RESUMEN
A detailed study aimed at understanding and confirming the reported highly promising performance of a La0.3Sr0.7Fe0.7Cr0.3O3-δ (LSFCr) perovskite catalyst in CO2/CO mixtures, for use in reversible solid oxide fuel cells (RSOFCs), is reported in this work, with an emphasis on chemical and performance stability. This work includes an X-ray diffraction (XRD), thermogravimetric analysis (TGA), and electrochemical study in a range of pO2 atmospheres (pure CO2, CO alone (balance N2), and a 90-70% CO2/10-30% CO containing mixture), related to the different conditions that could be encountered during CO2 reduction at the cathode. Powdered LSFCr remains structurally stable in 20-100% CO2 (balance N2, pO2 = 10-11-10-12 atm) without any decomposition. However, in 30% CO (balance N2, pO2 â¼ 10-26 atm), a Ruddlesden-Popper phase, Fe nanoparticles, and potentially some coke are observed to form at 800 °C. However, this can be reversed and the original perovskite can be recovered by heat treatment in air at 800 °C. While no evidence for coke formation is obtained in 90-70% CO2/10-30% CO (pO2 = 10-17-10-18 atm) mixtures at 800 °C, in 70 CO2/30 CO, minor impurities of SrCO3 and Fe nanoparticles were observed, with the latter potentially beneficial to the electrochemical activity of the perovskite. Consistent with prior work, symmetrical two-electrode full cells (LSFCr used at both electrodes), fed with the various CO2/CO gas mixtures at one electrode and air at the other, showed excellent electrochemical performance at 800 °C, both in the SOFC and in SOEC modes. Also, LSFCr exhibits excellent stability during CO2 electrolysis in medium-term potentiostatic tests in all gas mixtures, indicative of its excellent promise as an electrode material for use in symmetrical solid oxide cells.
RESUMEN
Spontaneous nanoripple formation on (110) surfaces of yttria-stabilized zirconia, YSZ-(110), is achieved by diffusional surface doping with rare-earth oxides. Periodic arrays of parallel nanobars separated by channels (period â¼100 nm) grow out of the dopant sources, covering relatively wide areas of the surface (â¼10 µm). The nanobars mound up on the surface by diffusion, exhibiting morphological uniformity and alignment, with their long axis lying parallel to the [11Ì 0] direction in the YSZ-(110) surface. The process for forming these nanobar arrays can be as simple as sprinkling of rare-earth oxide powder (dopant source) on YSZ-(110) surface and annealing in a high temperature air furnace. However, higher control on dopant dispersion on the surface is demonstrated with other techniques, including photolithography and inkjet printing. The ripple arrays extend anisotropically on the (110) surface, obeying the parabolic growth law, and showing principal values of the rate constant along [11Ì 0] (maximum) and [001] (minimum), as expected from the symmetry of the (110) surface. The self-patterned ceramic substrates are well-suited for pattern transfer by replica molding, as illustrated by single-step molding with polydimethylsiloxane (PDMS), which is a widely used biomaterial in cell-culture studies.
RESUMEN
We experimentally investigate the mechanism of formation of self-assembled arrays of nanoislands surrounding dopant sources on the (001) surface of yttria-stabilized zirconia. Initially, we used lithographically defined thin-film patches of gadolinia-doped ceria (GDC) as dopant sources. During annealing at approximately one-half the melting temperature of zirconia, surface diffusion of dopants leads to the breakup of the surface around the source, creating arrays of epitaxial nanoislands with a characteristic size (~100 nm) and alignment along elastically compliant directions, <110>. The breakup relieves elastic strain energy at the expense of increasing surface energy. On the basis of understanding the mechanism of island formation, we introduce a simple and versatile powder-based doping process for spontaneous surface patterning. The new process bypasses lithography and conventional vapor-source doping, opening the door to spontaneous surface patterning of functional ceramics and other refractory materials. In addition to using GDC solid-solution powders, we demonstrate the effectiveness of the process in another system based on Eu2O3.