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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Simulated Temperature Programmed Desorption of Acetaldehyde on CeO 2 (111): Evidence for the Role of Oxygen Vacancy and Hydrogen Transfer

The temperature programmed desorption of acetaldehyde adsorbed on partially reduced CeO 2 (111) has been studied in detail using microkinetic modeling based on self-consistent, periodic density functional theory calculations at the GGA-PW91+U level. Previous experimental studies (Chen et al. J. Phys. Chem. C 115: 3385, 2011; Calaza et al. J. Am. Chem. Soc. 134: 18034, 2012) have shown that, whereas on fully oxidized CeO 2 (111) acetaldehyde desorbs molecularly with a peak temperature of 210 K, the polymerization and enolization of acetaldehyde dominate the surface reactivity on partially reduced CeO 2 (111), resulting in acetaldehyde desorption at higher temperatures. Here we propose a comprehensive reaction mechanism that is consistent with the spectroscopic evidence of the identities of the surface intermediates and with the observed desorption activities, including the formation of ethylene and acetylene. Besides acetaldehyde (CH 3 CHO) and its enolate (CH 2 CHO), several other C 2 H x O species are proposed as key intermediates which are not seen spectroscopically, including ethoxy (CH 3 CH 2 O), ethyleneoxy (CH2CH2O), and formylmethylene (CHCHO). Our study suggests that oxygen vacancies play the critical role of activating the carbonyl bond and thereby facilitating b C–H bond scissions in acetaldehyde, leading to enolization, intermolecular hydrogen transfer, deoxygenation, and potentially C–C coupling reactions.

Zhao, Chuanlin↗
DOE OSTI2022

Effect of redox promoters (CeO x and CuO x ) and surface sulfates on the selective catalytic reduction (SCR) of NO with NH 3 by supported V 2 O 5 -WO 3 /TiO 2 catalysts

A series of TiO 2 -supported MO x catalysts (M=V, W, Ce, Cu and S) were investigated for their SCR activity. In situ Raman spectroscopy indicated that the supported MO x phases were completely dispersed as surface sites on the TiO 2 support. In situ IR revealed that surface VO x , WO x and SO x sites anchored at both CeO x /CuO x and TiO 2 sites. The number of surface Lewis acid sites decreased with the addition of basic (CeO x /CuO x ) and acidic (VO x /WO x ) sites in all catalysts, and acidic SO x in the unpromoted and Ce-promoted catalysts. The surface VO x , WO x and SO x sites introduced surface Brønsted acid sites. The redox promoters increased the NO conversion, but SO x impregnation inhibited their effect due to acid (SO x )-base (CeO x /CuO x ) interactions. Finally, the SCR reaction was shown to efficiently proceed via either surface NH 3 * or NH 4 +* species, resolving the long-standing dispute on the involvement of these species in the SCR reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Novel manganese-promoted inverse CeO 2 /CuO catalyst: In situ characterization and activity for the water-gas shift reaction

In this study, the behavior of a novel manganese-promoted inverse CeO 2 /CuO catalyst under water-gas shift (WGS) reaction conditions is studied. CeO 2 /CuO and CeO 2 /Mn-CuO catalysts are characterized by X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS). Structure/activity relationships and redox characteristics are established on the basis of such results along with those of in situ XRD and X-ray absorption fine structure (XAFS) experiments performed either under WGS or CO-temperature programmed reduction (TPR) conditions. The manganese coprecipitated together with the copper during the preparation of the samples and the Mn-CuO phase strongly affected the size and chemical properties of the catalytically-active ceria nanoparticles. A manganese-induced enhancement on the WGS activity was observed. As a result, differences in the characteristics of the supported ceria particles are proposed as most relevant to explain the observed Mn-promoting effect.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Effects of irradiation temperature on the response of CeO2, ThO2, and UO2 to highly ionizing radiation

Microcrystalline CeO 2 , ThO 2 , and UO 2 were irradiated with 198 MeV 132 Xe ions to the same fluence at temperatures ranging from 25°C to 700°C then characterized by synchrotron X-ray diffraction and X-ray absorption spectroscopy. All samples retain crystallinity and their nominal fluorite-type phase at a fluence of 1.5x10 13 ions/cm 2 . Both CeO 2 and ThO 2 display defect-induced unit cell expansion after irradiation at room temperature (~0.15% and ~0.10%, respectively), yet as irradiation temperature increases, the maximum swelling produced decreases to ~0.02%. Alternatively, UO 2 shows an initial contraction in unit cell parameter (approximately -0.05%), for room temperature irradiation most likely related to irradiation-enhanced annealing or irradiation-induced oxidation. At higher temperatures (above 200°C), UO 2 begins to swell, surpassing its unit cell parameter prior to irradiation (~0.05%), an effect which could be attributed to minor reduction in uranium oxidation state in vacuum. However, while CeO 2 irradiated at room temperature undergoes partial reduction, both UO 2 and ThO 2 exhibit no measurable change in cation oxidation state as evidenced by X-ray absorption spectroscopy. All samples display a decrease in irradiation-induced heterogeneous microstrain as a function of increasing irradiation temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Synthesis and VOC degradation ability of a CeO{sub 2}/WO{sub 3} thin-layer visible-light photocatalyst

Highlights: • Plasma-synthesized γ/ε-WO{sub 3} showed improvement of acetaldehyde decomposition. • Ferroelectricity of ε-WO{sub 3} slowed hole-electron recombination. • Synergistic effect between WO{sub 3} and CeO{sub 2} further enhanced photocatalytic activity. - Abstract: The plasma synthesis, characterization, and photocatalytic activity of WO{sub 3}, which consisted of a mixture of gamma WO{sub 3} and epsilon WO{sub 3} (γ/ε-WO{sub 3}), and physically mixed WO{sub 3} and CeO{sub 2} (WO{sub 3}/CeO{sub 2}) were investigated. Synergistic effects were observed in acetaldehyde photocatalysis experiments using γ/ε-WO{sub 3} or WO{sub 3}/CeO{sub 2}. The synergistic effect in the γ/ε-WO{sub 3} photocatalyst system is proposed to be the concurrent reduction of oxygen at gamma WO{sub 3} and oxidation of acetaldehyde at epsilon WO{sub 3}. It is hypothesized that acetaldehyde preferentially interacts with epsilon WO{sub 3} over gamma WO{sub 3} because of dipole–dipole interactions between them. In the case of the WO{sub 3}/CeO{sub 2} photocatalyst, the electron scavenging property of CeO{sub 2} aided charge carrier separation. As a result, WO{sub 3}/CeO{sub 2} exhibited excellent photocatalytic activity in volatile organic compound decomposition under visible light at room temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Size-Based Differential Transport, Uptake, and Mass Distribution of Ceria (CeO 2 ) Nanoparticles in Wetland Mesocosms

Trace metals associated with nanoparticles are known to possess reactivities that are different from their larger-size counterparts. However, the relative importance of small relative to large particles for the overall distribution and biouptake of these metals is not as well studied in complex environmental systems. In this work, we have examined differences in the long term fate and transport of ceria (CeO 2) nanoparticles of two different sizes (3.8 vs 185 nm), dosed weekly to freshwater wetland mesocosms over 9 months. While the majority of CeO 2 particles were detected in soils and sediments at the end of nine months, there were significant differences observed in fate, distribution, and transport mechanisms between the two materials. Small nanoparticles were removed from the water column primarily through heteroaggregation with suspended solids and plants, while large nanoparticles were removed primarily by sedimentation. A greater fraction of small particles remained in the upper floc layers of sediment relative to the large particles (31% vs 7%). Cerium from the small particles were also significantly more bioavailable to aquatic plants (2% vs 0.5%), snails (44 vs 2.6 ng), and insects (8 vs 0.07 $μ$g). Small CeO 2 particles were also significantly reduced from Ce(IV) to Ce(III), while aquatic sediments were a sink for untransformed large nanoparticles. These results demonstrate that trace metals originating from nanoscale materials have much greater potential than their larger counterparts to distribute throughout multiple compartments of a complex aquatic ecosystem and contribute to the overall bioavailable pool of the metal for biouptake and trophic transfer.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Below-Room-Temperature C–H Bond Breaking on an Inexpensive Metal Oxide: Methanol to Formaldehyde on CeO 2 (111)

C-H bond breaking is important for industrial commodity and specialty chemical transformations, including the upgrading of alcohols. Small primary alcohols – methanol and ethanol – are used industrially as precursors for the corresponding aldehydes at industrial scales. However, upgrading these primary alcohols involves C-H bond breaking and the processes are run at elevated temperatures (> 200 °C). In this work, new understanding from temperature programmed reaction (TPR) studies with methanol over a CeO 2 (111) surface show the C-H bond breaking and the subsequent desorption of formaldehyde, even below room temperature. This is of particular interests because CeO 2 is a naturally abundant, inexpensive metal oxide. We combine density functional theory (DFT) and kinetic Monte Carlo (KMC) to simulate the TPR of methanol on CeO 2 . Our simulations show that the low temperature C H bond breaking occurs via disproportionation of adjacent methoxy species to form methanol and formaldehyde which each then desorb. We further show from DFT calculations that the same transition state with comparably low activation energies should be possible for other sustainable primary alcohols, with ethanol, 1-propanol, and 1-butanol having been explicitly calculated. In conclusion, these findings point out a new class of transition states to search for in seeking low temperature C-H bond breaking over inexpensive metal oxides.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Integration of CeO 2 -Based Memristor with Vertically Aligned Nanocomposite Thin Film: Enabling Selective Conductive Filament Formation for High-Performance Electronic Synapses

The CeO 2 -based memristor has attracted significant attention due to its intrinsic resistive switching (RS) properties, large on/off ratio, and great plasticity, making it a promising candidate for artificial synapses. However, significant challenges such as high power consumption and poor device reliability hinder its broad application in neuromorphic microchips. To tackle these issues, in this work, we design a novel bilayer (BL) memristor by integrating a CeO 2 -based memristor with a Co-CeO 2 vertically aligned nanocomposite (VAN) layer and compare it with the single layer (SL) memristor. Preliminary electrical testing reveals that the BL memristor offers a reduced set/reset voltage (~67% lower), a higher on/off ratio (~5 × 10 2 ), enhanced device reliability, and improved device-to-device variation compared to the SL memristor. Insight from COMSOL simulation, coupled with microstructural analysis, provides a comprehensive elucidation on how the VAN layer facilitates the selective conductive filament (CF) formation. Subsequently, the plasticity of the BL memristor is evaluated through long-term potentiation/depression (LTP/LTD), paired-pulse facilitation (PPF), and spike-time-dependent plasticity (STDP). The spiking neural network (SNN) built upon the BL memristor achieves remarkable accuracy (~94%) after only 12 iterations, underscoring its potential for high-performance neural networks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Structural and Chemical Evolution of an Inverse CeO x /Cu Catalyst under CO 2 Hydrogenation: Tunning Oxide Morphology to Improve Activity and Selectivity

Small nanoparticles of ceria deposited on a powder of CuO display a very high selectivity for the production of methanol via CO 2 hydrogenation. CeO 2 /CuO catalysts with ceria loadings of 5%, 20%, and 50% were investigated. Among these, the system with 5% CeO x showed the best catalytic performance at temperatures between 200 and 350 °C. The evolution of this system under reaction conditions was studied using a combination of environmental transmission electron microscopy (E-TEM), in situ X-ray absorption spectroscopy (XAS), and time-resolved X-ray diffraction (TR-XRD). For 5% CeO x /Cu, the in situ studies pointed to a full conversion of CuO into metallic copper, with a complete transformation of Ce 4+ into Ce 3+ . Images from E-TEM showed drastic changes in the morphology of the catalyst when it was exposed to H 2 , CO 2 , and CO 2 /H 2 mixtures. Under a CO 2 /H 2 feed, there was a redispersion of the ceria particles that was detected by E-TEM and in situ TR-XRD. Finally, these morphological changes were made possible by the inverse oxide/metal configuration and facilitate the binding and selective conversion of CO 2 to methanol.

03 NATURAL GAS↗
DOE OSTI2022

Amorphous CeO 2 –Cu Heterostructure Enhances CO 2 Electroreduction to Multicarbon Alcohols

Electrochemical conversion of carbon dioxide (CO 2 ) gas to value-added chemicals such as multicarbon (C 2+ ) alcohols is a promising and attractive decarbonization strategy. However, there are tremendous challenges in tuning the intrinsic activity and selectivity of the catalysts to produce C 2+ alcohols. In this work, we prepared a CeO 2 –Cu composite catalyst via a combination of metallurgy and dealloying method. The interfacial sites of amorphous CeO 2 –Cu heterostructure improve the adsorption of key reaction intermediates *CO and promote the C–C coupling. Significantly, they also stabilize *CH 2 CHO at the bifurcation step, steering the reaction pathway toward the formation of C 2+ alcohols over ethylene. The CeO 2 –Cu catalyst achieves a remarkable faradaic efficiency of 32.9% ± 2.6% for C 2+ alcohols at -0.6 V vs RHE. Overall, this work demonstrates an effective strategy of improving the intrinsic activity and selectivity of the Cu-based catalysts for the generation of C 2+ alcohols.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Tuning Catalytic Reactivity via Wetting Control through Oxygen Vacancies: Ru Clusters on Anatase TiO 2 and CeO 2 Supports

The shape of supported metal particles regulates their catalytic reactivity and is determined by the degree of wetting between the metal particle and the support surface. Flattened particles that wet support surfaces were reported in various catalytic systems, particularly in the subnanometer size regime. Such consequential metal–support wetting phenomena are poorly understood, and methods to study them on powder catalysts under realistic conditions are lacking. Here, we investigate the size-dependent wetting behaviors of Ru particles on two reducible-oxide supports, anatase TiO 2 (TiO 2 -A) and CeO 2 , under reducing catalytic conditions. X-ray absorption spectroscopy (XAS), low-energy ion scattering (LEIS), and density functional theory (DFT) are combined to determine the shape of Ru particles. Ru particles remain three-dimensional without wetting the TiO 2 -A support within the coverage range studied (0.06–0.98 Ru nm –2 ). In contrast, at low coverages (<0.25 Ru nm –2 ), Ru wets the CeO 2 support to form flat, disordered structures. The higher wettability of CeO 2 than TiO 2 -A is attributed to oxygen vacancies in the near-surface region. The shape difference between small Ru particles or clusters on the two supports leads to drastically contrasting catalytic reactivities in polyolefin hydrogenolysis, despite similar diameters. As a result, this work highlights the implications of metal–support wetting, or cluster shape, on catalytic behaviors of small metal clusters, while establishing the foundation for future systematic studies of such a phenomenon in realistic systems, by delivering a multitechnique methodology and revealing governing fundamental principles.

42 ENGINEERING↗
DOE OSTI2015

Strongly enhanced oxygen ion transport through samarium-doped CeO 2 nanopillars in nanocomposite films

Enhancement of oxygen ion conductivity in oxides is important for low-temperature (<500 °C) operation of solid oxide fuel cells, sensors and other ionotronic devices. While huge ion conductivity has been demonstrated in planar heterostructure films, there has been considerable debate over the origin of the conductivity enhancement, in part because of the difficulties of probing buried ion transport channels. Here we create a practical geometry for device miniaturization, consisting of highly crystalline micrometre-thick vertical nanocolumns of Sm-doped CeO 2 embedded in supporting matrices of SrTiO 3 . The ionic conductivity is higher by one order of magnitude than plain Sm-doped CeO 2 films. By using scanning probe microscopy, we show that the fast ion-conducting channels are not exclusively restricted to the interface but also are localized at the Sm-doped CeO 2 nanopillars. This work offers a pathway to realize spatially localized fast ion transport in oxides of micrometre thickness.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2016

The role of the CeO 2 /BiVO 4 interface in optimized Fe–Ce oxide coatings for solar fuels photoanodes

Solar fuel generators entail a high degree of materials integration, and efficient photoelectrocatalysis of the constituent reactions hinges upon the establishment of highly functional interfaces. Our recent application of high throughput experimentation to interface discovery for solar fuels photoanodes has revealed several surprising and promising mixed-metal oxide coatings for BiVO 4 . Furthermore, when using sputter deposition of composition and thickness gradients on a uniform BiVO 4 film, we systematically explore photoanodic performance as a function of the composition and loading of Fe–Ce oxide coatings. This combinatorial materials integration study not only enhances the performance of this new class of materials but also identifies CeO 2 as a critical ingredient that merits detailed study. A heteroepitaxial CeO 2 (001)/BiVO4(010) interface is identified in which Bi and V remain fully coordinated to O such that no surface states are formed. Ab initio calculations of the integrated materials and inspection of the electronic structure reveals mechanisms by which CeO 2 facilitates charge transport while mitigating deleterious recombination. Our results support the observations that addition of Ce to BiVO 4 coatings greatly enhances photoelectrocatalytic activity, providing an important strategy for developing a scalable solar fuels technology.

14 SOLAR ENERGY↗
DOE OSTI2014

Epitaxial growth of CeO{sub 2}(111) film on Ru(0001): Scanning tunneling microscopy (STM) and x-ray photoemission spectroscopy (XPS) study

We formed an epitaxial film of CeO{sub 2}(111) by sublimating Ce atoms on Ru(0001) surface kept at elevated temperature in an oxygen ambient. X-ray photoemission spectroscopy measurement revealed a decrease of Ce{sup 4+}/Ce{sup 3+} ratio in a small temperature window of the growth temperature between 1070 and 1096 K, which corresponds to the reduction of the CeO{sub 2}(111). Scanning tunneling microscope image showed that a film with a wide terrace and a sharp step edge was obtained when the film was grown at the temperatures close to the reduction temperature, and the terrace width observed on the sample grown at 1060 K was more than twice of that grown at 1040 K. On the surface grown above the reduction temperature, the surface with a wide terrace and a sharp step was confirmed, but small dots were also seen in the terrace part, which are considerably Ce atoms adsorbed at the oxygen vacancies on the reduced surface. This experiment demonstrated that it is required to use the substrate temperature close to the reduction temperature to obtain CeO{sub 2}(111) with wide terrace width and sharp step edges.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Magnetic manipulation by resistance switching in CeO{sub 2}/PrBa{sub 2}Cu{sub 3}O{sub 7−δ}/Pt heterostructure: The role of oxygen vacancies

Pronounced bipolar resistance switching with a good retention property has been observed in CeO{sub 2}/PrBa{sub 2}Cu{sub 3}O{sub 7−δ}/Pt heterostructure. The low resistance state and high resistance state exhibited distinguished ferromagnetic signals, as compared to the nearly non-magnetic initial state. It is found that the migration of the oxygen vacancies under electric field is mainly responsible for the electric and the magnetic changes. The modified interfacial electronic structure by the oxygen vacancy migration and the trapping/detrapping of the carriers leads to the resistance switching. The exchange interaction of the hydrogen-like orbitals formed around the singly occupied oxygen vacancies in CeO{sub 2} is accounting for the emerged and modulated ferromagnetic signals. Temperature dependence of resistance in the low resistance state follows a variable range hopping law, further confirming that the amount of oxygen vacancies in the CeO{sub 2} layer directly affects the hydrogen-like orbital radius, which determines the strength of the ferromagnetic coupling.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Influence of solvent on the morphology and photocatalytic properties of ZnS decorated CeO{sub 2} nanoparticles

Herein, we report a theoretical and experimental study on the photocatalytic activity of CeO{sub 2} ZnS, and ZnS decorated CeO{sub 2} nanoparticles prepared by a microwave-assisted solvothermal method. Theoretical models were established to analyze electron transitions primarily at the interface between CeO{sub 2} and ZnS. As observed, the particle morphology strongly influenced the photocatalytic degradation of organic dye Rhodamine B. A model was proposed to rationalize the photocatalytic behavior of the prepared decorated systems taking into account different extrinsic and intrinsic defect distributions, including order-disorder effects at interfacial and intra-facial regions, and vacancy concentration.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Enhanced tunable magnetoresistance properties over a wide temperature range in epitaxial (La{sub 0.7}Sr{sub 0.3}MnO{sub 3}){sub 1−x}:(CeO{sub 2}){sub x} nanocomposites

Vertically aligned nanocomposite (VAN) (La{sub 0.7}Sr{sub 0.3}MnO{sub 3}){sub 1−x}:(CeO{sub 2}){sub x} (LSMO:CeO{sub 2}) thin films have been grown on SrTiO{sub 3} (001) substrates by pulsed laser deposition. Tunable magnetoresistance properties as well as microstructures are demonstrated in these VAN films by modulating the film composition (x = 0, 0.3, 0.4, 0.45, 0.5, and 0.55). The sample of x = 0.3 shows a large low-field magnetoresistance (LFMR) in a high temperature range, i.e., over 10% at the range of 280 K to 320 K under 1 T and with a peak value of ∼13.5% at 310 K. In addition, a vast enhancement of LFMR in a low temperature range of 20–150 K with peak of ≈34.3% at 45 K for 1 T could be achieved with x = 0.5. The enhanced LFMR properties can be attributed to both the phase boundary induced spin fluctuation and the magnetic tunneling effect through vertical ferromagnetic/insulator/ferromagnetic structures. The observed enhanced LFMR performance, especially at high temperatures, as well as its simple growth method, offers a great potential for LSMO:CeO{sub 2}nanocomposites to be used in spintronic devices in a large temperature range.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗