Wettability and surface free energy of electrolytically oxidized graphite fibers

Wettability of electrolytically oxidized graphite fibers has been investigated by contact angle measurements employing the Wilhelmy method. The atomic ratio of oxygen to carbon, O/C, in the surface layer of the graphite fiber increased with increasing electric specific charge. Contact angle hysteresis was not observed for the untreated graphite fiber (O/C=0.01). The contact angles decreased with increasing O/C, especially for the receding angle, and approached constant for O/C>0.2. The nondispersive and dispersive surface free energies of the oxidized graphite fibers were calculated from the experimentally determined contact angles. The nondispersive surface free energy increased by the oxidation, whereas the dispersive one decreased. From the results of surface analysis, it was found that the changes in the nondispersive and dispersive surface free energies were caused by the increase in O/C ratio and the decrease in surface crystallinity, respectively.     

Stability of atomic oxygen chemisorption on Pt‐alloy surfaces

A density functional theory calculation is used to investigate the atomic oxygen (O) stability over platinum (Pt) and Pt‐based alloy surfaces. Here, the stability is connected with the preferential adsorption sites for O chemisorptions and the adsorption energy. Thus, the interaction mechanism between atomic O and metal surfaces is studied by using charge transfer analysis. In this present paper, atomic structure and binding energy of oxygen adsorption on the Pt(111) are in a very good agreement with experiment and previous density functional theory calculations. Furthermore, we obtained that the addition of ruthenium (Ru) and molybdenum (Mo) on the pure Pt surface enhances the adsorption energy. Our charge transfer analysis shows that the largest charge transfer contributing to the metal‐O bonding formation is observed in the case of O/PtRuMo surface followed by O/PtRu surface. This is in consistency with metal d‐orbital characteristic, where Mo has much more empty d‐orbital than Ru in correspondence to accept electrons from atomic oxygen. Copyright © 2016 John Wiley & Sons, Ltd.     

Molecular dynamics simulations of the oxidation of aluminum nanoparticles

The oxidation of aluminum nanoparticles is studied with classical molecular dynamics and the Streitz-Mintmire (Streitz, F. H.; Mintmire, J. W. Phys. Rev. B 1994, 50, 11996) electrostatic plus (ES+) potential that allows for the variation of electrostatic charge on all atoms in the simulation. The structure and charge distributions of bulk crystalline alpha-Al(2)O(3), a surface slab of alpha-Al(2)O(3) with an exposed (0001) basal plane, and an isolated Al(2)O(3) nanoparticle are studied. Constant NVT simulations of the oxidation of aluminum nanoparticles are also performed with different oxygen exposures. The calculations simulate a thermostated one-time exposure of an aluminum nanoparticle to different numbers of surface oxygen atoms. In the first set of oxidation studies, the overall approximate ratios of Al to O in the nanoparticle are 1:1 and 2:1. The nanoparticles are annealed to 3000 K and are then cooled to 500, 1000, or 1500 K. The atomic kinetic energy is scaled during the simulation to maintain the desired temperature. The structure and charge distributions in the oxidized nanoparticles differ from each other and from those of the bulk Al(2)O(3) phases. In the Al(1)O(1) simulation, an oxide shell forms that stabilizes the shape of the particle, and thus the original structure of the nanoparticle is approximately retained. In the case of Al(1)O(0.5), there is insufficient oxygen to form a complete oxide shell, and the oxidation results in particles of irregular shapes and rough surfaces. The particle surface is rough, and the nanoparticle is deformed.     

氧化铜表面臭氧分解路径及表面氧物种生成机理研究

基于密度泛函理论（DFT）计算研究了O3在完整和具有氧空位的CuO(111)表面吸附的吸附位、吸附结构、吸附能和电子转移情况,比较了O3在完整表面和具有氧空位的表面分解的路径和能垒,分析了氧空位和表面吸附氧的生成机理。结果表明,在完整CuO表面,O3分子通过化学吸附或物理吸附表面结合,吸附能最高为-1.22eV（构型bri(2)）。O3在具有氧空位的CuO表面均为化学吸附,吸附能最高为-2.95eV（构型ovbri(3)）,显著高于完整表面的吸附能。O3吸附后,Cu吸附位的电荷密度减小,O3中的O原子附近的电荷密度显著增强,电荷从CuO表面转移到O3,并形成Cu-O离子键。O3分解后形成了超氧物种,提高了表面的氧化活性。在完整表面,以构型bri(2)为起始构型的路径反应能垒最低,为0.52eV;O2*在完整表面的脱附所需要的最低能量为0.42eV,形成氧空位的O2*脱附能为2.06eV。在具有氧空位的表面,O3分解的反应能垒为0.30eV（构型ovbri(1)）和0.12eV（构型ovbri(3)）,均低于完整表面的反应能垒;分解形成的O2*的最低脱附能也低于完整表面,为0.27eV。可见,氧空位的形成提高了吸附能,降低了反应能垒,使O3分子更容易吸附在CuO表面,并加快了O3的催化分解。     

Spatially anisotropic etching of graphite by hyperthermal atomic oxygen

The spatially anisotropic kinetics involved in the chemical reaction between highly ordered pyrolytic graphite (HOPG) and a beam containing hyperthermal (approximately 8 km s(-1)) O((3)P) atomic oxygen and molecular oxygen yields unique surface morphologies. Upon exposure at moderate sample temperatures (298-423 K), numerous multilayer circular pits embedded in the reacted areas have been observed with the use of atomic force microscopy and scanning tunneling microscopy. These pits have diameters spanning nanometers to micrometers and depths from a few to tens of nanometers. The most striking characteristic of these pits is the convex curvature of the pit bottoms, where the highest point on the pit bottom is at the center and the lowest point occurs around the peripheral edge. Such structure arises by the interplay between kinetics of pit nucleation, the spatially anisotropic kinetics involved in the lateral and downward reactivity of HOPG, and the fluence of atomic oxygen. These kinetics, which are also influenced by the high reactivity of the translationally hot impinging oxygen atoms, govern the overall morphological evolution of the surface.     

Nonstatistical behavior of reactive scattering in the (18)O+(32)O(2) isotope exchange reaction

The recombination of oxygen atoms with oxygen molecules to form ozone exhibits several strange chemical characteristics, including unusually large differences in formation rate coefficients when different isotopes of oxygen participate. Purely statistical chemical reaction rate theories cannot describe these isotope effects, suggesting that reaction dynamics must play an important role. We investigated the dynamics of the 18O + 32O2 --> O3(*) --> 16O + 34O2 isotope exchange reaction (which proceeds on the same potential energy surface as ozone formation) using crossed atomic and molecular beams at a collision energy of 7.3 kcal mol(-1), providing the first direct experimental evidence that the dissociation of excited ozone exhibits significant nonstatistical behavior. These results are compared with quantum statistical and quasi-classical trajectory calculations in order to gain insight into the potential energy surface and the dynamics of ozone formation.     

DFT and kinetics study of O/O2 mixtures reacting over a graphite (0001) basal surface

Spin-polarized density functional calculations were used to investigate the interaction of atomic and molecular oxygen on the basal graphite surface at several atomic coverages. Two carbon layers were enough to represent the graphite surface. Oxygen atoms bind mainly over C?CC bridge sites forming an epoxide-like structure with a two carbon puckering and with adsorption energies in the 0.95?C1.28?eV range, depending on the atomic coverage. Molecular oxygen only shows a very weak physisorption. Atomic adsorption and diffusion along with atomic recombination via Eley?CRideal and Langmuir?CHinshelwood mechanisms were studied. All surfaces processes were activated with energy barriers that decreased for lower atomic coverages. Relaxation effects were non-negligible. A microkinetic model with six elementary surface processes was proposed to see the overall behaviour of several initial O/O₂ mixtures flowing over a graphite surface at 300?C1,000?K. Thermal rate constants were derived from Density Functional Theory data and standard Transition State Theory. A very low steady-state atomic coverage (??_???<?0.5%) was predicted, and also very low atomic recombination coefficients were observed (??_O?<?5?×?10^?4). The Eley?CRideal together with the adsorption and desorption processes was much more important than the Langmuir?CHinshelwood reaction.     

Oxygen adsorption on β-quartz model surfaces: some insights from density functional theory calculations and semiclassical time-dependent dynamics

The O/β-quartz interaction is described by combining our time-dependent semiclassical approach to atom-molecule/surface scattering with first-principles electronic structure calculations at the DFT (PBE0) level of accuracy. In particular, the O, O(2) interaction potentials with an on-top Si atom and its nearest O atom both localized over three different silica clusters have been calculated as a function of the oxygen-silica approaching distance. The calculated DFT potential energy surface has been used in semiclassical trajectory calculations to investigate the sticking and inelastic reflection of oxygen atoms from a model β-quartz surface. The collisional mechanism, including the role played by the phonon dynamics, is brought to light and accurate sticking probabilities are calculated at five impact energies in the range [0.05-0.8] eV and T(S) = 1000 K. The different catalytic response of β-quartz and β-cristobobalite to the atomic oxygen flux is also discussed and highlighted.     

激光光解NO2产物——氧原子O(3PJ″)的REMPI离子谱

由Nd:YAG激光器三倍频, 输出波长为λ=355 nm（28 169 cm－1）的激光光解NO2分子产生的氧原子, 通过共振增强多光子电离（REMPI, resonance enhanced multiphoto ionization）及飞行时间（TOF, time of flight）质谱技术, 获得了自旋-轨道精细能级分辨的氧原子O(2p 3PJ″=2, 1, 0)离子谱.氧离子信号强度与UV电离激光能量（λ≈226 nm）之间的关系能用三次方曲线很好拟合, 它表明光解产物氧原子是通过（2＋1）多光子吸收过程而被电离的.由离子信号得到的氧原子基态三个自旋-轨道支能级布居比f1=I(3P1)/I(3P2)与f0=I(3P0)/I(3P2)分别为0.54±0.09和0.20±0.04, 并且在不同的光解激光能量下其布居比保持不变.这一比值与统计分布计算的值为0.6和0.2一致（即统计分布3P2∶3P1∶3P0=1:0.6:0.2）.这是由于样品(NO2)在较低的压力下（1.33×10－4 Pa）和极短的光解-电离时间范围内（10－8 s）, 产物O（3PJ″）支能级间几乎不可能发生碰撞能量转移, 因此, 氧原子三个自旋-轨道角动量分裂能级布居O（3PJ″=2, 1, 0）是统计分布的.     

Effect of reactive oxygen species generated with ultraviolet lamp and plasma on polyimide surface modification

Understanding the effect of reactive oxygen species (ROS), such as singlet oxygen molecule and atomic oxygen, on polyimide (PI) film properties, such as wettability, morphology, and chemical bonding state, is essential for further development of PI‐based surfaces. We investigated the effect of different ROS generated during ultraviolet (UV) and plasma treatment in oxygen gas on surface modification of Kapton PI. Different surface modification techniques, UV and plasma treatment, are known to generate different ROS. In this work, we demonstrate the effect of different ROS on PI surface modification. From the diagnostics of ROS by means of electron spin resonance and optical emission spectroscopy, we confirmed that during UV treatment, excited singlet oxygen molecules are the main ROS, while plasma treatment mainly generated atomic oxygen. The wettability of PI surface treated by UV and plasma resulted in hydrophilic PI surfaces. XPS results show that the wettability of PI samples is mainly determined by their surface O/C ratio. However, chemical bonding states were different: while UV treatment tended to generate C=O bonds, while plasma treatment tended to generate both C―O and C=O bonds. Singlet oxygen molecules are concluded to be the main oxidant during UV treatment, and their main reaction with PI was concluded to be of the addition type, leading to an increase of C=O groups on the surface of PI film. Meanwhile, atomic oxygen species were the main oxidant during plasma treatment, reacting with the PI surface through both etching and addition reaction, resulting in a wider variety of bonds, including both C―O and C=O groups.     

Atomic and electronic structure of unreduced and reduced CeO2 surfaces: a first-principles study

The atomic and electronic structure of (111), (110), and (100) surfaces of ceria (CeO2) were studied using density-functional theory within the generalized gradient approximation. Both stoichiometric surfaces and surfaces with oxygen vacancies (unreduced and reduced surfaces, respectively) have been examined. It is found that the (111) surface is the most stable among the considered surfaces, followed by (110) and (100) surfaces, in agreement with experimental observations and previous theoretical results. Different features of relaxation are found for the three surfaces. While the (111) surface undergoes very small relaxation, considerably larger relaxations are found for the (110) and (100) surfaces. The formation of an oxygen vacancy is closely related to the surface structure and occurs more easily for the (110) surface than for (111). The preferred vacancy location is in the surface layer for CeO2(110) and in the subsurface layer (the second O-atomic layer) for CeO2(111). For both surfaces, the O vacancy forms more readily than in the bulk. An interesting oscillatory behavior is found for the vacancy formation energy in the upper three layers of CeO2(111). Analysis of the reduced surfaces suggests that the additional charge resulting from the formation of the oxygen vacancies is localized in the first three layers of the surface. Furthermore, they are not only trapped in the 4f states of cerium.     

水在石墨(0001)面簇模型桥位上吸附的量子化学研究

用从头计算方法对水在石墨(0001)面桥位上的吸附进行了研究.用C₆H₈原子簇模拟石墨表面,在6-31G^*水平上计算了水在不同方向和位置上的吸附能量.研究表明:水在石墨面上的吸附很弱,属于物理吸附;在中性或带负电荷的石墨表面,当水分子中的氢原子靠近石墨面时,体系存在能量最小值,而在带正电荷的表面,当氧原子靠近石墨面时存在稳定的吸附点;不论表面带正电荷还是带负电荷,均对水分子的吸附起增强作用.     

Potential energy surfaces for oxygen adsorption, dissociation, and diffusion at the Pt(321) surface

We report a first-principles, periodic supercell analysis of oxygen adsorption, diffusion, and dissociation at the kinked Pt(321) surface. Binding energies and binding site preferences of isolated oxygen atoms and molecules have been determined, and we show that both atomic and molecular oxygen prefer binding in bridge sites involving coordinatively unsaturated kink Pt atoms. Binding energies of atomic and molecular oxygen in different sites correlate well with the average metallic Pt coordination number of Pt atoms forming each site, although differences exist between adsorbates in symmetrically similar sites due to the inherent chirality of the surface. Atomic O in the strongest binding bridge sites experiences relatively small energy barriers for diffusion to neighboring sites compared to O on Pt(111). However, due to the structure of the surface, O diffusion is only rapid between different sites around the kink Pt atom, whereas the effective long-range tracer diffusion, as determined from a simple course-grain model, is shown to be anisotropic and slower than on the Pt(111) surface. Four dissociation pathways for O(2) at low coverage are also reported and found to be in agreement with experimental observations of facile dissociation, even at low temperature.     

Local electronic structure of olivine phases of LixFePO4

Changes in the local electronic structure at atoms around Li sites in the olivine phase of LiFePO4 were studied during delithiation. Electron energy loss spectrometry was used for measuring shifts and intensities of the near-edge structure at the K-edge of O and at the L-edges of P and Fe. Electronic structure calculations were performed on these materials with a plane-wave pseudopotential code and with an atomic multiplet code with crystal fields. It is found that both Fe and O atoms accommodate some of the charge around the Li+ ion, evidently in a hybridized Fe-O state. The O 2p levels appear to be fully occupied at the composition LiFePO4. With delithiation, however, these states are partially emptied, suggestive of a more covalent bonding to the oxygen atom in FePO4 as compared to LiFePO4. The same behavior is found for the white lines at the Fe L2,3-edges, which also undergo a shift in energy upon delithiation. A charge transfer of up to 0.48 electrons is found at the Fe atoms, as determined from white line intensity variations after delithiation, while the remaining charge is compensated by O atoms. No changes are evident at the P L2,3-edges.     

Influence of stoichiometry and charge state on the structure and reactivity of cobalt oxide clusters with CO

Cationic and anionic cobalt oxide clusters, generated by laser vaporization, were studied using guided-ion-beam mass spectrometry to obtain insight into their structure and reactivity with carbon monoxide. Anionic clusters having the stoichiometries Co2O3(-), Co2O5(-), Co3O5(-) and Co3O6(-) were found to exhibit dominant products corresponding to the transfer of a single oxygen atom to CO, indicating the formation of CO 2. Cationic clusters, in contrast, displayed products resulting from the adsorption of CO onto the cluster accompanied by the loss of either molecular O 2 or cobalt oxide units. In addition, collision induced dissociation experiments were conducted with N 2 and inert xenon gas for the anionic clusters, and xenon gas for the cationic clusters. It was found that cationic clusters fragment preferentially through the loss of molecular O 2 whereas anionic clusters tend to lose both atomic oxygen and cobalt oxide units. To further analyze how stoichiometry and ionic charge state influence the structure of cobalt oxide clusters and their reactivity with CO, first principles theoretical electronic structure studies within the density functional theory framework were performed. The calculations show that the enhanced reactivity of specific anionic cobalt oxides with CO is due to their relatively low atomic oxygen dissociation energy which makes the oxidation of CO energetically favorable. For cationic cobalt oxide clusters, in contrast, the oxygen dissociation energies are calculated to be even lower than for the anionic species. However, in the cationic clusters, oxygen is calculated to bind preferentially in a less activated molecular O 2 form. Furthermore, the CO adsorption energy is calculated to be larger for cationic clusters than for anionic species. Therefore, the experimentally observed displacement of weakly bound O 2 units through the exothermic adsorption of CO onto positively charged cobalt oxides is energetically favorable. Our joint experimental and theoretical findings indicate that positively charged sites in bulk-phase cobalt oxides may serve to bind CO to the catalyst surface and specific negatively charged sites provide the activated oxygen which leads to the formation of CO 2. These results provide molecular level insight into how size, stoichiometry, and ionic charge state influence the oxidation of CO in the presence of cobalt oxides, an important reaction for environmental pollution abatement.     

A first-principles investigation of the effect of Pt cluster size on CO and NO oxidation intermediates and energetics

As catalysis research strives toward designing structurally and functionally well-defined catalytic centers containing as few active metal atoms as possible, the importance of understanding the reactivity of small metal clusters, and in particular of systematic comparisons of reaction types and cluster sizes, has grown concomitantly. Here we report density functional theory calculations (GGA-PW91) that probe the relationship between particle size, intermediate structures, and energetics of CO and NO oxidation by molecular and atomic oxygen on Pt(x) clusters (x = 1-5 and 10). The preferred structures, charge distributions, vibrational spectra, and energetics are systematically examined for oxygen (O(2), 2O, and O), CO, CO(2), NO, and NO(2), for CO/NO co-adsorbed with O(2), 2O, and O, and for CO(2)/NO(2) co-adsorbed with O. The binding energies of oxygen, CO, NO, and of the oxidation products CO(2) and NO(2) are all markedly enhanced on Pt(x) compared to Pt(111), and they trend toward the Pt(111) levels as cluster size increases. Because of the strong interaction of both the reactants and products with the Pt(x) clusters, deep energy sinks develop on the potential energy surfaces of the respective oxidation processes, indicating worse reaction energetics than on Pt(111). Thus the smallest Pt clusters are less effective for catalyzing CO and NO oxidation in their original state than bulk Pt. Our results further suggests that oxidation by molecular O(2) is thermodynamically more favourable than by atomic O on Pt(x). Conditions and applications in which the Pt(x) clusters may be effective catalysts are discussed.     

Highly efficient electron stimulated desorption of O+ from gadolinia-doped ceria surfaces

Highly efficient electron stimulated desorption of O+ from gadolinia-doped ceria (GDC) surfaces annealed at 850 K in ultrahigh vacuum is observed and investigated. O+ desorption has a major threshold of approximately 40 eV and an intrinsic kinetic energy of approximately 5.6 eV. Since the threshold energy is close to Ce 5s and Gd 5s core levels, Auger decay of core holes is likely associated with O+ desorption from sites related to oxygen vacancies. The interactions of water and molecular oxygen with GDC surfaces result in a decrease in O+ desorption, suggesting that water and oxygen molecules adsorb mainly to oxygen vacancies. The dependence of O+ kinetic energies on the incident electron energy and temperature reveals surface charging as a result of electron trapping, hole trapping, and electron-hole recombination. The activation energy for surface charge dissipation is found to be 0.43 eV, close to the activation energy for ionic conduction (0.47 to 0.6 eV) in the same material.     

Adsorption of atomic and molecular oxygen on the LaMnO3(001) surface: ab initio supercell calculations and thermodynamics

We present and discuss the results of ab initio DFT plane-wave supercell calculations of the atomic and molecular oxygen adsorption and diffusion on the LaMnO(3) (001) surface which serves as a model material for a cathode of solid oxide fuel cells. The dissociative adsorption of O(2) molecules from the gas phase is energetically favorable on surface Mn ions even on a defect-free surface. The surface migration energy for adsorbed O ions is found to be quite high, 2.0 eV. We predict that the adsorbed O atoms could penetrate the electrode first plane when much more mobile surface oxygen vacancies (migration energy of 0.69 eV) approach the O ions strongly bound to the surface Mn ions. The formation of the O vacancy near the O atom adsorbed atop surface Mn ion leads to an increase of the O-Mn binding energy by 0.74 eV whereas the drop of this adsorbed O atom into a vacancy possesses no energy barrier. Ab initio thermodynamics predicts that at typical SOFC operation temperatures (approximately 1200 K) the MnO(2) (001) surface with adsorbed O atoms is the most stable in a very wide range of oxygen gas pressures (above 10(-2) atm).     

Initial oxidation of a Rh(110) surface using atomic or molecular oxygen and reduction of the surface oxide by hydrogen

The formation conditions, morphology, and reactivity of thin oxide films, grown on a Rh(110) surface in the ambient of atomic or molecular oxygen, have been studied by means of laterally resolved core level spectroscopy, scanning tunneling microscopy and low energy electron diffraction. Exposures of Rh(110) to atomic oxygen lead to subsurface incorporation of oxygen even at room temperature and facile formation of an ordered, laterally uniform surface oxide at approximately 520 K, with a quasi-hexagonal structure and stoichiometry close to that of RhO(2). In the intermediate oxidation stages, the surface oxide coexists with areas of high coverage adsorption phases. After a long induction period, the reduction of the Rh oxide film with H(2) is very rapid and independent of the coexisting adsorption phases. The growth of the oxide film by exposure of a Rh(110) surface to molecular oxygen requires higher pressures and temperatures. The important role of the O(2) dissociation step in the oxidation process is reflected by the complex morphology of the oxide films grown in O(2) ambient, consisting of microscopic patches of different Rh and oxygen atomic density.