Entropy-driven adsorption of carbon nanotubes on (0 0 1) and (1 1 1) surfaces of CeO2 islands grown on sapphire substrate

According to the aim to compose combinatorial material by adsorption of carbon nanotubes onto the structured CeO₂ surface the interaction of the armchair (5,5) and zigzag (8,0) nanotubes with the (0 0 1) and (1 1 1) surfaces of CeO₂ islands have been investigated by theoretical methods. The thermodynamics of the adsorption were studied at the low surface coverage region. The interaction energy between the nanotube and the different CeO₂ surfaces shows significant increase when the size of the interface reaches 7–8 unit cells of CeO₂ and it remains unchanged in the larger interface region. However, the entropy term of the adsorption is significantly high when the distances of CeO₂ islands are equal to 27 nm (adsorption of armchair (5,5) nanotube) or 32 nm (adsorption of zigzag (8,0) nanotube). This property supports adsorption of nanotubes onto CeO₂ surfaces which possesses a very specific surface morphology. A long-wave vibration of nanotubes was identified as background of this unexpected phenomenon. This observation could be applicable in the development of such procedures where the nanotube adsorption parallel to the surface is aimed to perform.     

Preparation of YBCO film for microwave filter using a hybrid route

Pure (0 0 l)-textured CeO₂ buffer layers were deposited on single crystal r-plane Al₂O₃ (1–102) substrate by a hybrid process which was combined with magnetron sputtering for the seed layer and metal–organic deposition for the subsequent layer. Strongly c-axis oriented YBCO films were deposited on the CeO₂ buffered r-cut Al₂O₃ (1–102) substrates. Atomic force microscope and scanning electronic microscopy results show that the prepared buffers and YBCO films are relatively dense and smooth. The critical current of the YBCO films exceeds 1.5 MA/cm² at 77 K with the superconducting transition temperature of 90 K. The surface resistivity is as below as 14 μΩ at 1 GHz frequency. The results demonstrate that the hybrid route is a very promising method to prepare YBCO films for microwave application, which can combine the sputtering advantage for preparing of highly c-axis oriented CeO₂ buffer layers and the advantages of metal–organic deposition with rapid processing, low cost and easy preparation of large-area YBCO films.     

Reduction of thin-film ceria on Pt(111) by supported Pd nanoparticles probed with resonant photoemission

Local defects present in CeO_2 ? x films result in a mixture of Ce³⁺ and Ce⁴⁺ oxidation states. Previous studies of the Ce 3d region with XPS have shown that depositing metal nanoparticles on ceria films causes further reduction, with an increase in Ce³⁺ concentration. Here, we compare the use of XPS and resonant photoemission spectroscopy (RESPES) to estimate the concentration of Ce³⁺ and Ce⁴⁺ in CeO_2 ? x films grown on Pt (111), and the variation of this concentration as a function of Pd deposition. Due to the nature of the electronic structure of CeO_2 ? x, resonant peaks are observed for the 4d–4f transitions when the photon energy matches the resonant energy; (hν = 121.0 eV) for Ce³⁺ and (hν = 124.5 eV) for Ce⁴⁺. This results in two discrete resonant photoemission peaks in valence band spectra. The ratio of the difference of these peaks with off-resonance scans gives an indication of the relative contribution of Ce³⁺. Results from RESPES indicate reduction of CeO_2 ? x on deposition of Pd, confirming earlier findings from XPS studies.     

Crystal structure,thermochemical stability,electrical and magnetic properties of the two-phase composites in the La0.8Sr0.2MnO3 ± δ–CeO2 system

Crystal structure, thermochemical stability, transport and magnetic properties of compositions in the (100-x) La_0.8Sr_0.2MnO_3 ± δ xCeO₂ (LSMC) system were studied. All compositions in the LSMC series containing more than 2 mol% CeO₂ were two phase and consisted of the modified perovskite constituent with rhombohedral structure (R3?c) and ceria as a secondary phase with cubic structure (Fm3?m). The presence of both Ce⁴⁺and Ce³⁺ cations in LSMC compositions was revealed by X-ray Photoelectron Spectroscopy (XPS). CeO₂ and compositions in the LSMC series showed good thermochemical stability in air and argon. However, in H₂–Ar atmosphere all LSMC compositions underwent reduction followed by decomposition. Transport and magnetic properties change in a non-linear way with the increase in the CeO₂ content. The LSMC2 composition showed enhanced electronic conductivity and magnetic characteristics. Metallic type conductivity was observed for LSMC compositions with x ≤ 36 mol% CeO₂ in a narrow temperature range of 770–900 °C. A small degree of substitution of Ce into LSM was found to change structural, magnetic and electrical properties.     

Ti/CeOx(111) interfaces studied by XPS and STM

Low coverage of Ti was deposited on the well-ordered CeO_x(111) (1.5 < x < 2) thin films grown on Ru(0001) by physical vapor deposition at room temperature. The structure and interaction of Ti/ceria interfaces were investigated with X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM) techniques under ultrahigh vacuum conditions. XPS data indicate that the deposition of Ti on both oxidized and reduced ceria surfaces causes the partial reduction of Ce from + 4 to + 3 state. Ti is formally in the + 4 state. STM data show the formation of small atomic-like titania features at 300 K, which coalesce to form chain structures upon heating. It is demonstrated in the study that the deposition of Ti can form mixed metal oxides at the interface and modify both electronic and structural properties of the ceria support. The structural study of Ti/ceria interfaces can be a key for understanding the higher catalytic activity of the Ti–CeO_x mixed oxide catalysts as compared with the individual pure oxides.     

Density functional theory study of water adsorption on FeOOH surfaces

Using density functional theory (DFT) calculations with an on-site Coulomb repulsion term, we study the composition, stability, and electronic properties of the most common FeOOH surfaces goethite(101), akaganeite(100), and lepidocrocite(010), and their interaction with water. Despite the differences in surface structure, the trends in surface stability of these FeOOH polymorphs exhibit remarkable similarities. We find that the reactivity and the binding configuration of adsorbates depend strongly on the coordination of surface iron: at the fourfold coordinated Fe2 site water is chemisorbed, whereas at the fivefold coordinated Fe1 water is only loosely bound with hydrogen pointing towards the surface. Our results show that the oxidation state of surface iron can be controlled by the surface termination where ferryl (Fe^4 +) species emerge for oxygen terminated surfaces and ferrous iron (Fe^2 +) at iron and water terminations leading to a reduced band gap. In contrast, the fully hydroxylated surfaces, identified as stable surface configurations at standard conditions from the surface phase diagram, show electronic properties and band gaps closest to bulk FeOOH with ferric surface iron (Fe^3 +). Only in the case of goethite(101), a termination with mixed surface hydroxyl and aquo groups is stabilized.     

Structural and electronic properties of cobalt carbide Co2C and its surface stability: Density functional theory study

Density functional theory calculations have been performed to investigate the structural and electronic properties of bulk Co₂C and the stability of low index Co₂C surfaces. We found that the formation of Co₂C is exothermic with the formation energy of ? 0.81 eV/Co₂C with respect to Co under the presence of syngas (mixture of CO and H₂). While formed Co₂C can be decomposed further to metal Co and graphite carbon with modest energy gain of 0.37 eV/Co₂C. This suggests that Co₂C is only metastable in Fischer–Tropsch synthesis, which agrees well with experimental findings. The density of states (DOSs) reveals that the Co₂C is paramagnetic and strong metallic-like. The difference of charge density analysis indicates that the bond of Co₂C is of the mixtures of metallic, covalent, and ionic properties. A variety of low index Co₂C surfaces with different terminations are studied. We find that the surface energy of low index stoichiometric Co₂C highly relies on the surface area, the number of coordination of surface atoms and the surface dipole, with the decreased stability order of (101) > (011) > (010) > (110) > (100) > (001) = (111). Our results indicate that under Co-poor condition, the formation of non ? stoichiometric surface (011) and (111) without terminated cobalt is energetically more favorable, while under Co-rich condition the formation of non ? stoichiometric (111) surface with cobalt overlayer are preferential.     

Effective utilization of spray pyrolyzed CeO2 as optically passive counter electrode for enhancing optical modulation of WO3

Nanocrystalline cerium oxide (CeO₂) thin films were deposited onto the fluorine doped tin oxide coated glass substrates using methanolic solution of cerium nitrate hexahydrate precursor by a simple spray pyrolysis technique. Thermal analysis of the precursor salt showed the onset of crystallization of CeO₂ at 300 °C. Therefore, cerium dioxide thin films were prepared at different deposition temperatures from 300 to 450 °C. Films were transparent (T ~ 80%), polycrystalline with cubic fluorite crystal structure and having band gap energy (Eg) in the range of 3.04–3.6 eV. The different morphological features of the film obtained at various deposition temperatures had pronounced effect on the ion storage capacity (ISC) and electrochemical stability. The larger film thickness coupled with adequate degree of porosity of CeO₂ films prepared at 400 °C showed higher ion storage capacity of 20.6 mC cm^? 2 in 0.5 M LiClO₄ + PC electrolyte. Such films were also electrochemically more stable than the other studied samples. The Ce⁴⁺/Ce³⁺ intervalancy charge transfer mechanism during the bleaching–lithiation of CeO₂ film was directly evidenced from X-ray photoelectron spectroscopy. The optically passive behavior of the CeO₂ film (prepared at 400 °C) is affirmed by its negligible transmission modulation upon Li⁺ ion insertion/extraction, irrespective of the extent of Li⁺ ion intercalation. The coloration efficiency of spray deposited tungsten oxide (WO₃) thin film is found to enhance from 47 to 53 cm² C^? 1 when CeO₂ is coupled with WO₃ as a counter electrode in electrochromic device. Hence, CeO₂ can be a good candidate for optically passive counter electrode as an ion storage layer.     

Adsorption and interaction energy of π ethene on Pt(1 1 1) and Pt alloys: A detailed analysis of vibrational,energetic and electronic properties

We present a detailed analysis of the electronic and geometric bonding properties of the model alkene ethene on different mono- and bimetallic surfaces to establish the difference between adsorption energy and interaction energy and to elucidate the chemical character of a single platinum atom in different chemical environments. The adsorption of ethene on Pt(1 1 1) at 100 K leads to two adsorption states, which are commonly described as being of di-σ-type (bidentate, μ₂η²) and π-type (monodentate, μ₁η²). While the later is the minority species on Pt(1 1 1) it is of larger abundance on the platinum alloys. We have chosen π-bonded ethene for our study since it can be found on Pt(1 1 1), the Pt₃Sn and Pt₂Sn surface alloys, and Cu₃Pt(1 1 1). Density functional theory calculations of the adsorption structures, site and decomposed densities of states, as well as partial charge densities in conjunction with vibrational spectroscopy show that the bonding, i.e. the interaction energy, of the π ethene is only weakly influenced by alloying. Even in a copper matrix – as in the case of Cu₃Pt(1 1 1) – the bonding platinum atom essentially keeps its chemical identity and the interaction energy is reduced by only 14% compared to Pt(1 1 1). This observation suggests that bonding on surfaces is a strongly localized phenomenon. However, the adsorption energy decreases significantly due to alloying, which is attributed to the varying local relaxation of the different metal surfaces.     

Texture analysis of RF-sputtered CeO2 buffer layers and superconducting MOD-YBCO films

CeO₂ buffer layers were deposited on YSZ single-crystal substrates using an RF-sputtering method. The development of crystalline textures of sputtered CeO₂ films at different sputtering pressure and their effects on YBCO films, deposited by Metal Organic Deposition (MOD), were investigated. Both CeO₂ and subsequent YBCO films grew well epitaxially. The relative XRD peak intensities of CeO₂ (2 0 0) to substrate YSZ (2 0 0) increased with deposition pressure in the range of 3–5 mTorr and were inversely proportional to the θ–2θ scan FWHM values of CeO₂ (2 0 0). Also, the reaction layers of BaCeO₃ were thicker in the samples with lower CeO₂ (2 0 0) intensities and poor out-of-plane alignment when CeO₂ were deposited at the lower pressure of 3.3 mTorr. It is noted, however, that the superconducting layer grew well epitaxially on these BaCeO₃ layers, possibly due to the epitaxial relation between CeO₂ and YBCO. The superconducting critical currents of MOD-YBCO films showed an increasing tendency as both the Δ2θ (CeO₂) and BaCeO₃ peak intensities decreased.     

Ab initio determination of atomic structure and energy of surface states of bare and hydrogen covered GaN (0001) surface — Existence of the Surface States Stark Effect (SSSE)

Density Functional Theory (DFT) calculations indicate that energetically stable structure of clean GaN(0001) surface posses (2 × 1) reconstruction, having every second row of Ga located near plane of N atoms, that gives rise to Ga-related dispersionless surface electronic state, already identified by angle resolved photoelectron spectroscopy (ARPES) measurements [S.S. Dhesi et al. Phys. Rev. B 56 (1997) 10271, L. Plucinski et al. Surf. Sci 507-10 (2002) 223, S. M. Widstrand et al. Surf. Sci. 584 (2005) 169]. The energy reduction in reconstruction proceeds via change of the hybridization of the occupied Ga surface states from sp³ to sp², transforming the empty states to p_z type. It is also shown that the electric subsurface field, modeled in new slab model which allows to simulate electric fields at the semiconductor surfaces [P. Kempisty et al., J. Appl. Phys. 106 (2009) 054901], strongly affects the energy of electronic states of GaN(0001) surfaces. The change of the field may shift the energy of surface states of bare and hydrogen covered GaN(0001) surface, by several eV with respect to the band states. The phenomenon, denoted as Surface States Stark Effect (SSSE), explains various band bending values, measured at differently doped n-type GaN(0001) surfaces. It is shown also that, for the adsorbate density up to one H atom for each Ga surface atom i.e. 1 monolayer coverage (1 ML), the hydrogen adatoms are located at the on-top positions, i.e. directly above Ga atoms. For these adsorbate densities, the H-related quantum surface state is located slightly below the valence band maximum (VBM) in the case of p-type GaN surface. For n-type GaN, the H-related surface state is located deeply in the valence band, about 2 eV below VBM. For higher, 1.25 ML hydrogen coverage, the two H adatoms create either surface attached H₂ ad-molecule (energetically stable) or triple bridge configuration is created (metastable). The H₂ ad-molecule is weekly attached to the surface, having the desorption energy barrier equal to 0.16 eV. For 1.25 ML coverage the DFT results were obtained for p-type GaN only. They show that in the ad-molecule case, a new surface electronic state arises which is located about 6.7 eV below VBM. In the case of the bridge configuration, the bridge related surface state is located closely to the conduction band minimum (CBM).     

Structural,electronic, stability and reduction properties of perovskite surfaces: The case of rhombohedral BaCeO3

The (100), (110) and (111) surfaces of rhombohedral phase BaCeO₃ perovskite with two kinds of surface terminations are investigated using a periodic DFT + U method. We show that the lowest energy for surface formation via crystal cutting (cleavage energy) corresponds to (100) terminations. Out of all studied terminations, only BaO(100) and BaCeO(110) are stable with respect to precipitation of oxide phases and metals in respective ranges of oxygen chemical potentials, whereas CeO2(100) termination is not stable with respect to CeO₂ precipitation for all temperatures and oxygen partial pressures. Analyzing the electronic properties of the surfaces, we have established that reduction of the cerium oxidation state occurs in response to the local stoichiometry (lack of surface oxygen's, etc.) rather than as a result of breaking of cerium–oxygen bonds and formation of under-coordinated cerium ions. This equally applies to cerium reduction in the case of surface vacancy formation. We have calculated the vacancy formation energies as these can be viewed as a measure of surface activity in the catalytic reaction with various adsorbates. We find that CeO2 termination of the (100) surface and modified O2 termination of the (110) surface (O termination) have the lowest vacancy formation energies.     

Quantification of local oxygen defects around Yttrium ions for yttria-doped ceria–zirconia ternary system

Local coordination structure around Yttrium ions in CeO₂–Y₂O₃ binary and [(CeO₂)_x(ZrO₂)_1?x]_0.8(YO_1.5)_0.2 (x = 0.0 ~ 1.0) ternary system has been investigated by ⁸⁹Y MAS-NMR. NMR spectra are found to be consisted of multiple peaks that can be assigned to 6-, 7- and 8-oxygen coordinated Yttrium ions. Compositional dependence of the spectrum was observed and compared with the previous results for ZrO₂–Y₂O₃ binary system. The present investigation suggested the degree of localization of the oxygen vacancy around the cation is in the order of Zr⁴⁺ > Y³⁺ > Ce⁴⁺. The degree of the oxygen vacancy preference for each cation was quantitatively determined for CeO₂–ZrO₂–Y₂O₃ ternary system the first time.     

Theoretical studies on chemisorption of oxygen on β-Mo2C catalyst and its surface oxidation

Oxygen chemisorption on β-Mo₂C surface and its oxidation have been investigated by using the density functional theory with the periodic models. Two surfaces of (011) and (101) were chosen to perform the calculations and the most stable surface structures together with the energetics of oxygen stepwise adsorption were identified. Thermodynamic effect of temperature and reactant pressure on the chemisorption and surface oxidation was investigated. The results suggest that the (101) surface is more active than the (011) surface towards the oxygen adsorption. The (101) surface can be fully oxidized by O₂ at P_O2/P⁰ of 10^? 21–10⁴ and temperature of 100–700 K. For the (011) surface with O₂ as the oxidant, the most stable structure is that with 1/2 ML or 7/8 ML oxygen coverage, depending on the temperature and P_O2/P⁰ value. The increase of gaseous oxidant pressure or decrease of temperature can enhance the oxidation of β-Mo₂C surface and lead a more negative reaction Gibbs free energy. High temperature and low oxidant pressure may hinder the surface oxidation process.     

Low temperature oxidation of Fe2+ surface sites on the (2 × 1) reconstructed surface of α-Fe2O3(011­2)

Temperature programmed desorption (TPD), electron energy loss spectroscopy (ELS) and low energy electron diffraction (LEED) were used to study the interaction of molecular oxygen with the (2 × 1) reconstructed surface of hematite α-Fe₂O₃(011­2) under UHV conditions. The (2 × 1) surface is formed from vacuum annealing of the ‘ideal’ (1 × 1) surface and possesses Fe²⁺ surface sites based on ELS. While O₂ does not stick to the (1 × 1) surface at 120 K, the amount of O₂ that can be reversibly adsorbed at 120 K on the (2 × 1) surface was estimated to be ～ 0.5 ML (where 1 ML is defined as the Fe³⁺ surface coverage on the ideal (1 × 1) surface), with additional O₂ that is irreversibly adsorbed based on subsequent H₂O TPD. Molecularly and dissociatively adsorbed O₂ modifies the surface chemistry of H₂O both in terms of enhanced OH stability (relative to either the (1 × 1) or (2 × 1) surfaces) and in the blocking of H₂O adsorption sites. While O₂ adsorption at 120 to 300 K does not transform the (2 × 1) surface into the (1 × 1) surface, the influence of O₂ on the (2 × 1) surface involves both charge transfer from surface Fe²⁺ sites and formation of an ordered c(2 × 2) structure resulting from O₂ dissociation.     

Preparation of novel CeO2-biochar nanocomposite for sonocatalytic degradation of a textile dye

The sonocatalytic performance of CeO₂ nanoparticles synthesized by a hydrothermal method (CeO₂-H) and CeO₂@biochar (CeO₂-H@BC) nanocomposite, were evaluated for the degradation of Reactive Red 84 (RR84) under ultrasonic irradiation. For comparison purposes the corresponding performance of bare biochar (BC) and commercial CeO₂ (CeO₂-C) samples were also assessed. A complementary characterization study, involving scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Transmission electron microscopy (TEM), dynamic light scattering (DLS), X-ray diffraction (XRD), N₂ adsorption at −196 °C (Brunauer–Emmett–Teller (BET) method) and Fourier transform infrared spectroscopy (FT-IR) was undertaken to gain insight into the structure-performance relationships. The effect of various parameters such as initial RR84 concentration, solution pH, catalyst amount and ultrasonic power on the sonodegradation of RR84 was studied in detail. The results indicated that the CeO₂-H@BC nanocomposite exhibited the best RR84 degradation efficiency, which is enhanced with the increase of CeO₂-H@BC amount and ultrasonic power but diminished with the increment in RR84 concentration and pH value. A 98.5% degradation was obtained with a CeO₂-H@BC amount of 1 g/L, ultrasonic power of 450 W, pH of 6.5 and initial RR84 concentration of 10 mg/L. The quenching effects of various scavengers proposed that OH radical plays the key role in the process. Analyses of intermediates by Gas chromatography-Mass spectroscopy (GC–MS) identified several by-products and accordingly the main pathway was proposed.     

Periodic density functional theory studies of the VOx/TiO2 (anatase) catalysts: Structure and stability of monomeric species

Periodic density functional theory has been utilized to investigate the structure and stability of monomeric HVO_x species on anatase support. The three most stable surfaces of anatase were investigated, namely the (001), (100) and (101) surfaces. Unlike previous theoretical studies it was found that on the (001) surface vanadia species with five-coordinated vanadium atom are more stable than those with tetrahedrally coordinated vanadium atom. On the other hand, on the (100) and (101) surfaces, the vanadium atom in the vanadia species is still tetrahedrally coordinated. The stability of different VO_x/TiO₂ structures which are not fully dehydrated has been systematically studied and the results show that the vanadia species on the three surfaces follow an order of TiO₂ (001) > TiO₂ (100) > TiO₂ (101). This can be understood from the acidity and basicity of the three anatase surfaces. The results suggest that monomeric VO_x species may be better stabilized if the support exposes more (001) surfaces. Our analyses on electronic structure of the most stable VO_x/TiO₂ structure (D₀₀₁) suggest that its bridging V–O–Ti oxygen atoms may have higher reactivity than the terminal vanadyl oxygen atoms.     

Epitaxial growth of La2Zr2O7 buffer layers for YBa2Cu3O7−δ coated conductors on metallic substrates using pulsed laser deposition

In the present work, La₂Zr₂O₇ (LZO) buffer layers were deposited using pulsed laser deposition (PLD) on various metallic substrates including epitaxial pure Ni on a LaAlO₃ (LAO) substrate as well as highly textured Ni–5 at.%W tapes. It is shown that the LZO deposited on pure Ni-buffered LAO exhibits a mixed orientation while LZO on Ni–5 at.%W grows epitaxially. This difference may be explained by the existence of a sulphur superstructure on the surface of Ni–5 at.%W tapes, promoting the epitaxial (0 0 l) nucleation of seed layers. Highly textured YBa₂Cu₃O_7?δ layers were prepared either by using a single buffer layer of LZO or bilayer buffers of CeO₂/LZO on Ni–5 at.%W. The superconducting transition temperature (T_c) increases with the LZO thickness, reaching a value of 90 K with a very narrow transition width (1.5 K) for 240 nm thick LZO layers. Inductive J_c measurements at 77 K in self-field show a value of about 0.96 MA/cm² for the thickest LZO layers, which is comparable to the value observed on standard buffer architectures such as CeO₂/YSZ/Y₂O₃.     

Electronic and optical properties of defect chalcopyrite HgAl2Se4

The structural, electronic and optical properties of HgAl₂Se₄ are investigated using the full potential linear augmented plane wave method based on density functional theory. The calculated structural parameters using LDA are in excellent agreement with the available experimental result. The obtained energy band gap (2.24 eV) using EV-GGA approximation is in excellent agreement with experimental data (2.20 eV). Variation in the energy band gap as a function of the unit cell lattice parameter has been studied. The optical properties show a considerable anisotropy, which makes this compound very useful for various linear–nonlinear optical devices.