Electrical reduction of perovskite electrodes for accelerating exsolution of nanoparticles

This work was supported through the Leading Graduate School Program: Academy for Co-creative Education of Environment and Energy Science (ACEEES) funded by the Ministry of Education, Culture, Sports, Science and Technology (MEXT, Japan).Growth of finely dispersed nanocatalysts by exsolution of metal nanoparticles from perovskite oxides under reducing conditions at elevated temperature is a promising approach of producing highly active catalytic materials. An alternative method of exsolution using an applied potential has been recently shown to potentially accelerate the exsolution process of nanoparticles that can be achieved in minutes rather than the hours required in chemical reduction. In the present study, we investigate exsolution of nanoparticles from perovskite oxides of La0.43Ca0.37Ni0.06Ti0.94O3-γ (LCTNi) and La0.43Ca0.37Ni0.03Fe0.03Ti0.94O3-γ (LCTNi-Fe) under applied potentials in carbon dioxide atmosphere. The impedance spectra of single cells measured before and after electrochemical poling at varying voltages showed that the onset of exsolution process occurred at 2 V of potential reduction. An average particle size of the exsolved nanoparticles observed after testing using a scanning electron microscopy was about 30–100 nm. The cells with the reduced electrodes exhibited desirable electrochemical performances not only in pure carbon dioxide (current density of 0.37 A cm−2 for LCTNi and 0.48 A cm−2 for LCTNi-Fe at 1.5 V) but also in dry hydrogen (0.36 W cm−2 for LCTNi and 0.43 W cm−2 for LCTNi-Fe).PostprintPeer reviewe

Microarray-based global mapping of integration sites for the retrotransposon, intracisternal A-particle, in the mouse genome

Mammalian genomes contain numerous evolutionary harbored mobile elements, a part of which are still active and may cause genomic instability. Their movement and positional diversity occasionally result in phenotypic changes and variation by causing altered expression or disruption of neighboring host genes. Here, we describe a novel microarray-based method by which dispersed genomic locations of a type of retrotransposon in a mammalian genome can be identified. Using this method, we mapped the DNA elements for a mouse retrotransposon, intracisternal A-particle (IAP), within genomes of C3H/He and C57BL/6J inbred mouse strains; consequently we detected hundreds of probable IAP cDNA–integrated genomic regions, in which a considerable number of strain-specific putative insertions were included. In addition, by comparing genomic DNAs from radiation-induced myeloid leukemia cells and its reference normal tissue, we detected three genomic regions around which an IAP element was integrated. These results demonstrate the first successful genome-wide mapping of a retrotransposon type in a mammalian genome

Effect of Electronic Conductivities of Iridium Oxide/Doped SnO2 Oxygen-Evolving Catalysts on the Polarization Properties in Proton Exchange Membrane Water Electrolysis

We have developed IrOx/M-SnO2 (M = Nb, Ta, and Sb) anode catalysts, IrOx nanoparticles uniformly dispersed on M-SnO2 supports with fused-aggregate structures, which make it possible to evolve oxygen efficiently, even with a reduced amount of noble metal (Ir) in proton exchange membrane water electrolysis. Polarization properties of IrOx/M-SnO2 catalysts for the oxygen evolution reaction (OER) were examined at 80 °C in both 0.1 M HClO4 solution (half cell) and a single cell with a Nafion® membrane (thickness = 50 μm). While all catalysts exhibited similar OER activities in the half cell, the cell potential (Ecell) of the single cell was found to decrease with the increasing apparent conductivities (σapp, catalyst) of these catalysts: an Ecell of 1.61 V (voltage efficiency of 92%) at 1 A cm−2 was achieved in a single cell by the use of an IrOx/Sb-SnO2 anode (highest σapp, catalyst) with a low Ir-metal loading of 0.11 mg cm−2 and Pt supported on graphitized carbon black (Pt/GCB) as the cathode with 0.35 mg cm−2 of Pt loading. In addition to the reduction of the ohmic loss in the anode catalyst layer, the increased electronic conductivity contributed to decreasing the OER overpotential due to the effective utilization of the IrOx nanocatalysts on the M-SnO2 supports, which is an essential factor in improving the performance with low noble metal loadings

Development of Polymer Composite Membranes with Hydrophilic TiO₂ Nanoparticles and Perfluorosulfonic Acid-Based Electrolyte for Polymer Electrolyte Fuel Cells Operating over a Wide Temperature Range

Commercial perfluorosulfonic acid-based electrolyte membranes (PFSA, e.g., Nafion) are essential components in polymer electrolyte fuel cells (PEFCs) operated in the normal temperature range from 60 to 80 °C. Toward the widespread use of heavy-duty vehicles (HDVs) equipped with PEFCs, it will be necessary to approach higher temperature operation, up to approximately 120 °C, in addition to the normal temperature range, leading to the concept of so-called wide temperature range operation. We here propose a composite PFSA membrane with a hydrophilic filler of Ta-doped TiO2 (Ta-TiO2) for wide temperature range operation. A composite PFSA membrane (9 cm × 9 cm × 25 μmt) prepared by die coating was flexible, without pores or cracks. The hydrophilic Ta-TiO2 filler with a unique fused-aggregate network microstructure was well-dispersed in the composite membrane. The proton conductivity of the composite membrane was found to be 1.3 times higher than that of a commercial Nafion membrane at 80 °C over a wide humidity range, from 20% RH to 80% RH. Small-angle X-ray scattering (SAXS) profiles indicated a morphological change of the composite membrane compared with a commercial Nafion membrane and the preservation of a constant water cluster size over a wide range of humidity. The proton conductivity also increased, without an increase in water uptake, most likely due to enhanced hopping between the clusters. The mechanical strength of the composite membrane was similar to that of the commercial membrane. The current–voltage performance of a single cell using the composite membrane was higher than that for a cell using a commercial Nafion membrane at 120 °C, 20% RH, and was equivalent to that of a cell using Nafion at 80 °C, 100% RH. Thus, the newly developed composite membrane can be considered as an effective candidate to be applied in PEFCs operating over a wide temperature range

Synthesis and Evaluation of Ni Catalysts Supported on BaCe0.5Zr0.3−xY0.2NixO3−δ with Fused-Aggregate Network Structure for the Hydrogen Electrode of Solid Oxide Electrolysis Cell

Nickel nanoparticles loaded on the electron–proton mixed conductor BaCe0.5Zr0.3−xY0.2NixO3−δ (Ni/BCZYN, x = 0 and 0.03) were synthesized for use in the hydrogen electrode of a proton-conducting solid oxide electrolysis cell (SOEC). The Ni nanoparticles, synthesized by an impregnation method, were from 45.8 nm to 84.1 nm in diameter, and were highly dispersed on the BCZYN. The BCZYN nanoparticles, fabricated by the flame oxide synthesis method, constructed a unique microstructure, the so-called “fused-aggregate network structure”. The BCZYN nanoparticles have capability of constructing a scaffold for the hydrogen electrode with both electronically conducting pathways and gas diffusion pathways. The catalytic activity on Ni/BCZYN (x = 0 and 0.03) catalyst layers (CLs) improved with the circumference length of the Ni nanoparticles. Moreover, the catalytic activity on the Ni/BCZYN (x = 0.03) CL was higher than that of the Ni/BCZYN (x = 0) CL. BCZYN (x = 0.03) possesses higher electronic conductivity than BCZYN (x = 0) due to the Ni doping, resulting in an enlarged effective reaction zone (ERZ). We conclude that the proton reduction reaction in the ERZ was the rate-determining step on the hydrogen electrode, and the reaction was enhanced by improving the electronic conductivity of the electron–proton mixed conductor BCZYN

Pt nanorods supported on Nb-doped ceria: A promising anode catalyst for polymer electrolyte fuel cells

For polymer electrolyte fuel cells (PEFCs), platinum nanoparticles supported on carbon black (Pt/C) serve as the commonly used hydrogen anode catalyst, exhibiting high activity for the hydrogen oxidation reaction (HOR), while the carbon support is susceptible to corrosion under PEFC operation. Here, a highly active HOR anode catalyst of Pt nanorod supported on niobium (Nb)-doped ceria without using corrosive carbon support was developed, which exhibits high durability at high potentials associated with hydrogen starvation. The production of hydrogen peroxide (H2O2), which can degrade the polymer electrolyte membrane, was also found to be significantly suppressed on the Pt nanorod/doped ceria catalyst. Density functional theory (DFT) calculations suggests that the Pt nanorod geometry and interaction with Nb and Ce favor HOR activity and stability while suppressing H2O2 production by modulating the adsorption of key reaction intermediates. This new catalyst has the potential to be used as an anode for high-performance and high-durability PEFCs

Electrical reduction of perovskite electrodes for accelerating exsolution of nanoparticles

Growth of finely dispersed nanocatalysts by exsolution of metal nanoparticles from perovskite oxides under reducing conditions at elevated temperature is a promising approach of producing highly active catalytic materials. An alternative method of exsolution using an applied potential has been recently shown to potentially accelerate the exsolution process of nanoparticles that can be achieved in minutes rather than the hours required in chemical reduction. In the present study, we investigate exsolution of nanoparticles from perovskite oxides of La0.43Ca0.37Ni0.06Ti0.94O3-γ (LCTNi) and La0.43Ca0.37Ni0.03Fe0.03Ti0.94O3-γ (LCTNi-Fe) under applied potentials in carbon dioxide atmosphere. The impedance spectra of single cells measured before and after electrochemical poling at varying voltages showed that the onset of exsolution process occurred at 2 V of potential reduction. An average particle size of the exsolved nanoparticles observed after testing using a scanning electron microscopy was about 30–100 nm. The cells with the reduced electrodes exhibited desirable electrochemical performances not only in pure carbon dioxide (current density of 0.37 A cm−2 for LCTNi and 0.48 A cm−2 for LCTNi-Fe at 1.5 V) but also in dry hydrogen (0.36 W cm−2 for LCTNi and 0.43 W cm−2 for LCTNi-Fe)