Fast proton conductors for low humidity: hydrophilic sulfonated and phosphonated polysilsesquioxanes with Al-O-P crosslinks.

Proton-conducting polysilsesquioxane oligomers with core-shell structures consisting of hydrophilic silica-rich cores surrounded by an organic layer with sulfonic and phosphonic acid groups were synthesized. They were crosslinked by mixing with phosphoric acid and aluminum ions to form a hydrophilic Al-O-P framework. The resulting polymers were clear, uniform, flexible, and exhibited a high proton conductivity above 100 °C in non-humidified low-humidity air (∼22 mS cm-1 at 120 °C and ∼1%RH) because of their high sulfonic acid concentration and high water retention capability.

Crystal structures of the alkali aluminoboracites A4B4Al3O12Cl (A = Li, Na).

Single crystals of alkali aluminoboracites, A 4B4Al3O12Cl (A = Li, Na), were grown using the self-flux method, and their isotypic cubic crystal structures were determined by single-crystal X-ray diffraction. Na4B4Al3O12Cl is the first reported sodium boracite, and its lattice parameter [13.5904 (1) Å] is the largest among the boracites consisting of a cation-oxygen framework reported so far. For both crystals, structure models refined in the cubic space group F 3c, which assume that all cubic octant subcells in the unit cell are equivalent, converged with R1 factors of ∼0.03. However, the presence of weak hhl reflections with odd h and l values indicates that refinements in the space group F23, which presume a checkerboard-like ordering of two types of subcells with slightly different atomic positions, are more appropriate.

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.

Temperature dependence of narrow-band UVB photoluminescence of silica-(Gd,Pr)PO4transparent glass-ceramic phosphors.

The effect of temperature on photoluminescence (PL) due to the6Pj→8S7/2(j= 5/2, 7/2) transitions of Gd3+ions was examined between 200 and 500 K for a sol-gel-derived silica-(Gd,Pr)PO4transparent glass-ceramic phosphor with negligible concentration quenching under excitation into the 5d-4f transition of Pr3+ions at 220 nm. The intensity of the narrow-band ultraviolet B (UVB) PL at ∼313 nm associated with the6P7/2→8S7/2transition slightly increased between 200 and 300 K, but was decreased to ∼86% and ∼62% of that at 300 K when temperature was raised to 400 and 500 K, respectively. The observed magnitude of the thermal quenching of the UVB PL intensity was agreed well with that recorded in a prototype narrow-band UVB lamp consisting of another silica-(Gd,Pr)PO4transparent glass-ceramic window and a KrCl excimer lamp as a light source at 222 nm. The silica-(Gd,Pr)PO4transparent glass-ceramics was more resistant to the thermal quenching of the narrow-band UVB PL than a conventional powder phosphor, probably because of the encapsulation of (Gd,Pr)PO4nanocrystals with low quenching centre concentrations in inert silica glass matrix.

Poly(cyclohexylsilsesquioxane)-Based Hydrophilic Thermoset-Resistant Deep-Ultraviolet-Transparent Glasses with Low Melting Temperatures.

Silsesquioxane (SQ)-based glasses with low melting temperatures were prepared by the cosolvent-free (solventless) hydrolytic polycondensation of organotrimethoxysilanes with cyclopentyl (c-Pe) and cyclohexyl (c-Hx) groups. Copolymers consisting of phenylsilsesquioxane (Ph-SQ) units and c-Pe-SQ units [poly(Ph-co-c-Pe-SQ)] or c-Hx-SQ units [poly(Ph-co-c-Hx-SQ)] were melted at 140 °C and formed clear glasses. The glasses prepared by this method contained many residual SiOH groups and exhibited high adhesive strength to microscope glass plates, metals, and several polymers. The glass-transition temperature of poly(c-Hx-SQ) was lower than that of poly(Ph-SQ) by only a small margin, whereas that of poly(c-Pe-SQ) was much lower. The poly(c-Hx-SQ)-based glasses were stiff at room temperature and transparent in the deep-ultraviolet spectral region (≲300 nm). They formed fragile melts with kinetic fragility parameters as high as ∼0.8. The melts of poly(c-Hx-SQ) and poly(c-Hx-co-Et-SQ) exhibited better resistance to thermal curing than that of poly(Ph-SQ) and maintained thermoplasticity even after heat treatment at 200 °C for 6 h.

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.