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At least 163 records · Page 9

Microstructure characterization and electrical transport of nanocrystalline ZrO{sub 2}–CeO{sub 2} solid solution

Graphical abstract: - Highlights: • Monoclinic ZrO{sub 2} phase has been changed to cubic ZrO{sub 2} phase within a short milling. • Conductivity increases due to change of phase from monoclinic to cubic. • A maximum has been observed in the s–T curve. • A transformation from −ve to +ve ac magnetoconductance has been observed. - Abstract: Nanocrystalline ZrO{sub 2}–CeO{sub 2} (ZC) solid solution is synthesized by high energy ball-milling the powder mixture of monoclinic (m) ZrO{sub 2}–10 mol% CeO{sub 2} in air medium. X-ray powder diffraction (XRD) patterns show that the method IS effective to synthesize cubic (c) ZrO{sub 2} phase within a short milling time. Formation mechanism, structural and microstructural changes of different phases and relative phase abundances have been estimated by Rietveld analysis of XRD patterns. The dc conductivity has been enhanced due to monoclinic to cubic phase transformation. A transformation from small polaron hopping to correlated barrier hoping has been observed from the of temperature dependence frequency exponent study. A crossover from negative to positive ac magnetoconductance has been observed at temperature T = 280 K and 230 K for unmilled (ZC0H) and 8 h (ZC8H) milled samples, respectively.

36 MATERIALS SCIENCE↗

A 17 O paramagnetic NMR study of Sm 2 O 3 , Eu 2 O 3 , and Sm/Eu-substituted CeO 2

We report that paramagnetic solid-state NMR of lanthanide ( Ln ) containing materials can be challenging due to the high electron spin states possible for the Ln ƒ electrons, which result in large paramagnetic shifts, and these difficulties are compounded for 17 O due to the low natural abundance and quadrupolar character. In this work, we present examples of 17 O NMR experiments for lanthanide oxides and strategies to overcome these difficulties. In particular, we record and assign the 17 O NMR spectra of monoclinic Sm 2 O 3 and Eu 2 O 3 for the first time, as well as performing density functional theory (DFT) calculations to gain further insight into the spectra. The temperature dependence of the Sm 3+ and Eu 3+ magnetic susceptibilities are investigated by measuring the 17 O shift of the cubic sesquioxides over a wide temperature range, which reveal non-Curie temperature dependence due to the presence of low-lying electronic states. This behaviour is reproduced by calculating the electron spin as a function of temperature, yielding shifts which agree well with the experimental values. Using the understanding of the magnetic behaviour gained from the sesquioxides, we then explore the local oxygen environments in 15 at% Sm- and Eu-substituted CeO 2 , with the 17 O NMR spectrum exhibiting signals due to environments with zero, one and two nearest neighbour Ln ions, as well as further splitting due to oxygen vacancies. Finally, we extract an activation energy for oxygen vacancy motion in these systems of 0.35 ± 0.02 eV from the Arrhenius temperature dependence of the 17 O T1 relaxation constants, which is found to be independent of the Ln ion within error. Finally, the relation of this activation energy to literature values for oxygen diffusion in Ln -substituted CeO 2 is discussed to infer mechanistic information which can be applied to further develop these materials as solid-state oxide-ion conductors.

36 MATERIALS SCIENCE↗

Tuning the Placement of Pt “Single Atoms” on a Mixed CeO 2 –TiO 2 Support

Defect sites on the oxide supports can be used to anchor and activate "single-atoms" catalysts (SACs). By engineering the anchoring sites for supporting SACs, one can alter their electronic and atomic structures which, in turn, define their activity, selectivity, and stability for catalytic reactions. To create and tune unique sites for Pt SACs on CeO 2 support, in this work, we synthesized a system consisting of CeO 2 decorated on TiO 2 nano-oxides for supporting the Pt SACs and investigated the effect of Pt weight loading. Here, a combination of multiple structural characterization methods including diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) were employed to characterize the distribution of charge states of single atoms and evaluate the heterogeneity of their binding sites. We have found that the placement of Pt atoms can be tuned on a mixed oxide surface by changing the weight loading of Pt.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Theoretical Study of Trimethylacetic Acid Adsorption on CeO 2 (111) Surface

We investigated trimethylacetic acid (TMAA) adsorption on stoichiometric and oxygen-deficient CeO 2 (111) surfaces using density functional theory that accounts for the on-site Coulomb interaction via a Hubbard term (DFT+U) and long-range dispersion correction. Both the molecular state and dissociative state (TMAA → TMA– + H + ) were identified on stoichiometric and oxygen-deficient CeO 2 (111) surfaces. For the stoichiometric surface, two thermodynamically favorable configurations with adsorption energies of the order of -30 kcal/mol are identified; one is a molecule adsorption state, and the other one is a dissociative state. For the oxygen-deficient surface, dissociative states are more favorable than molecular states. Moreover, the most favorable configuration is the dissociative adsorption of TMAA with the adsorption energy of the order of -77 kcal/mol. The dissociated TMA moiety takes the position of oxygen vacancy, forming three Ce–O bonds. The signature vibrational frequencies for these thermodynamically stable structures are reported as well as their electronic structures. The effects of long-range dispersion interactions are found to be negligible for geometries but important for adsorption energies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coupling of Acetaldehyde to Crotonaldehyde on CeO 2– x (111): Bifunctional Mechanism and Role of Oxygen Vacancies

Selective C–C coupling of oxygenates is pertinent to the manufacture of fuel and chemical products from biomass and from derivatives of C 1 compounds (i.e., oxygenates produced from methane and CO 2 ). Here we report a combined experimental and theoretical study on the temperature-programmed reaction (TPR) of acetaldehyde (AcH) on a partially reduced CeO 2– x (111) thin film surface. The experiments have been carried out under ultra-high-vacuum conditions without continuous gas exposure, allowing better isolation of active sites and reactive intermediates than in flow reaction conditions. AcH does not undergo aldol condensation in a typical TPR procedure, even though the enolate form of AcH (CH 2 CHO) is readily produced on CeO 2– x (111) with oxygen vacancies. We find however that a tailored “double-ramp” TPR procedure is able to successfully produce an aldol adduct, crotonaldehyde (CrA). Using density functional theory calculations and microkinetic modeling we explore several possible C–C coupling pathways. We conclude that the double-ramp procedure allows surface oxygen vacancy dimers, stabilized by adsorbate occupation, to form dynamically during the TPR. The vacancy dimers in turn enable C–C coupling to occur between an enolate and an adjacent AcH molecule via a bifunctional enolate–keto mechanism that is distinct from conventional acid- or base-catalyzed aldol condensation reactions. Here, the proposed mechanism indicates that CrA desorption is rate-limiting while C–C coupling is facile.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Study of Particle Precipitation in Metal-Doped CeO2 during Thermal Treatment and Ion Irradiation for Emulation of Irradiating Fuels

Metallic particles formed in oxide fuels (e.g., UO 2 ) during neutron irradiation have an adverse impact on fuel performance. A fundamental investigation of particle precipitation is needed to predict the fuel performance and potentially improve fuel designs and operations. In this study, we report on the precipitation of Mo-dominant β-phase particles in polycrystalline CeO 2 (surrogate for UO 2 ) films doped with Mo, Pd, Rh, Ru, and Re (surrogate for Tc). In situ heating scanning transmission electron microscopy indicates that particle precipitation starts at ~1073 K with a limited particle growth to ~10 nm. While particle concentration increases with increasing temperature, particle size remains largely unchanged up to 1273 K. There is a dramatic change in the microstructure following vacuum annealing at 1373 K, probably due to phase transition of reduced cerium oxide. At the high temperature, particles grow up to 75 nm or larger with distinctive facets. The particles are predominantly composed of Mo with a body-centered cubic structure (β phase). An oxide layer was observed after storage at ambient conditions. In situ heating X-ray photoelectron spectroscopy reveals an increasing reduction of Ce charge state from 4+ to 3+ in the doped CeO 2 film at temperatures from 673 to 1273 K. In situ ion irradiation transmission electron microscopy with 2 MeV Al 2+ ions up to a dose of ~20 displacements per atom at nominally room temperature does not lead to precipitation of visible particles. However, irradiation with 1.7 MeV Au 3+ ions to ~10 dpa at 973 K produces ~2 nm sized pure Pd particles; Au 3+ irradiation at 1173 K appears to result in precipitates of ~6 nm in size. Some of the defects produced by ion irradiation could be nucleation sites for precipitation, leading to generation of smaller particles with a higher concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Local Structure and Electronic State of Atomically Dispersed Pt Supported on Nanosized CeO 2

Single atom catalysts (SACs) have shown high activity and selectivity in a growing number of chemical reactions. Many efforts aimed at unveiling the structure–property relationships underpinning these activities and developing synthesis methods for obtaining SACs with the desired structures are hindered by the paucity of experimental methods capable of probing the attributes of local structure, electronic properties, and interaction with support—features that comprise key descriptors of their activity. Here in this work, we describe a combination of experimental and theoretical approaches that include photon and electron spectroscopy, scattering, and imaging methods, linked by density functional theory calculations, for providing detailed and comprehensive information on the atomic structure and electronic properties of SACs. This characterization toolbox is demonstrated here using a model single atom Pt/CeO 2 catalyst prepared via a sol–gel-based synthesis method. Isolated Pt atoms together with extra oxygen atoms passivate the (100) surface of nanosized ceria. A detailed picture of the local structure of Pt nearest environment emerges from this work involving the bonding of isolated Pt 2+ ions at the hollow sites of perturbed (100) surface planes of the CeO 2 support, as well as a substantial (and heretofore unrecognized) strain within the CeO 2 lattice in the immediate vicinity of the Pt centers. The detailed information on structural attributes provided by our approach is the key for understanding and improving the properties of SACs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanistic Insights and Rational Design of Ca-Doped CeO 2 Catalyst for Acetic Acid Ketonization

Carboxylic acid ketonization has recently gained significant attention to produce biomass-derived hydrocarbon fuels as it not only removes the highly reactive carboxylic functional group but also increases the size of the carbon chain. In this work, Ca-doped CeO 2 -based catalysts were investigated for acetic acid ketonization using a combined experimental and computational approach. Acetic acid conversion was performed across a range of temperatures including higher temperatures relevant to catalytic hot gas filtration (450 °C). Ca addition slightly decreases overall acetic acid ketonization reactivity yet stabilizes the catalyst at the higher temperatures necessary for catalytic hot gas filtration. From density functional theory calculations of the ketonization reaction mechanism, the C–C coupling and water formation steps are identified as two of the most energy-consuming steps on a CeO 2 surface with a proximal oxygen vacancy and the presence of a Ca dopant stabilizes the key intermediates. Calculations predict an optimal structure comprising three Ca ensembles to minimize the reaction free energies for C–C coupling and water formation steps. These findings provide a priori information to guide future experiments for ketonization catalyst design and development.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inverse Catalysts for CO Oxidation: Enhanced Oxide–Metal Interactions in MgO/Au(111), CeO 2 /Au(111), and TiO 2 /Au(111)

Au(111) does not bind CO and O 2 well. The deposition of small nanoparticles of MgO, CeO 2 , and TiO 2 on Au(111) produces excellent catalysts for CO oxidation at room temperature. In an inverse oxide/metal configuration there is a strong enhancement of the oxide–metal interactions, and the inverse catalysts are more active than conventional Au/MgO(001), Au/CeO 2 (111), and Au/TiO 2 (110) catalysts. An identical trend was seen after comparing the CO oxidation activity of TiO2/Au and Au/TiO 2 powder catalysts. In the model systems, the activity increased following the sequence: MgO/Au(111) < CeO 2 /Au(111) < TiO 2 /Au(111). Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) was used to elucidate the role of the titania–gold interface in inverse TiO 2 /Au(111) model catalysts during CO oxidation. Stable surface intermediates such as CO(ads), CO 3 2– (ads), and OH(ads) were identified under reaction conditions. CO 3 2– (ads) and OH(ads) behaved as spectators. The concentration of CO(ad) initially increased and then decreased with increasing TiO 2 coverage, demonstrating a clear role of the Ti–Au interface and the size of the TiO 2 nanostructures in the catalytic process. Overall, our results show an enhancement in the strength of the oxide–metal interactions when working with inverse oxide/metal configurations, a phenomenon that can be utilized for the design of efficient catalysts useful for green and sustainable chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Au and Pt Remain Unoxidized on a CeO 2 -Based Catalyst during the Water–Gas Shift Reaction

The active form of Au and Pt in CeO 2 based catalysts for the WGS reaction is an issue that although it has been widely studied remains unclear. On one hand, ionic species might be responsible of weakening the Ce-O bonds increasing the oxygen mobility and WGS activity. On the other hand, the close contact of Au or Pt atoms with CeO 2 oxygen vacancies at the metal/CeO 2 interface might provide the active sites for an efficient reaction. In this work, by using in-situ X-ray absorption spectroscopy, we demonstrate that both Au and Pt remain unoxidized during the reaction. Here, remarkable differences involving the dynamics established by both species under WGS atmospheres were recognized. For the pre-reduced Pt catalyst, an increase of the conversion coincided with a re-structuration of the Pt atoms into cuboctahedrical metallic particles without significant variations on the overall particle size. Contrary to the relatively static behavior of Pt 0 , Au 0 nanoparticles exhibited a sequence of particle splitting and agglomeration whilst maintaining a zero oxidation state, even though not being located in a metallic environment during the process. High WGS activity was obtained when Au atoms were surrounded by oxygen. The fact that Au preserves its unoxidized state indicates that the chemical interaction between Au and oxygen must be necessarily electrostatic being such electrostatic interaction fundamental for a top performance in the WGS process.

36 MATERIALS SCIENCE↗

Transformation of CeO 2 Nanoparticles into Atomically Dispersed Ce Cations Leads to Enhanced Reactivity for Automotive Emissions Control

Nanosized cerium oxide (CeO 2 ) has been extensively used as the oxygen storage component in automotive emission control systems. However, the possible influence of atomically dispersed Ce in these catalysts has not been recognized. Here, in this study, we demonstrate the controllable transformation of ceria nanoparticles into isolated cerium cations on γ-Al 2 O 3 via reductive atom trapping in 10% H 2 at 800 °C, achieving over half-monolayer coverage. Dispersed Ce 1 ions anchored by surface penta- and octa-coordinated Al sites exhibit outstanding thermal stability in air up to 500 °C, enabling further loading of active metals with well-defined catalyst structures. With this strategy, supported single-atom Rh 1 surrounded by dispersed Ce 1 is confirmed to exhibit much superior performance to Rh 1 on bare Al 2 O 3 or nanocrystalline CeO 2 in catalyzing NO reduction by CO, exhibiting a striking one-order-of-magnitude increase in activity. Dispersed Ce 1 exhibits greatly enhanced oxygen transfer capability compared to ceria nanoparticles and introduces a modified reaction mechanism that involves an adjacent Rh 1 –Ce 1 motif, resulting in a greatly decreased activation barrier (from 192 to 96 kJ/mol). The reactivity enhancements are also seen with Ce 1 -promoted Pt nanoparticles for oxidation of CO and hydrocarbons.

Jiang, Dong [Washington State Univ., Pullman, WA (↗

Low-Temperature Restructuring of CeO 2 -Supported Ru Nanoparticles Determines Selectivity in CO 2 Catalytic Reduction

CO 2 reduction to higher value products is a promising way to produce fuels and key chemical building blocks while reducing CO 2 emissions. The reaction at atmospheric pressure mainly yields CH 4 via methanation and CO via the reverse water-gas shift (RWGS) reaction. Describing catalyst features that control the selectivity of these two pathways is important to determine the formation of specific products. At the same time, identification of morphological changes occurring to catalysts under reaction conditions can be crucial to tune their catalytic performance. In this contribution we investigate the dependency of selectivity for CO 2 reduction on the size of Ru nanoparticles (NPs) and on support. We find that even at rather low temperatures (210 °C), oxidative pretreatment induces redispersion of Ru NPs supported on CeO 2 and leads to a complete switch in the performance of this material from a well-known selective methanation catalyst to an active and selective RWGS catalyst. By utilizing in situ X-ray absorption spectroscopy, we demonstrate that the low-temperature redispersion process occurs via decomposition of the metal oxide phase with size-dependent kinetics, producing stable single-site RuO x /CeO 2 species strongly bound to the CeO 2 support that are remarkably selective for CO production. Furthermore, these results show that reaction selectivity can be heavily dependent on catalyst structure and that structural changes of the catalyst can occur even at low temperatures and can go unseen in materials with less defined structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning Pt-CeO 2 interactions by high-temperature vapor-phase synthesis for improved reducibility of lattice oxygen

In this work, we compare the CO oxidation performance of Pt single atom catalysts (SACs) prepared via two methods: (1) conventional wet chemical synthesis (strong electrostatic adsorption–SEA) with calcination at 350 °C in air; and (2) high temperature vapor phase synthesis (atom trapping–AT) with calcination in air at 800 °C leading to ionic Pt being trapped on the CeO 2 in a thermally stable form. As-synthesized, both SACs are inactive for low temperature (<150 °C) CO oxidation. After treatment in CO at 275 °C, both catalysts show enhanced reactivity. Despite similar Pt metal particle size, the AT catalyst is significantly more active, with onset of CO oxidation near room temperature. A combination of near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and CO temperature-programmed reduction (CO-TPR) shows that the high reactivity at low temperatures can be related to the improved reducibility of lattice oxygen on the CeO 2 support.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modifying redox properties and local bonding of Co 3 O 4 by CeO 2 enhances oxygen evolution catalysis in acid

Developing efficient and stable earth-abundant electrocatalysts for acidic oxygen evolution reaction is the bottleneck for water splitting using proton exchange membrane electrolyzers. Here, we show that nanocrystalline CeO 2 in a Co 3 O 4 /CeO 2 nanocomposite can modify the redox properties of Co 3 O 4 and enhances its intrinsic oxygen evolution reaction activity, and combine electrochemical and structural characterizations including kinetic isotope effect, pH- and temperature-dependence, in situ Raman and ex situ X-ray absorption spectroscopy analyses to understand the origin. The local bonding environment of Co 3 O 4 can be modified after the introduction of nanocrystalline CeO 2 , which allows the CoIII species to be easily oxidized into catalytically active CoIV species, bypassing the potential-determining surface reconstruction process. Co 3 O 4 /CeO 2 displays a comparable stability to Co 3 O 4 thus breaks the activity/stability tradeoff. This work not only establishes an efficient earth-abundant catalysts for acidic oxygen evolution reaction, but also provides strategies for designing more active catalysts for other reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Functional CeO x nanoglues for robust atomically dispersed catalysts

Single-atom catalysts make exceptionally efficient use of expensive noble metals and can bring out unique properties. However, applications are usually compromised by limited catalyst stability, which is due to sintering. Although sintering can be suppressed by anchoring the metal atoms to oxide supports, strong metal–oxygen interactions often leave too few metal sites available for reactant binding and catalysis, and when exposed to reducing conditions at sufficiently high temperatures, even oxide-anchored single-atom catalysts eventually sinter. Here we show that the beneficial effects of anchoring can be enhanced by confining the atomically dispersed metal atoms on oxide nanoclusters or ‘nanoglues’, which themselves are dispersed and immobilized on a robust, high-surface-area support. We demonstrate the strategy by grafting isolated and defective CeO x nanoglue islands onto high-surface-area SiO 2 ; the nanoglue islands then each host on average one Pt atom. Further, we find that the Pt atoms remain dispersed under both oxidizing and reducing environments at high temperatures, and that the activated catalyst exhibits markedly increased activity for CO oxidation. We attribute the improved stability under reducing conditions to the support structure and the much stronger affinity of Pt atoms for CeO x than for SiO 2 , which ensures the Pt atoms can move but remain confined to their respective nanoglue islands. The strategy of using functional nanoglues to confine atomically dispersed metals and simultaneously enhance their reactivity is general, and we anticipate that it will take single-atom catalysts a step closer to practical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Assessing Hubbard-corrected AM05+ U and PBEsol+ U density functionals for strongly correlated oxides CeO 2 and Ce 2 O 3

The structure–property relationships of bulk CeO 2 and Ce 2 O 3 have been investigated using AM05 and PBEsol exchange–correlation functionals within the frameworks of Hubbard-corrected density functional theory (DFT+ U ) and density functional perturbation theory (DFPT+ U ). Compared with conventional PBE+ U , RPBE+ U , PW91+ U and LDA+ U functionals, AM05+ U and PBEsol+ U describe experimental crystalline parameters and properties of CeO 2 and Ce 2 O 3 with superior accuracy, especially when + U is chosen close to its value derived by the linear-response approach. Lastly, the present findings call for a reexamination of some of the problematic oxide materials featuring strong f- and d-electron correlation using AM05+ U and PBEsol+ U .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing the low-temperature performance of Pt-based three-way catalysts using CeO 2 (core)@ZrO 2 (shell) supports

Developing robust Pt/CeO 2 -based three-way catalysts (TWCs) with enhanced oxygen buffering capability and low-temperature activity is highly desirable. In this study, a new TWC family, Pt/(1 − x)CeO 2 (core)@xZrO 2 (shell) (where x = 0–0.5), was prepared and evaluated at degreened (DG) and hydrothermally aged (HTA) states. Incorporation of 0.1 molar concentration of ZrO 2 resulted in a decreased temperature that 50% (T 50 ) (CO: 167 °C, THCs: 218 °C, NO: 228 °C) and 90% (T 90 ) (CO: 207 °C, THCs: 237 °C, NO: 244 °C) conversions achieved over HTA 1.8 wt% Pt/0.9CeO 2 @0.1ZrO 2 compared to the HTA 1.8 wt% Pt/CeO 2 sphere (CO: T50,90 = 179, 222 °C, THCs: 234, 252 °C, NO x : 240, 260 °C). An enhanced oxygen storage capacity and oxygen release rate were observed over Pt/0.9CeO 2 @0.1ZrO 2 compared to the Pt/CeO 2 sphere. Increasing the ZrO 2 molar concentration to values greater than 0.2 resulted in increased T 50 s (224, 265 274 °C) and T 90 s (251, 289, 292 °C) for CO, THCs, and NO x , respectively, over 1.8 wt.% Pt/0.5CeO 2 @0.5ZrO 2 . Overall, this work highlights the potential of forming a ZrO 2 shell on CeO 2 spheres as a support for TWC applications.

Liu, Chih-Han [State Univ. of New York (SUNY), Buf↗

Magnetic characteristics of phase-separated CeO 2 :Co thin films

Herewith, we are reporting the magnetic properties of phase-separated Co-doped CeO 2 films (with a Ce:Co atomic-ratio of 0.97:0.03) grown on single-crystal SrTiO 3 (001) substrates. A comparison of the magnetic characteristics of these films with those of homogenously doped CeO 2 :Co films of the same composition illustrates the significant differences in their magnetic behavior. Here, these behavioral characteristics provide a model for determining if the magnetic behavior observed in this, as well as in other diluted magnetic dielectric systems, is due to homogeneous doping, a mixture of doping and transition metal cluster formation, or exists purely as a result of transition metal clustering.

36 MATERIALS SCIENCE↗