ABSTRACT
Oxyhydrides are promising compounds as supports for ammonia synthesis catalysts because they suppress hydrogen poisoning on the catalyst surface and enhance the ammonia synthesis activity. Herein, we developed a facile method for preparing BaTiO2.5H0.5, a perovskite oxyhydride, on a TiH2 surface via the conventional wet impregnation method using TiH2 and Ba hydroxide. Scanning electron microscopy and high-angle annular dark-field scanning transmission electron microscopy observations revealed that BaTiO2.5H0.5 crystallized as nanoparticles of ca. 100-200 nm on the TiH2 surface. The Ru-loaded catalyst Ru/BaTiO2.5H0.5-TiH2 exhibited 2.46 times higher ammonia synthesis activity (3.05 mmol-NH3 g-1 h-1 at 400 °C) than the benchmark Ru catalyst Ru-Cs/MgO (1.24 mmol-NH3 g-1 h-1 at 400 °C) because of the suppression of hydrogen poisoning. The analysis of reaction orders showed that the effect of suppressing hydrogen poisoning on Ru/BaTiO2.5H0.5-TiH2 was equivalent to that of the reported Ru/BaTiO2.5H0.5 catalyst, thus supporting the formation of BaTiO2.5H0.5 perovskite oxyhydride. This study demonstrated that the selection of appropriate raw materials facilitates the formation of BaTiO2.5H0.5 oxyhydride nanoparticles on the TiH2 surface using the conventional synthesis method.
ABSTRACT
Ru/Ce0.5La0.5-xTixO1.75+0.5x solid solutions with cubic fluorite structure were successfully synthesized via the polymerized complex method. While the Ti substitution enhanced Ce4+ reducibility by compensating for oxygen vacancies, the reducibility showed no correlation with ammonia synthesis activity. However, Ru/Ce0.5La0.4Ti0.1O1.8 showed the highest activity originating from the facilitated formation of mesopores.
ABSTRACT
Ca-Bridged siloxenes (Ca-siloxenes) composed of two-dimensional siloxene planes with Ca bridging were prepared and their photocatalytic properties for nitrogen oxide (NO) removal were investigated. Ca-Siloxenes were synthesized via a solid-state metathesis reaction using TaCl5 to extract Ca from CaSi2 with different Cl2/Ca molar ratios of 0.25, 1.25 and 2.5 (CS0.25, CS1.25 and CS2.5, respectively) in an attempt to control the extent of Ca extraction. Ca-Siloxenes have a wide optical absorption band from the visible to ultraviolet region with absorption edges of 1.5, 2.9, and 3.1 eV for CS0.25, CS1.25, and CS2.5, respectively. Ca-Siloxenes exhibited photocatalytic activity for NO removal under irradiation with visible (λ > 400 nm (<3.10 eV)) and ultraviolet light (λ > 290 nm (<4.28 eV)). The photocatalytic activity was particularly improved by mixing the Ca-siloxene with acetylene black as a conductive material, which might have inhibited the recombination of photogenerated electrons and holes. The mixture of Ca-siloxene and acetylene black exhibited improved photocatalytic activity in the presence of 1O2 as one of the active oxygen species formed under ultraviolet light irradiation.
ABSTRACT
The photocatalytic decomposition of nitrogen monoxide (NO) was achieved for the first time using Si-based nanomaterials. Nanocomposite powders composed of Si nanoflakes and metallic particles (Ni and Ni3Si) were synthesized using a simple one-pot reaction of layered CaSi2 and NiCl2. The synthesized nanocomposites have a wide optical absorption band from the visible to the ultraviolet. Under the assumption of a direct transition, the photoabsorption behavior is well described and an absorption edge of ca. 1.8 eV is indicated. Conventional Si and SiO powders with indirect absorption edges of 1.1 and 1.4 eV, respectively, exhibit considerably low photocatalytic activities for NO decomposition. In contrast, the synthesized nanocomposites exhibited photocatalytic activities under irradiation with light at wavelengths >290 nm (<4.28 eV). The photocatalytic activities of the nanocomposites were confirmed to be constant and did not degrade with the light irradiation time.
ABSTRACT
A Ca-bridged siloxene (Ca-siloxene) composed of two-dimensional siloxene planes with Ca bridging was synthesized via a solid state metathesis reaction using TaCl5 to extract Ca from CaSi2. Three different Ca-siloxenes synthesized at Cl2/Ca molar ratios of 0.25, 1.25 and 2.5 (CS0.25, CS1.25 and CS2.5, respectively) were fabricated and investigated as anode active materials for lithium-ion batteries. Both secondary and primary Ca-siloxene particles, which serve to increase the contact interfaces with conductive materials and to generate accessible sites for lithium ions, respectively, were found to become smaller and to have increased pore volumes as the Cl2/Ca molar ratio was increased. These Ca-siloxenes exhibited stable charge/discharge performance as anode materials, with 69-99% capacity retention after 50 charge/discharge cycles (compared with 36% retention for a conventional Kautsky-type siloxene). The charge capacity also increased with increases in the Cl2/Ca molar ratio, such that the CS2.5 showed the highest capacity after 50 charge/discharge cycles. This may reflect the formation of Si6Li6 rather than SiLi4.4 and suggests the maintenance of layered Si planes for large capacity retention after charge/discharge cycling. The increase of contact interfaces between acetylene black (as a conductive material) and Ca-siloxenes was found to effectively increase the lithium-ion capacity of Ca-siloxene during high rate charge/discharge cycling.
ABSTRACT
Silicon-based nanocomposites with slitlike nanopores were prepared by heating a mixture of layered CaSi2 and NiCl2. The formation mechanism is based on a solid-state exfoliation reaction wherein the formation of CaCl2 promotes the extraction of Ca from CaSi2, thereby exfoliating the layered structure. The nanocomposites showed anode capacity for lithium ion batteries up to 804â mA h g(-1).
