The noticeable crystal structural dependence of the electrocatalytic CO2 reduction reaction properties of A1- and B2-structured CuPd NPs was demonstrated.

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.

Strategy to Design-Synthesize Bimetallic Nanostructures Using the Alcohol Reduction Method.

Bimetallic nanomaterials have attracted much attention from various fields such as catalysis, optics, magnetism, and so forth. The functionality of such particles is influenced very much by the intermetallic interactions than their individual contribution. However, compared with the synthesis of monometallic nanoparticles, the reaction parameters that need to be controlled for tuning the size, shape, composition, and crystal structure of bimetallic nanoparticles becomes challenging. This study focuses on synthesizing of bimetallic nanostructures using the alcohol reduction method, where the control over the reducing power is conceivable by varying the combination of the alcohol type, complexing agent, and metal salts. Consequently, various Cu-Co nanostructures such as Cu-Co core-shell (size ranged between 40 and 15 nm) and hollow alloy nanoparticles and nanotubes were successfully synthesized by incorporating diffusion and etching phenomena during the reduction reaction. Moreover, time-resolved sampling revealed that the formation of a Cu-Co alloy hollow nanostructure has been realized by the diffusion of the Cu core into the Co shell by controlling the reduction time gap between Cu and Co and the crystal structure besides the reduction sequences. It should be noted that the synthesis of a high-temperature (∼1300 °C) Cu-Co alloy phase was carried out at 170 °C. Among the Cu-Co alloy nanostructures, Cu-Co hollow alloy nanoparticles exhibited enhanced catalytic activity compared to metallic Cu and other Cu-Co nanostructures from the degradation reaction of methylene blue. The enhanced catalytic performance was considered to be mainly due to the alloy structure.

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.

Selection Criteria for Metal Precursors and Solvents for Targeted Synthesis of Metallic Nanostructures Via Kinetic Control in the Polyol Process.

Development of a technology for the synthesis of monometallic or multimetallic nanoparticles is exceptionally vital for the preparation of novel magnetic, optical. and catalytic functional materials. In this context, the polyol process is a safe and scalable method for preparation of metal nanoparticles with controlled sizes and shapes in large scales. However, there is no systematic investigation that discusses the criteria for the selection of metal salt and solvent type that determine the kinetics of reduction reaction that influences the morphology of the particles. Consequently, the design of metallic nanoparticles, which is controlled by the kinetics and thermodynamics of the reduction reaction, has become difficult. In this paper, the selection criterion for metal salt precursor is established based on the presumption that the ligand of the metal precursor promotes the formation of active species of the solvent, and the criterion for the selection of the solvent type is based on the highest occupied molecular orbital (HOMO) energy value estimated using molecular orbital theory. The results suggested that the dissociation constants of metal salt precursors and HOMO energy of the polyol solvent can be tuned to control the kinetics of the reduction reaction. The reduction potential of polyol depends on the number of carbon atoms and the location of hydroxyl ligands within the molecule. Among the polyols considered in this study, 1,4-butanediol had the highest reduction potential. The predictions have been experimentally verified by synthesizing metallic Co and Fe nanoparticles. The findings could be extended to other techniques such as thermal decomposition and alcohol reduction for the synthesis of noble metal-transition metal magnetic and catalytic nanoparticles with novel properties.

Estimation of Magnetic Anisotropy of Individual Magnetite Nanoparticles for Magnetic Hyperthermia.

Ideal interaction-free magnetite nanoparticles were prepared, and their magnetic properties were measured to clarify the true nature of magnetic anisotropy of individual magnetite nanoparticles at the nanoscale and to analyze the shape, surface, and crystalline anisotropy contributions. Spherical (17.7 nm), cubic (10.6 nm), and octahedral-shaped magnetite nanoparticles with average sizes ranging from 7.6 to 23.4 nm were synthesized using solution techniques. Then, these nanoparticles were coated with silica at appropriate shell thicknesses to prepare magnetic interaction-free samples, and their noninteractive nature was confirmed through first-order reversal curve diagrams. For these well-isolated nanoparticles, remanent magnetizations of the hysteresis loops are just equal to a half of the saturation magnetization. This result clearly indicates that uniaxial magnetic anisotropy is predominant in each nanoparticle. In order to clarify the details of the uniaxial magnetic anisotropy, the analysis of blocking temperature-switching field distribution diagrams is constructed based on thermal decay curves of isothermal remanent magnetization at various applied fields. The obtained effective magnetic anisotropy constant Keff is distributed around 10-20 kJ/m3 and has insignificant size dependence. This result seems inconsistent with the inverse proportion relation of Keff with size predicted for surface magnetic anisotropy. The theoretical calculation suggested that the crystalline magnetic anisotropy plays a major role in magnetic properties of the magnetite nanoparticles at lower temperatures. However, it should be noted that Keff seems slightly different for the different shapes. The above study indicates that control size, shape, and interparticle interactions is required to strictly discuss such delicate differences of magnetic anisotropy of individual magnetite nanoparticles for the design of thermal seeds for magnetic hyperthermia.

Design of monoalcohol - Copolymer system for high quality silver nanowires.

Research to improve the dimensional properties of silver nanowires (Ag NWs) for transparent conductive film (TCF) applications are being carried out intensively. However, the protocol for the designed synthesis of high-quality Ag NWs is yet to be developed due to the inadequacy of knowledge on the role of parameters. Here, we attempt to elucidate the role played by the parameters and propose a monoalcohol-copolymer based system for the designed synthesis of Ag NWs superior in quality to the one synthesized using conventional ethylene glycol (EG)-polyvinylpyrrolidone (PVP) system. The key findings of the study are as follows: (1) the solubility of Ag source and the partially formed AgCl particles in monoalcohols was found to play an important role not only in the reduction to metallic Ag but also on the uniaxial growth, (2) the adsorption of capping agents on Ag NWs was carried through O and N atoms in the base molecule and their binding energies indicated that the strength is the key parameter to obtain Ag NWs with high aspect ratio, (3) the properties of nanowire could be enhanced through copolymerization of VP and base molecules that have O- and N-based ligands, and (4) the influence of copolymerization on the physical and chemical properties of the surface active agent has been theoretically and experimentally verified. Consequently, we succeeded in the development of a new technique to synthesize high yield of Ag NWs with improved aspect ratio than EG-PVP system by using benzyl alcohol as reducing solvent and N-vinylpyrrolidone/N,N-diethylaminoethyl metacrylate copolymer as a capping agent. The optical transmittance and electrical resistivity of TCFs prepared using the Ag NWs with an average diameter of 43 nm, and an average length of 13 µm were 98.6% and R: 49.1 Ω/□, respectively.