Papers by Author: Hidenobu Shiroishi

Abstract: Hollandite-type Mn oxides were synthesized by a co-precipitation (CP) and a hydrothermal (HT) method as the cathode catalysts for anion-exchange membrane fuel cells (AEMFCs), and their oxygen reduction reaction (ORR) activities and AEMFC single cell performances were evaluated. In this study, we prepared two kinds of hollandite oxides K_0.14MnO₂·0.12H₂O(KMO-CP) and K_0.12MnO₂·0.06H₂O(KMO-HT) and their partially Co-substituted ones K_0.11(Mn_0.88 Co_0.12)O₂・0.16H₂O(KMC_0.12-CP) and K_0.11(Mn_0.88Co_0.12)O₂· 0.08H₂O(KMC_0.12-HT), and examined the ORR activities with a rotating ring-disk electrode (RRDE) in 0.1 M KOH at 50°C. All the samples showed high onset potentials of ORR, ca. 0.9 V vs. reversible hydrogen electrode (RHE), and relatively high ORR currents at 0.75 V and high efficiencies for 4-electron reduction (Eff₄) of around 90% were obtained for the HT samples owing to higher crystallinity and higher specific surface area than those of the CP ones. The AEMFC single cells prepared with KMO-HT and KMC_0.12-HT cathode catalysts were operated stably and exhibited the maximum power densities of ca. 49 and 42 mW cm^-2, respectively, which were comparable to that of the single cell using a conventional 50 wt% Ag/C catalyst.

Abstract: The Mn-doped pyrochlores Pb2Ru1.5Mn0.5O7- (PRMns) samples were synthesized by a precipitation method, followed by heat-treatments at temperatures of 300-800oC. Effects of the heat-treatments on their electrocatalytic activities for oxygen reduction reaction (ORR) were examined by semi-steady state voltammetry with a rotating ring-disk electrode in 0.1 M KOH solution at 70oC. The PRMns showed the best ORR activity for the 500oC-heat-treated PRMn. The onset potential of the ORR current was over 1.0 V vs RHE, and the efficiency of 4-electron reduction was almost 100%. The maximum in the ORR activity for the 500°C-heat-treated PRMn resulted from a trade-off effect between their crystallinity and specific surface areas.

Abstract: Proton conducting ZrO2－yP2O5 (y = 1.0, 1.2, 1.4. 1.6, 1.8) electrolytes based on a shell-core structure were synthesized with diammonium hydrogen phosphate by a solid state reaction, and their conductivities were investigated by ac-impedance spectroscopy. Among the ZrO2-yP2O5 compositions, ZrO2－1.6P2O5 showed the highest proton conductivity of 0.13 Scm-1 at 250°C. The conductivity increased with increasing P2O5 molar ratio and were significantly influenced by heat-treatments in the preparation process. Polytetraflouroethylene (PTFE) was also mixed into these electrolytes in order to improve the mechanical strength and long term durability.

Abstract: The trirutile oxides MTa2O6 (M=Co,Ni,Mg) [MTs] and the substitution products M1-xNxTa2-yLyO6 (N=Mn, L=Sn,Ti,Zr) [M1-xNxTa2-yLy] were prepared by a conventional solid-state reaction. The oxygen reduction reaction (ORR) activities were evaluated with the onset potentials (Eon) of the ORR currents, the disk current densities (iD) and the efficiencies (Eff4) of 4-electron reduction, measured by a rotating ring-disk electrode (RRDE) technique. All the samples showed ORR activities and the Eon values were around +0.8 V vs. RHE in 0.1 M KOH. The CoTa2O6 electrocatalyst showed the best ORR property of the MTs samples: its Eff4 value was as high as ~80%. With substitution of Ti or Sn, the ORR activities of MgTa1.9T0.1O6, CoTa1.8Sn0.2O6 and NiTa1.9Ti0.1O6 were improved in alkaline solution, compared with those of MTa2O6. In acid solution, the same substitution of Ti and Sn resulted in improvement of Eff4, but no significant improvements of Eon and iD.

Abstract: Photocatalytic proton reduction and water oxidation have been studied in a tris(2,2’-bipyridyl)ruthenium complex-catalyst system. Pyrochlore-type oxides have been used as proton reduction catalysts with a sacrificial electron donor (Na2EDTA) at pH 7 and as water oxidation catalysts with a sacrificial electron acceptor (K2S2O8) at pH 3. Rate constants for the proton reduction were estimated on the basis of photochemical processes. Yb2Ru2O7-δ was found to be the most active catalyst for proton reduction and water oxidation catalyst in this system.

Abstract: The ternary oxide compositions xZrO2-(0.5–x/2)Al2O3-yP2O5(x=0.8, 0.9, 0.95, 1.0; y=1.0, 1.2, 1.4) and 0.9ZrO2-0.05In2O3-1.4P2O5, xSiO2-(0.5–x/2)Al2O3-1.4P2O5(x=0.9, 1.0) were synthesized by sol-gel methods, and their conductivities were investigated by ac-impedance spectroscopy. The conductivity increased with increasing P2O5 content and with decreasing heat-treatment temperature. The maximum conductivities reached over 10-2 Scm-1 at 150°C for 0.9ZrO2-0.05Al2O3-1.4P2O5 and at 225°C for 0.9SiO2-0.05Al2O3-1.4P2O5.

Abstract: Two types of oxide nanosheet-based materials, a H3O+-exchanged layered titanate and restacked titania nanosheets (H3O+-RE) were synthesized by soft chemical methods, and their oxygen reduction reaction (ORR) activities were examined by semi-steady-state voltammetry with a rotating ring-disc electrode at 70°C in 0.05 M H2SO4. Both samples showed similar onset potentials of the ORR, ~ 0.50 vs. reversible hydrogen electrode, while the efficiencies (Eff4) of the 4-electron reduction of oxygen depended on their nanostructures, i.e. the stacking morphology of nanosheets, specific surface area and kinds of cation between the nanosheets. Both H3O+-form samples showed high Eff4 values are compared with Cs+-form layered titanate.and the H+-form restacked titania nanosheets. This reveals that the H3O+ions and the number of the active sites for ORR are related to the ORR activity. The H3O+-RE exhibited the best Eff4 value (> 90%), which is comparable to that of a conventional 20 mass% Pt/C catalyst.

Abstract: Shell-core type TiP2O7-based electrolytes were synthesized by a low-temperature sol-gel method, and their conductivities were investigated by ac-impedance spectroscopy. The samples heat-treated at 500°C showed higher proton conductivities of 3.8 × 10-2 - 1 × 10-2 Scm-1 at intermediate temperatures (100 - 300°C). The conductivity decreased by reheat-treatments at 600°C and 700°C due to a decrease in the amount of the conductive amorphous shells. However, the mechanical strength of the sample pellet significantly increased by the reheat-treatment. The sample reheat-treated at 600°C kept high conductivities of 8.8 × 10-3 - 1 × 10-3 Scm-1 in a range of 100°C - 300°C.

Abstract: Two series of compositions, BaCe0.8-xGd0.2RuxO3-δ (BCGRx, x=0-0.8) and BaGd1-yRuyO3-δ (BGRy, y=0.5-1.0), were synthesized and their crystal phases were examined. The BCGR0.15 and BGR0.5 oxides were a single phase of perovskite solid solution, while BCGR0.67 and BGR0.67 were a perovskite-related superstructure phase. The onset voltage (Vo) of the reduction current and the efficiency (E4) of the 4-electron reduction of oxygen were evaluated by semi-steady state voltammetry with rotating ring-disk electrodes. In the BCGRx series, the activities for electrochemical oxygen reduction (EOR) increased with increasing Ru content. In the BGRy series, the BGR0.67 superstructure phase showed a higher EOR activity than the perovskite BGR0.5 and the hexagonal(4H) BaRuO3. This indicates that the EOR activity depends on the crystal phase. The BGR0.67 exhibited the best EOR activity of all the samples. The Vo value was 0.80 V vs. reversible hydrogen electrode and the E4 value was almost 100 %.

Abstract: The activities of the pyrochlores Pb2Ru2-xMxO7-δ (M=Mn,Fe,Co,Ni)[PRM(0x)] toward electrochemical oxygen reduction (EOR) were examined in 0.1 M KOH and 0.05 M H2SO4 aqueous solutions. The onset voltage (Vo) and the efficiency (E4) of 4-electron reduction of oxygen for PRM(0x) were evaluated by semi-steady state voltammetry with rotating ring-disk electrodes. In PRM01, the order of the EOR activities was PRMn01 > PRCo01 > PRNi01 > PRFe01 in both solutions. This was consistent with the variation of the lattice parameters, i.e. PRM01 with a smaller lattice parameter showed higher EOR activity. In addition, PRMn05 showed higher EOR activity than PRMn01. The onset voltages Vo were 0.95 and 0.50 V vs. reversible hydrogen electrode in 0.1 M KOH and 0.05 M H2SO4, respectively, while E4 was almost 100 % in both solutions. These results indicate that the EOR activity of PRM(0x) depends on the incorporated metal ions on the B-sites and their contents.