DFT study of Ni-CeO2 interaction: Adsorption and insertion

DFT-GGA calculations are used to investigate interaction of atomic nickel with ceria. Nickel adsorption on surfaces is compared with insertion into the bulk and subsurfaces using VASP calculations. The adsorption is considered upon the (1 1 1) and (1 1 0) surfaces of ceria since these surfaces are the most stable ones being formally generated from the least number of bond cleavages (one or two Ce-O bonds per Ce, respectively). When Ni atom is adsorbed on the (1 1 1) surface, it occupies a position atop whereas over the (1 1 0) surface it occupies a bridging position. The adsorption quenches the spin. Results for insertion both in the bulk material and in the (1 1 1) and (1 1 0) subsurfaces are presented. For the bulk, it is shown that an increase of Ni amount from 1/4 to 1 makes insertion more exothermic. The later is accompanied by a lattice expansion and a reduction of symmetry. For an amount 1/4, the Ni is inserted to a tetrahedral site. At larger concentration, it is in trigonal environment of three oxygen atoms, additional oxygen ligands being less tightly bound. For insertion in the sublayers of the (1 1 1) subsurface, the nickel atom occupies a similar position, also a ternary site. The interaction energy for nickel atom insertion is comparable to that for nickel adsorption, slightly larger for (1 1 1), slightly smaller for (1 1 0) surface. Diffusion into the bulk is thus likely. When inserted, the distance Ni-Ce is becomes short, 2.70 Å, in agreement with experiment and the system may evolve with the formation of a Ni₂Ce alloy.     

DFT study of CO and NO adsorption on low index and stepped surfaces of gold

Adsorption energies and vibrational frequencies of CO and NO adsorbed on gold (1 1 1), (1 0 0), (1 1 0) and (3 1 0) surfaces, as well as on adatoms on Au(1 0 0) have been calculated using density functional theory. The results clearly show that the adsorption energy of the molecules increases considerably with increasing the degree of coordinative unsaturation of the gold atoms to which the molecules bind, and thus support the view that defects, steps and kinks on the surface determine the activity of gold catalysts.     

Influence of the physico-chemical properties of CeO2-ZrO2 mixed oxides on the catalytic oxidation of NO to NO2

Commercial and home-made Ce-Zr catalysts prepared by co-precipitation were characterised by XRD, Raman spectroscopy, N₂ adsorption at −196 °C and XPS, and were tested for NO oxidation to NO₂. Among the different physico-chemical properties characterised, the surface composition seems to be the most relevant one in order to explain the NO oxidation capacity of these Ce-Zr catalysts. As a general trend, Ce-Zr catalysts with a cerium-rich surface, that is, high XPS-measured Ce/Zr atomic surface ratios, are more active than those with a Zr-enriched surface. The decrease in catalytic activity of the Ce-Zr mixed oxided upon calcinations at 800 °C with regard to 500 °C is mainly attributed to the decrease in Ce/Zr surface ratio, that is, to the surface segregation of Zr. The phase composition (cubic or t′′ for Ce-rich compositions) seems not to be a direct effect on the catalytic activity for NO oxidation in the range of compositions tested. However, the formation of a proper solid solution prevents important surface segregation of Zr upon calcinations at high temperature. The effect of the BET surface area in the catalytic activity for NO oxidation of Ce-Zr mixed oxides is minor in comparison with the effect of the Ce/Zr surface ratio.     

O-vacancy and surface on CeO2: A first-principles study

Atomic and electronic structures of CeO₂ (1 1 1), (1 1 0) and (1 0 0) surfaces are investigated using the first-principles density functional theory taking into account the on-site Coulomb interaction. Both the stoichiometric and O-deficient surfaces are examined in order to clarify the overall features. The CeO₂ (1 1 1) is found to be the most stable surface, followed by the (1 1 0) and (1 0 0) surfaces, consistent with experimental observations. Three surfaces exhibit different features of relaxation. Large relaxations are found at the (1 1 0) and (1 0 0) surfaces, while very small changes are observed at the (1 1 1) surface. It is found that the O-vacancy occurs more readily at the (1 1 0) surface as compared with the (1 1 1) surface. Furthermore, the formation energies of the O-vacancy in the surfaces are lower than that in the bulk. The energetically favorable O-vacancy locates in the second O-atomic layer for the (1 1 1) while at the surface layer for the (1 1 0). The excess electrons left with the removal of the O atom are distributed in the first two layers with certain (a considerable) fraction filling the Ce-4f states.     

Magnetic state of the bulk, surface and nanoclusters of CaMnO3: A DFT study

The electronic structures of bulk, 2D slabs and clusters of CaMnO₃ in various magnetic configurations are presented. The obtained results including optimized cell constant, band-gap, Mn magnetic moment, on-site Coulomb repulsion potential and p-d charge separation potential are in good agreement with experiment data. The energetically most preferable configuration was an insulating charge-transfer ground state with G-type antiferromagnetic (AF) configuration (classified according to Wollan and Koehler, Phys. Rev. 100 (1955) 545). For the finite 2D layers the C-type AF ground state was found to be most stable. The surface effect on magnetism of finite quasi 2D systems appeared to originate in the pyramidal field splitting of Mn 3d levels, which induced the formation of ferromagnetic (FM) regions within the AF matrix and the extension of FM correlation deep through 7 subsurface layers (2.7 nm from the surface). All finite systems (clusters and slabs) were found non-conducting due to the localization of electrons and the cancellation of surface excess carriers (holes) after surface relaxation, although the band-gaps of 2D systems were sufficiently reduced in comparison with that of the bulk.     

Adsorption of NH3 and NO2 molecules on C48B6N6 heterofullerene: A DFT study on electronic properties

Adsorption of NH₃ and NO₂ molecules on the external surface of C₄₈B₆N₆ heterofullerene is investigated using DFT method. Attachment of NH₃ and NO₂ on C₄₈B₆N₆ heterofullerenes are compared with the bare C₄₈B₆N₆ model optimized at the B3LYP/6-31G^? level. The high surface binding energies indicates that ammonia undergoes chemical adsorption and could be compatible with the long recovery time but C₄₈B₆N₆ should be good NO₂ sensors with quick response as well as short recovery time. Total (TDOS) and partial (PDOS) density of state calculations is also considered to elucidate the difference in the NH₃ and NO₂ gas detection mechanism of C₄₈B₆N₆. The overlap population density of state (OPDOS) indicated that the chemical adsorption is due to the overlap of atomic orbitals below the Fermi level. The calculated results suggest that the C₄₈B₆N₆ heterofullerene is a suitable sensor material for NO₂ and is an ideal material for elimination and filtering of ammonia.     

Adsorption of CO, CO2 and NO molecules on a BaTiO3 (0 0 1) surface

Since the development of Scanning Tunnelling Microscopy (STM) technique, considerable attention has been devoted to various molecules adsorbed on various surfaces. Also, a new concept emerged with molecules on surfaces considered as nano machines by themselves. In this context, a thorough knowledge of surfaces and adsorbed molecules at an atomic scale are thus particularly invaluable. The present work describes the first Density Functional Theory (DFT) study of adsorption of CO, CO₂ and NO molecules on a BaTiO₃ surface following a first preliminary calculation of O and O₂ adsorption on the same surface. In the previously considered work, we found that a (0 0 1) surface with BaO termination is more stable than the one with TiO₂-termination. Consequently, we extended our study to CO, CO₂ and NO molecules adsorbed on a (0 0 1) surface with BaO termination. The present calculation was performed on a (1 × 1) cell with one monolayer of adsorbed molecules. Especially, a series of cases implying CO molecules adsorbed in various geometrical configurations has been examined. The corresponding adsorption energy varies in the range of −0.17 to −0.10 eV. The adsorption energy of a CO₂ molecule directly located above an O surface atom (called O_s) is of the order of −0.18 eV. The O-C distance length is then 1.24 Å and the O-C-O and O-C-O_s angles are 134.0° and 113.0°, respectively. For NO adsorption, the most important induced structural changes are the followings: (i) the N-O bond is broken when a NO molecule is absorbed on a Ba-O_s bridge site. In that case, N and O atoms are located above an O and a Ba surface atom, respectively, whereas the O-Ba-O_s and N-O_s-Ba angles are 106.5° and 63.0°, respectively. The N-O distance is as large as 2.58 Å and the adsorption energy is as much as −2.28 eV. (ii) In the second stable position, the NO molecule has its N atom adsorbed above an O_s atom, the N-O axis being tilted toward the Ba atom. The N-O_s-Ba angle is then 41.1° while the adsorption energy is only −0.10 eV. At last, the local densities of states around C, O as well as N atoms of the considered adsorbed molecules have also been discussed.     

Heterogeneous fixation of N2: Investigation of a novel mechanism for formation of NO

Formation of NO initiated by heterogeneous fixation of N₂ during pyrolysis is investigated experimentally and theoretically. The experiments were conducted with beech wood as well as with the pure biomass components cellulose, xylan, and lignin. The NO formation during char oxidation was recorded as function of pyrolysis atmosphere (N₂ or Ar), pyrolysis temperature (700–1050 °C), and oxidizing atmosphere (O₂ in N₂ or Ar). The results confirm earlier reports that biomass char may be enriched in N during pyrolysis at 900 °C and above. The N-uptake involves re-capture of N-volatiles as well as uptake of N₂. During char oxidation, the captured N is partly oxidized to NO, resulting in increased NO formation. The NO yield from oxidation of beech wood char made in N₂ increases with pyrolysis temperature, and is about a factor of two higher at 1050 °C than the corresponding yield from chars made in Ar. The experiments with pure materials show that the lignin char has the strongest ability to form NO from uptake of N₂, while xylan char forms only small amounts of NO from N₂. Density Functional Theory (DFT) calculations on model chars have revealed a number of chemisorption sites for N₂, many of which are weakly bound and therefore expected to have a short half-life at the higher pyrolysis temperatures. However, the chemisorption of N₂ across a single ring of the armchair surface was found to have an activation energy of 344 ± 30 kJ mol⁻¹ and form a stable, exothermic product with cyano groups. This demonstrates that at least one channel exists for the high-temperature incorporation of N₂ into a char which could give rise to the observed increase in NO release in subsequent char oxidation.     

Cu/CeO2(110)界面特性的第一性原理研究

Cu-CeO₂体系因其特殊的催化能力而在固体氧化物燃料电池和水煤气转化反应等多个催化领域有重要应用. 采用基于密度泛函理论的第一性原理方法, 在原子和电子层面上系统地研究了单个Cu原子及Cu小团簇在CeO₂(110)面上的吸附构型, 价键特性和电子结构, 结果表明: 1) 单个Cu原子的最稳定吸附位是两个表面O的桥位; 2) Cu团簇的稳定吸附构型为扭曲的四面体结构; 3) Cu原子及Cu团簇的吸附在CeO₂(110)面的gap区域引入了间隙态, 这些间隙态主要来自于Cu及其近邻的O和表层还原形成的Ce³⁺, 间隙态的出现表明Cu的吸附增强了CeO₂(110)表面的活性; 4) 吸附的单个Cu原子及Cu团簇分别被CeO₂(110)面表层的Ce⁴⁺离子氧化形成了Cu^δ+和Cu₄^δ+, 并伴随着Ce³⁺离子的形成, 这个反应可归结为Cu_x/Ce⁴⁺→Cu_x^δ+/Ce³⁺; 5) Cu团簇的吸附比Cu单原子的吸附引入了更多的Ce³⁺离子, 进而形成了更多的Cu^δ+-Ce³⁺催化活性中心. 结合已报道的Cu/CeO₂(111)界面特性, 更加全面地探明了Cu与CeO₂(111)和(110)两个较稳定低指数表面的协同作用特性, 较为系统地揭示了Cu增强CeO₂催化特性的原因及Cu与CeO₂协同作用的内在机理. 关键词： 2')" href="#">Cu/CeO₂ U')" href="#">DFT+U 吸附 电子结构     

The effect of NO/O2 ratio in NO-CO-O2 reaction on a catalytic surface: A computer simulation study

The interaction among the reacting species in the NO-CO-O₂ reaction on a metal catalytic surface that proceeds according to the Langmuir-Hinshelwood mechanism is studied by means of Monte Carlo simulation. The study of this three-component system is essential for the understanding of the influence of NO/O₂ ratio on the catalytic reduction of NO into N & O and oxidation of CO to CO₂. It is found that this complex system, which has not been studied on these lines before, exhibits irreversible phase transitions between active states with sustained reaction and poisoned states with the catalytic surface fully covered by the reactants. The phase diagrams of the surface coverage with CO, N or O and the steady state production of CO₂ are evaluated as a function of the partial pressure of CO in the gas phase. From this study, it is observed that with the addition of NO in the CO-O₂ reaction, the critical points in the phase diagram move towards lower values of CO partial pressure but the width of reaction window remains almost the same. However, the maximum production rate of CO₂ decreases continuously. On the other hand, the addition of O₂ in the NO-CO reaction shifts the critical points towards higher values of CO pressure. Moreover, the width of reaction window as well as the production rate of CO₂ increases with the increase in O₂ concentration.     

低温等离子体分解N2/O2/NO气氛中NO试验研究

利用自行设计的介质阻挡放电型低温等离子体反应器,研究了NO初始浓度、O₂初始浓度、放电功率、电源频率等因素对NTP转化N₂/O₂/NO气氛中NO的影响规律。研究发现,NO去除率随功率增大而升高,到达一最大值后随功率增大而降低;NO去除率随O₂初始浓度增加而降低,随NO初始浓度增大而减小。相同放电功率下,同一组分中NO去除率随电源频率的增加而降低,因此相同放电功率下降低电源频率可提高NO去除率。O₂初始浓度不高于5%时,NO_x大部分为NO,NO₂和O₃浓度均随放电功率增大而降低,NO₂、O₃生成量随O₂初始浓度升高而增多。     

Electronic structure and optical properties of Sb2S3 crystal

The electronic and optical properties of Sb₂S₃ are studied using the full potential linearized augmented plane wave (FP-LAPW) method as implemented in Wien2k. In this approach, the alternative form of the generalized gradient approximation (GGA) proposed by Engel and Vosko (EV-GGA) was used for the exchange correlation potential. The calculated band structure shows a direct band gap. The contribution of different bands was analyzed from total and partial density of states curves. Moreover, the optical properties, including the dielectric function, absorption spectrum, refractive index, extinction coefficient, reflectivity and energy-loss spectrum are all obtained and analyzed in detail.     

Adsorption of CO, NH3 and O2 on Fe site of La0.875Sr0.125FeO3 (0 1 0) surface by density function theory calculation

The adsorption of CO, NH₃ and O₂ gas molecules on Fe site of La_0.875Sr_0.125FeO₃ (0 1 0) surface has been investigated based on the density functional theory (DFT) with the spin polarized generalized gradient approximation (GGA). The optimal adsorption orientations as well as the adsorption energies for these molecules adsorption on Fe site of La_0.875Sr_0.125FeO₃ (0 1 0) surface are derived. Results show that adsorption configurations with C-down for CO, N-down for NH₃ are stable. For the O₂ molecule adsorption, the mode with an angle about 120° between the oxygen molecule and La_0.875Sr_0.125FeO₃ (0 1 0) surface is stable.     

A DFT study the solvent effects of H2 adsorption on Cu(h k l) surface

Density functional theory (DFT) combined with conductor-like solvent model (COSMO) have been performed to study the solvent effects of H₂ adsorption on Cu(h k l) surface. The result shows H₂ can not be parallel adsorbed on Cu(h k l) surface in gas phase and only vertical adsorbed. At this moment, the binding energies are small and H₂ orientation with respect to Cu(h k l) surfaces is not a determining parameter. In liquid paraffin, when H₂ adsorbs vertically on Cu(h k l) surface, solvent effects not only influences the adsorptive stability, but also improves the ability of H₂ activation; When H₂ vertical adsorption on Cu(h k l) surface at 1/4 and 1/2 coverage, H-H bond is broken by solvent effects. However, no stable structures at 3/4 and 1 ML coverage are found, indicating that it is impossible to get H₂ parallel adsorption on Cu(h k l) surfaces at 3/4 and 1 ML coverages due to the repulsion between adsorbed H₂ molecules.     

A photoemission study of the interaction of Ga with CeO2(1 1 1) thin films

The interaction of gallium with CeO₂(1 1 1) layers was studied using standard and resonant photoelectron spectroscopy, by means of both a laboratory X-ray source and tunable synchrotron light. Firstly a 1.5-nm thick CeO₂ film was grown on a Cu(1 1 1) substrate. Secondly Ga was deposited in six steps up to a thickness of 0.35 nm, at room temperature. The interaction of gallium with the oxide layer induced partial CeO₂ reduction, and gallium oxidation. The photoemission data suggest that a mixed Ga-Ce-O oxide was established similarly to the Sn-Ce-O case for Sn deposited on cerium oxide layers. As a consequence, gallium-induced weakening of Ce-O bonds provides a higher number of active sites on the surface that play a major role in its catalytic behaviour.     

Characterization and catalytic performance of pure and Li2O-doped CuO/CeO2 catalysts

Pure and Li₂O-doped CuO/CeO₂ catalysts calcined at 500 °C were prepared by impregnation method. The catalysts are characterized by DTA, TG-DTG, XRD, IR, TEM, nitrogen adsorption at −196 °C and the catalytic decomposition of hydrogen peroxide at 30 °C.The effects of molar ratio, heat treatment time and the doping on the structural, surface and catalytic properties of nanocrystalline Cu/Ce-mixed oxides system have been studied. It was found that the catalytic activity of ceria-supported copper oxide catalysts increased by increasing both the heat treatment time and dopant content. However, the pure Cu/Ce-mixed oxide solids containing 10 wt.% CuO exhibited the best performance. The characterization results indicated that the higher surface area, the formation of solid solution between copper and cerium oxides, and the high dispersion of copper species on the ceria were responsible for the high catalytic activity of the CuO/CeO₂ catalysts.     

NO与C2H2的康普顿轮廓研究

基于第三代同步辐射光源, 在20 keV的入射X射线能量下测量了NO与C₂H₂分子的康普顿轮廓. 考虑到本次实验结果在p_z ≈ 0附近的统计精度达到了0.2%, 本文报道的NO和C₂H₂的康普顿轮廓可以作为严格检验理论的实验基准. 除此之外, 还分别采用HF方法及密度泛函方法选用不同的基组计算了NO 与C₂H₂康普顿轮廓. 通过对比实验结果与理论计算, 发现对于NO分子, 加入弥散函数基组理论计算结果与实验符合更好, 说明NO分子基态的电子分布较为弥散. 对于C₂H₂分子, HF方法理论计算的结果与实验符合较好.     

Low-temperature and ambient-pressure synthesis and shape evolution of nanocrystalline pure, La-doped and Gd-doped CeO2

Nanocrystalline cuboidal ceria has been synthesized by low-temperature hydrothermal reaction of cerium nitrate hexahydrate with hexamethylene tetramine. The particles have been doped with La and Gd by adding aqueous solution of the nitrate salts of the metals to the reaction mixture. The pure and doped particles are cubic in crystal structure and 10-25 nm in size. The pure and La-doped ceria are cuboidal in morphology, whereas the Gd-doped particles are irregular in shape. High-resolution TEM imaging and image simulation indicates that atomic level steps are present on the particle surfaces. The particles are faceted parallel to the {1 1 1} and {1 0 0} crystallographic planes and a continuous switching takes place between the two possible surface facets. It appears that the surface energies of the {1 1 1} and {1 0 0} facets are quite similar in magnitude and the interplay of surface energy determines the particle shape. Chemically sensitive imaging and spectroscopy shows that the dopants are homogeneously distributed within the particles and that the oxidation state of Ce is a mixture of +3 and +4. No preferential segregation either of the dopant or the oxidation state was observed. However, since the facet switching does depend on the chemistry of the dopant, there must be an affect on the atomic scale.     

Coadsorption of gold with chlorine on CeO2 (111) surfaces: A first principles study

To investigate the effects of chlorine on the Au/ceria catalysts,the adsorption of gold or chlorine and their coadsorpiton on the stoichiometric and partially reduced CeO₂（111） surfaces are studied from the first principles.It is found that the adsorption of Au is significantly enhanced by the chlorine preadsorption on the stoichiometric CeO₂（111） surface;while on the partially reduced CeO₂（111） surface,the preadsorbed chlorine inhabits the oxygen vacancy（which is the preferred adsorption site for gold）,leading to a CeOCl phase and the dramatical weakening of the Au adsorption.Therefore,chlorine on the CeO₂（111） surface can affect the Au adsorption thus the activity of the Au/CeO₂ catalyst.