Vacancy formation and CO adsorption on gold-doped ceria surfaces

We study the effect of gold doping on oxygen vacancy formation and CO adsorption on the (1 1 0) and (1 0 0) surfaces of ceria by using density functional theory, corrected for on-site Coulomb interactions (DFT + U). The Au dopant substitutes a Ce atom in the surface layer, leading to strong structural distortions. The formation of one oxygen vacancy near a dopant atom is energetically “downhill” while the formation of a second vacancy around the same dopant requires energy. When the surface is in equilibrium with gaseous oxygen at 1 atm and room temperature there is a 0.4 probability that no oxygen atom left the neighborhood of a dopant. This means that the sites where the dopant has not lost oxygen are very active in oxidation reactions. Above 400 K almost all dopants have an oxygen vacancy next to them and an oxidation reaction in such a system takes place by creating a second vacancy. The energy required to form a second vacancy is smaller on (1 1 0) than on (1 0 0). On the (1 1 0) surface, it is much easier to form a second vacancy on the doped surface than the first vacancy on the undoped surface. The energy required to form a second oxygen vacancy on (1 0 0) is comparable to that of forming the first vacancy on the undoped surface. Thus doping makes the (1 1 0) surface a better oxidant but it has a small effect on the oxidative power of the (1 0 0) surface. On the (1 1 0) surface CO adsorption results in formation of a carbonate-like structure, similar to the undoped surface, while on the (1 0 0) surface direct formation of CO₂ is observed, in contrast to the undoped surface. The Au dopant weakens the bond of the surrounding oxygen atoms to the oxide making it a better oxidant, facilitating CO oxidation.     

The Na-adsorbed Ge(0 0 1) surface: Structure and STM image simulations

Sodium adsorbed on the Ge(0 0 1) surface causes reconstruction of the surface with the type of reconstruction depending on the amount of the adsorbate. We present theoretical investigations of the structure and electronic properties of Na-adsorbed Ge(0 0 1) for the coverage of 0.5 monolayer using the combination of two methods: a plane-wave basis method and a local-orbital minimal-basis method. Two possible minimum-total-energy atomic configurations have been found, namely, the Na/Ge(0 0 1)-p(2 ×1) and Na/Ge(0 0 1)-p(4 × 1) reconstructions. The surface electronic structure for all calculated configurations occurs to be metallic. Our investigations are completed by a simulation of STM images for the obtained atomic structures.     

Efficient channel of the associative oxygen desorption from Pt(1 1 1)

Mechanism of the associative desorption of oxygen from the Pt(1 1 1) surface has been studied on atomic level by means of density-functional calculations. Key to the association of two oxygen adatoms into the O₂ molecule is the excitation of one of the adatoms to on-top site, where it becomes essentially neutral. The related redistribution of the electronic density at the O adatom leads to the appearance of the lateral attraction with the other O atom, thus providing an efficient channel for associative desorption. Calculated local densities of states resemble the transformation of the electronic structure of adsorbed O adatoms from the reactive to bound state in the course of association.     

Surface modification of pitch-based spherical activated carbon by CVD of NH3 to improve its adsorption to uric acid

Surface chemistry of pitch-based spherical activated carbon (PSAC) was modified by chemical vapor deposition of NH₃ (NH₃-CVD) to improve the adsorption properties of uric acid. The texture and surface chemistry of PSAC were studied by N₂ adsorption, pH_PZC (point of zero charge), acid-base titration and X-ray photoelectron spectroscopy (XPS). NH₃-CVD has a limited effect on carbon textural characteristics but it significantly changed the surface chemical properties, resulting in positive effects on uric acid adsorption. After modification by NH₃-CVD, large numbers of nitrogen-containing groups (especially valley-N and center-N) are introduced on the surface of PSAC, which is responsible for the increase of pH_PZC, surface basicity and uric acid adsorption capacity. Pseudo-second-order kinetic model can be used to describe the dynamic adsorption of uric acid on PSAC, and the thermodynamic parameters show that the adsorption of uric acid on PSAC is spontaneous, endothermic and irreversible process in nature.     

The dynamics of hydrogen adsorption on polycrystalline uranium

The dynamics of dissociative hydrogen adsorption on clean polycrystalline uranium has been studied using temperature programmed desorption and supersonic molecular beams. The initial sticking probability was measured as a function of incident kinetic energy between 3 and 255 meV. Two adsorption channels were observed; a non-activated direct channel was shown to be active over the entire energy range studied and a low energy indirect channel that was characterised by a decrease in sticking probability with increasing beam energy, and an insensitivity to both surface temperature and a range of hydrogen coverages. Together these results suggest the existence of an unaccommodated molecular precursor that has sufficient lifetime and mobility to locate favourable sites and dissociatively adsorb.     

Ferromagnetism of MnxLiyZn1−x−yO films

We had prepared Mn-doped ZnO and Li, Mn codoped-ZnO films with different concentrations using spin coating method. Crystal structure and magnetic measurements demonstrate that the impurity phases (ZnMnO₃) are not contributed to room temperature ferromagnetism and the ferromagnetism in Mn-doped ZnO film is intrinsic. Interesting, saturated magnetization decreases with Mn or Li concentration increase, showing that some antiferromagnetism exists in the samples with high Mn or Li concentration. In addition, Mn_0.05Zn_0.95O film annealed in vaccum shows larger ferromagnetism than the as-prepared sample and more oxygen vacancies induced by annealing in reducing atmosphere enhance ferromagnetism, which supports the bound magnetic polaron model on the origin of room temperature ferromagnetism.     

State selective detection of sputtered Al neutrals by resonant laser ionization SNMS

It is important to optimize the resonance ionization efficiency of the sputtered particle by evaluating the internal energy of it. And also the dependence of the change of the internal energy of it on primary ion species and accelerating voltages was investigated. For this study, we developed proto-type resonance laser ionization SNMS instrument, which is a quadrupole SIMS apparatus combined with a wavelength tunable laser. The internal energy of the sputtered aluminum atoms, which has lowly lying excited state (112 cm⁻¹) on the ground state, was monitored. As the results, the internal energy of the sputtered aluminum atoms was not influenced by the change of the surface work function and primary ion beam energy at all. On the contrary, the density on lowly lying excited state drastically increased due to the existence of the oxygen on aluminum surface.     

Molecular depth profiling of polymers with very low energy ions

The need for a molecular depth profiling technique to study organic layers has become a strong incentive in the SIMS community in the last few years, especially with the recent successes obtained with cluster ion beam depth profiling. In this work, we have investigated a thoroughly different approach by using very low energy (down to 200 eV) monoatomic or diatomic ions to sputter organic matter. Quite surprisingly, we were able to retain specific molecular information on various polymers even at very high fluence.Polymethylmethacrylate (PMMA) and polyethylene terephthalate (PET) films were depth-profiled with 200 eV Cs⁺ and 500 eV O₂⁺ ions. With 200 eV Cs ions, the best profiles were obtained in the negative mode, due to a strong negative ionisation yield enhancement related to Cs retention in the polymer. A relatively high and stable signal from the most characteristic ions was measured all over the layer.With 500 eV O₂⁺, real molecular depth-profiles were also obtained in both the positive and the negative modes. Once again, the main characteristic fragments of PET or PMMA remain detectable with stable yields all over the profile.     

CH_4/N_2混合气体在CMS上的低温吸附分离实验研究

将煤层气液化后运往终端市场是一种十分有效的利用方式。与常规天然气不同,抽放煤层气含氮量高,采用有效的方式实现CH4/N2分离是煤层气液化流程中重要的环节。吸附分离是提高煤层气中甲烷浓度的可行方法。为了与低温液化过程紧密结合,探讨在低温下实现CH4/N2吸附分离的可行性,文中对CH4/N2在碳分子筛(CMS)上的低温分离特性进行了实验研究,并与常温下的实验结果进行了对比。实验结果表明,低温下CH4/N2吸附分离的特性与常温下有明显差别。