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Mori, Toshiyuki

Publications and source records attributed to Mori, Toshiyuki.

Activating Nitrogen–doped Graphene Oxygen Reduction Electrocatalysts in Acidic Electrolytes using Hydrophobic Cavities and Proton–conductive Particles

Although pyridinic-nitrogen (pyri-N) doped graphene is highly active for the oxygen reduction reaction (ORR) of fuel cells in alkaline media, the activity critically decreases under acidic conditions. Herein we report on how to prevent the deactivation based on the mechanistic understanding that O 2 + pyri–NH ⁺ + e – → O 2,a + pyri–NH governs the ORR kinetics. First, we considered that the deactivation is due to the hydration of pyri-NH + , leading to a lower shift of the redox potential. Introducing the hydrophobic cavity prevented the hydration of pyri-NH + but inhibited the proton transport. We then increased proton conductivity in the hydrophobic cavity by introducing SiO 2 particles coated with ionic liquid polymer/Nafion® which kept the high onset potentials with an increased current density even in acidic media.

25 ENERGY STORAGE↗

Evidence for participation of GCS1 in fertilization of the starlet sea anemone Nematostella vectensis: Implication of a common mechanism of sperm–egg fusion in plants and animals

Highlights: • GCS1 is a sperm transmembrane protein that is essential for gamete fusion in flowering plants. • The GCS1 gene is present not only in angiosperms but also in unicellular organisms and animals. • NvGCS1 gene is expressed in the testis and GCS1 protein exists in sperm of a sea anemone. • Anti-GCS1 antibodies inhibited the fertilization, showing the participation in fertilization. - Abstract: It has been reported that GCS1 (Generative Cell Specific 1) is a transmembrane protein that is exclusively expressed in sperm cells and is essential for gamete fusion in flowering plants. The GCS1 gene is present not only in angiosperms but also in unicellular organisms and animals, implying the occurrence of a common or ancestral mechanism of GCS1-mediated gamete fusion. In order to elucidate the common mechanism, we investigated the role of GCS1 in animal fertilization using a sea anemone (Cnidaria), Nematostella vectensis. Although the existence of the GCS1 gene in N. vectensis has been reported, the expression of GCS1 in sperm and the role of GCS1 in fertilization are not known. In this study, we showed that the GCS1 gene is expressed in the testis and that GCS1 protein exists in sperm by in situ hybridization and proteomic analysis, respectively. Then we made four peptide antibodies against the N-terminal extracellular region of NvGCS1. These antibodies specifically reacted to NvGCS1 among sperm proteins on the basis of Western analysis and potently inhibited fertilization in a concentration-dependent manner. These results indicate that sperm GCS1 plays a pivotal role in fertilization, most probably in sperm–egg fusion, in a starlet sea anemone, suggesting a common gamete-fusion mechanism shared by eukaryotic organisms.

60 APPLIED LIFE SCIENCES↗

Defects clustering and ordering in di- and trivalently doped ceria

Graphical abstract: Display Omitted Highlights: ► Defect structures in trivalently and divalently doped ceria has been elucidated. ► Dumbbell structure is a universal basic vacancy structure in fluorite oxides. ► Electrostatic attraction dominates elastic interaction in doped ceria. ► Provide a physical picture of conductivity behavior in aliovalently doped ceria. -- Abstract: The formation and growth of defect clusters in CeO{sub 2}-M{sub 2}O{sub 3} (M = La{sup 3+}, Pr{sup 3+}, Sm{sup 3+}, Gd{sup 3+}, Dy{sup 3+}, Y{sup 3+}, Yb{sup 3+}) and CeO{sub 2}-DO (N = Cd{sup 2+}, Ca{sup 2+}, Sr{sup 2+}, Ba{sup 2+}) binary solid solutions have been comparatively studied by atomistic simulations based on energy minimization of atomic interactions. The calculation ensemble, including both divalent and trivalent dopants, shows a similar energetic tendency for defect species (dopants and associated oxygen vacancies) to aggregate and grow. The dumbbell structure has been verified as a universal vacancy structure in oxygen deficient fluorite lattice. Nevertheless, it also demonstrates different tendencies of dopant–vacancy associations that depend on dopant valence and radius. The dopant is site-selective in trivalent defect clusters correlated with dopant size. While in divalent solid solutions, clusters adopt similar dopant–vacancy locations. Furthermore, all clusters in divalently doped ceria have stronger dopant–vacancy associations/interactions compared to those in trivalent ones. As a consequence, the correlation of the dopant size as well as valence effects on oxygen-ion conductivity has been illustrated based on an ordered defect cluster model. This study thereby offers insight into the physical picture of ionic conductivity behavior experimentally obtained in aliovalently doped ceria.

36 MATERIALS SCIENCE↗

Incubational domain characterization in lightly doped ceria

Microstructures of both Gd- and Y-doped ceria with different doping level (i.e., 10 at% and 25 at%) have been comprehensively characterized by means of high resolution transmission electron microscopy and selected area electron diffraction. Coherent nano-sized domains can be widely observed in heavily doped ceria. Nevertheless, it was found that a large amount of dislocations actually exist in lightly doped ceria instead of heavily doped ones. Furthermore, incubational domains can be detected in lightly doped ceria, with dislocations located at the interfaces. The interactions between such linear dislocations and dopant defects have been simulated accordingly. As a consequence, the formation mechanism of incubational domains is rationalized in terms of the interaction between intrinsic dislocations of doped ceria and dopant defects. This study offers the insights into the initial state and related mechanism of the formation of nano-sized domains, which have been widely observed in heavily rare-earth-doped ceria in recent years. - Graphical abstract: Interactions between dislocations and dopants lead to incubational domain formation in lightly doped ceria. Highlights: Black-Right-Pointing-Pointer Microstructures were characterized in both heavily and light Gd-/Y-doped ceria. Black-Right-Pointing-Pointer Dislocations are existed in lightly doped ceria rather than heavily doped one. Black-Right-Pointing-Pointer Interactions between dislocations and dopant defects were simulated. Black-Right-Pointing-Pointer Formation of dislocation associated incubational domain is rationalized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanodomain formation and distribution in Gd-doped ceria

Highlights: Black-Right-Pointing-Pointer Comprehensive investigation of nanodomain formation and distribution in Gd-doped ceria. Black-Right-Pointing-Pointer Direct experimental evidence of nanodomain formation at grain boundaries. Black-Right-Pointing-Pointer Nanodomain at grain boundaries would be another possible reason for grain boundary resistivity. -- Abstract: A comprehensive study, with a combination of diverse analytical techniques, was performed to investigate nanodomain formation and distribution in gadolinium-doped ceria. It is illustrated that the nanodomain formation, originating from the aggregation and segregation of dopant cations together with associated charge-compensating oxygen vacancies, is ubiquitous throughout doped ceria. The formation of nanodomains is not limited to bulk areas as previously reported but exists at grain boundaries as well. With enhanced ordering level, such nanodomains formed at grain boundaries will decrease the ionic conductivity as a result of hindered the mobility of oxygen vacancies in doped ceria. Particularly, the nanodomains formed at grain boundaries, with strong defect interactions due to enrichment of dopants and ordered oxygen vacancies, are suggested to be another possible reason for the grain-boundary resistance, other than the widely accepted space-charge layers.

36 MATERIALS SCIENCE↗

Two types of diffusions at the cathode/electrolyte interface in IT-SOFCs

Analytical transmission electron microscopy, in particular with the combination of energy dispersive X-ray spectroscopy (EDX) and electron energy-loss spectroscopy (EELS), has been performed to investigate the microstructure and microchemistry of the interfacial region between the cathode (La{sub 0.6}Sr{sub 0.4}Co{sub 0.8}Fe{sub 0.2}O{sub 3}, LSCF) and the electrolyte (Gd-doped ceria, GDC). Two types of diffusions, mutual diffusion between cathode and electrolyte as well as the diffusion along grain boundaries, have been clarified. These diffusions suggest that the chemical stability of LSCF and GDC are not as good as previously reported. The results are more noteworthy if we take into consideration the fact that such interdiffusions occur even during the sintering process of cell preparation. - Graphical Abstract: Two types of diffusions, the mutual diffusion and the diffusion along grain boundaries, occurred at the cathode/electrolyte interface of intermediate temperature solid state fuel cells, during cell preparation. The mutual diffusion is denoted by black arrows and the diffusion along grain boundaries assigned by pink arrows. Highlights: > All the cations in cathode (LSCF) and electrolyte (GDC) can mutually diffuse into each other. > Diffusing elements will segregate at grain boundaries or triple junctions around the cathode/electrolyte interface. > Two types of diffusions, the mutual diffusion and diffusion along grain boundaries, have been clarified thereafter.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗