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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Kinetics and Thermodynamics of Sr Permeation in CeO 2 -Based Barrier Layers for Solid-Oxide Electrolyzer Cells

Solid-oxide electrolyzer cells (SOECs) convert steam to hydrogen efficiently at high temperatures. However, during operation, the diffusion of cations or impurities through the cells due to electrode degradation can cause unwanted secondary phases to form, which may degrade device performance. Here, in this study, we use atomistic and mesoscale simulations coupled with experimental analysis to study the diffusion of Sr through the Gd-doped CeO 2 (GDC) barrier layer used to protect the yttria-stabilized zirconia (YSZ) electrolyte in SOECs. From our atomistic calculations, we find Sr diffusion to be negligibly slow in bulk GDC; however, surface diffusion is much more favorable. Subsequent mesoscale simulations show that Sr diffusion is activated when the porosity of GDC exceeds ∼10% and significantly exceeds diffusion in bulk and grain boundary regions. We also find that SrO-based species can accumulate at GDC surfaces; however, SrO aggregation and coarsening will be limited by the large lattice mismatch between GDC and SrO. Energy-dispersive X-ray spectroscopy (EDS) and electron diffraction confirm that Sr can accumulate within GDC pores and form disperse Sr-containing secondary phases. Altogether, Sr diffusion in dense GDC is unlikely to give rise to thick SrO layers, which would severely limit device performance. The formation of Sr-containing secondary phases can largely be avoided by restricting the porosity of the GDC layer as much as possible.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Hydrolysis of Acetamide on Low-Index CeO 2 Surfaces: Ceria as a Deamidation and General De-esterification Catalyst

Using DFT calculations and acetamide as the main example, we show that ceria is a potential catalyst for the hydrolysis of amide and similar bonds. The overall reaction is endergonic in the gas phase, yielding acetic acid and ammonia, but is slightly exergonic in the aqueous phase, which facilitates ionization of the products (CH 3 COO – and NH 4 + ). Neighboring Ce and O sites on the CeO 2 (111), (110), and (100) facets are conducive to the formation of an activated metastable tetrahedral intermediate (TI) complex, followed by C–N bond scission. With van der Waals and solvation effects taken into account, the overall reaction energetics is found to be most favorable on the (111) facet as desorption of acetic acid is much more uphill energetically on (110) and (100). We further suggest that the Ce–O–Ce sites on ceria surfaces can activate X(=Y)–Z type bonds in amides, amidines, and carboxylate and phosphate esters, among many others that we term “generalized esters”. A Brønsted-Evans–Polanyi relationship is identified correlating the stability of the transition and final states of the X–Z generalized ester bond scission. A simple descriptor (ΣΔχ) based on the electronegativity of the atoms that constitute the bond (X, Y, Z) versus those of the catalytic site (O, Ce, Ce) captures the trend in the stability of the transition state of generalized ester bond scission and suggests a direction for modifying ceria for targeting specific organic substrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Room-temperature activation of methane and dry re-forming with CO 2 on Ni-CeO 2 (111) surfaces: Effect of Ce 3+ sites and metal–support interactions on C–H bond cleavage

The results of core-level photoemission indicate that Ni-CeO 2 (111) surfaces with small or medium coverages of nickel are able to activate methane at 300 K, producing adsorbed CH x and CO x (x = 2, 3) groups. Calculations based on density functional theory predict a relatively low activation energy of 0.6–0.7 eV for the cleavage of the first C–H bond in the adsorbed methane molecule. Ni and O centers of ceria work in a cooperative way in the dissociation of the C–H bond at room temperature, where a low Ni loading is crucial for the catalyst activity and stability. The strong electronic perturbations in the Ni nanoparticles produced by the ceria supports of varying natures, such as stoichiometric and reduced, result in a drastic change in their chemical properties toward methane adsorption and dissociation as well as the dry reforming of methane reaction. Lastly, the coverage of Ni has a drastic effect on the ability of the system to dissociate methane and catalyze the dry re-forming process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Atomically Dispersed Pd–O Species on CeO 2 (111) as Highly Active Sites for Low-Temperature CO Oxidation

Ceria-supported Pd is a promising heterogeneous catalyst for CO oxidation relevant to environmental cleanup reactions. Pd loaded onto a nanorod form of ceria exposing predominantly (111) facets is already active at 50 °C. Here we report a combination of CO-FTIR spectroscopy and theoretical calculations that allows assigning different forms of Pd on the CeO 2 (111) surface during reaction conditions. Single Pd atoms stabilized in the form of PdO and PdO 2 in a CO/O 2 atmosphere participate in a catalytic cycle involving very low activation barriers for CO oxidation. In conclusion, the presence of single Pd atoms on the Pd/CeO 2 -nanorod, corroborated by aberration-corrected TEM and CO-FTIR spectroscopy, is considered pivotal to its high CO oxidation activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Growth of highly strained CeO 2 ultrathin films

Large biaxial strain is a promising route to tune the functionalities of oxide thin films. However, large strain is often not fully realized due to the formation of misfit dislocations at the film/substrate interface. In this work, we examine the growth of strained ceria (CeO 2 ) thin films on (001)-oriented single crystal yttria-stabilized zirconia (YSZ) via pulsed-laser deposition. By varying the film thickness systematically between 1 and 430 nm, we demonstrate that ultrathin ceria films are coherently strained to the YSZ substrate for thicknesses up to 2.7 nm, despite the large lattice mismatch (~5%). The coherency is confirmed by both X-ray diffraction and high-resolution transmission electron microscopy. This thickness is several times greater than the predicted equilibrium critical thickness. Partial strain relaxation is achieved by forming semirelaxed surface islands rather than by directly nucleating dislocations. In situ reflective high-energy electron diffraction during growth confirms the transition from 2-D (layer-by-layer) to 3-D (island) at a film thickness of ~1 nm, which is further supported by atomic force microscopy. We propose that dislocations likely nucleate near the surface islands and glide to the film/substrate interface, as evidenced by the presence of 60° dislocations. Finally, an improved understanding of growing oxide thin films with a large misfit lays the foundation to systematically explore the impact of strain and dislocations on properties such as ionic transport and redox chemistry.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Low-temperature conversion of methane to methanol on CeO x /Cu 2 O catalysts: Water controlled activation of the C–H Bond

Here, an inverse CeO 2 /Cu 2 O/Cu(111) catalyst is able to activate methane at room temperature producing C, CH x fragments and CO x species on the oxide surface. The addition of water to the system leads to a drastic change in the selectivity of methane activation yielding only adsorbed CH x fragments. At a temperature of 450 K, in the presence of water, a CH 4 → CH 3 OH catalytic transformation occurs with a high selectivity. OH groups formed by the dissociation of water saturate the catalyst surface, removing sites that could decompose CH x fragments, and generating centers on which methane can directly interact to yield methanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Equilibrium oxygen storage capacity of ultrathin CeO 2-δ depends non-monotonically on large biaxial strain

Elastic strain is being increasingly employed to enhance the catalytic properties of mixed ion–electron conducting oxides. However, its effect on oxygen storage capacity is not well established. Here, we fabricate ultrathin, coherently strained films of CeO 2-δ between 5.6% biaxial compression and 2.1% tension. In situ ambient pressure X-ray photoelectron spectroscopy reveals up to a fourfold enhancement in equilibrium oxygen storage capacity under both compression and tension. This non-monotonic variation with strain departs from the conventional wisdom based on a chemical expansion dominated behaviour. Through depth profiling, film thickness variations and a coupled photoemission–thermodynamic analysis of space-charge effects, we show that the enhanced reducibility is not dominated by interfacial effects. On the basis of ab initio calculations of oxygen vacancy formation incorporating defect interactions and vibrational contributions, we suggest that the non-monotonicity arises from the tetragonal distortion under large biaxial strain. Finally, these results may guide the rational engineering of multilayer and core–shell oxide nanomaterials.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Stochastic memristive nature in Co-doped CeO{sub 2} nanorod arrays

In this Letter, bipolar resistive switching characteristics of electrochemically deposited pure and Cobalt doped CeO{sub 2} nanorods architectures were reported. A conducting filament based model to address resistive switching process in these devices was proposed. Furthermore, the randomness in individual switching events and the prediction of switching probabilities were studied by imposing weak programming conditions. The present study offers insights into scrutinize the inherent stochastic nature in resistive switching characteristics within these devices rather than stressfully achieve high switching probabilities using excess voltage or time.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

Optical and magneto-optical properties of Co-doped CeO{sub 2−δ} films in the 0.5 to 4 eV range

Magnetically doped Ce{sub 1−x}Co{sub x}O{sub 2−δ} (nominal x = 0.05 and 0.10) films were systematically studied by spectroscopic ellipsometry and magneto-optical spectroscopy. The samples were prepared by pulsed laser deposition on MgO(100) substrates and grew as textured polycrystalline films with thickness between 200 and 750 nm. They exhibited room temperature ferromagnetism and an out-of-plane easy axis attributed to magnetoelastic effects from the in-plane compressive strain. The dispersion of dielectric function of Ce{sub 1−x}Co{sub x}O{sub 2−δ} films was parametrized by the sum of Tauc-Lorentz and damped Lorentz oscillators and adjusted numerically. Deduced optical band gaps were similar to those of pure CeO{sub 2}, but the Co doping increased the optical absorption. The magneto-optical spectroscopy was carried out in both Faraday and Kerr configurations in the photon energy range from 0.5 to 4 eV, showing a strong dependence of the magneto-optical effect on the Co content near the optical band edge.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Hydrogen activation, diffusion, and clustering on CeO{sub 2}(111): A DFT+U study

We present a comprehensive density functional theory+U study of the mechanisms underlying the dissociation of molecular hydrogen, and diffusion and clustering of the resulting atomic species on the CeO{sub 2}(111) surface. Contrary to a widely held view based solely on a previous theoretical prediction, our results show conclusively that H{sub 2} dissociation is an activated process with a large energy barrier ∼1.0 eV that is not significantly affected by coverage or the presence of surface oxygen vacancies. The reaction proceeds through a local energy minimum – where the molecule is located close to one of the surface oxygen atoms and the H–H bond has been substantially weaken by the interaction with the substrate –, and a transition state where one H atom is attached to a surface O atom and the other H atom sits on-top of a Ce{sup 4+} ion. In addition, we have explored how several factors, including H coverage, the location of Ce{sup 3+} ions as well as the U value, may affect the chemisorption energy and the relative stability of isolated OH groups versus pair and trimer structures. The trimer stability at low H coverages and the larger upward relaxation of the surface O atoms within the OH groups are consistent with the assignment of the frequent experimental observation by non-contact atomic force and scanning tunneling microscopies of bright protrusions on three neighboring surface O atoms to a triple OH group. The diffusion path of isolated H atoms on the surface goes through the adsorption on-top of an oxygen in the third atomic layer with a large energy barrier of ∼1.8 eV. Overall, the large energy barriers for both, molecular dissociation and atomic diffusion, are consistent with the high activity and selectivity found recently in the partial hydrogenation of acetylene catalyzed by ceria at high H{sub 2}/C{sub 2}H{sub 2} ratios.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Momentum transfer driven textural changes of CeO{sub 2} thin films

The influence of the target erosion depth on the film texture was investigated during DC reactive magnetron sputter deposition of CeO{sub 2} thin films. Three fluxes towards the substrate surface (the relative negative oxygen ion flux, the material flux, and the energy flux) were measured and related to the ongoing erosion of a cerium target. As the deposition rate increased for more eroded targets, both the energy flux and the negative ion flux decreased. Cerium oxide thin films that were deposited at different target erosion states, exhibited a change in preferential crystalline orientation from [200] to [111]. This textural change cannot be explained in terms of the energy per arriving atom concept. Instead, it is shown that the momentum of the high energetic negative ions is an essential condition to clarify the witnessed trends.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Study of the thermodynamic properties of CeO{sub 2} from ab initio calculations: The effect of phonon-phonon interaction

The thermodynamic properties of CeO{sub 2} have been reevaluated by a simple but accurate scheme. All our calculations are based on the self-consistent ab initio lattice dynamical (SCAILD) method that goes beyond the quasiharmonic approximation. Through this method, the effects of phonon-phonon interactions are included. The obtained thermodynamic properties and phonon dispersion relations are in good agreement with experimental data when considering the correction of phonon-phonon interaction. We find that the correction of phonon-phonon interaction is equally important and should not be neglected. At last, by comparing with quasiharmonic approximation, the present scheme based on SCAILD method is probably more suitable for high temperature systems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Interplay of structural, optical and magnetic properties in Gd doped CeO{sub 2}

In this research wok systematic investigation on the synthesis, characterization, optical and magnetic properties of Ce{sub 1-x}Gd{sub x}O{sub 2} (where x=0.02, 0.04, 0.06, and 0.10) synthesized using the Solid-state method. Structural, Optical and Magnetic properties of the samples were investigated by X-ray diffraction (XRD), UV-VIS-NIR spectroscopy and VSM. Fluorite structure is confirmed from the XRD measurement on Gd doped CeO{sub 2} samples. Magnetic studies showed that the Gd doped polycrystalline samples display room temperature ferromagnetism and the ferromagnetic ordering strengthens with the Gd concentration.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗