Organic ion species sputtered from contaminated water ice by 1.5 MeV N2+ ions

Electronic sputtering of organic species being mixed to water ice by residual-gas condensation is analyzed by secondary ion time-of-flight mass spectrometry. The ice samples were prepared at 15 K by deposition from a H₂O gas-flow and irradiated by 1.5 MeV N²⁺ ions while the temperature was raised up to 216 K. Desorption ion yields of positive H₂O specific ions as of some organic ion species are measured as a function of temperature. Remarkably high desorption yield variations, mainly of the C_nH_m ions, were observed during the enrichment of organics hiding the emission of (H₂O)_nH₃O+ cluster ions.     

Luminescent properties of green- or red-emitting Eu-doped Sr3Al2O6 for LED

Eu²⁺-doped Sr₃Al₂O₆ (Sr_3−xEu_xAl₂O₆) was synthesized by a solid-state reaction under either H₂ and N₂ atmosphere or CO atmosphere. When H₂ was used as the reducing agent, the phosphor exhibited green emission under near UV excitation, while CO was used as the reducing agent, the phosphor mainly showed red emission under blue light excitation. Both emissions belong to the d-f transition of Eu²⁺ ion. The relationship between the emission wavelengths and the occupation of Eu²⁺ at different crystallographic sites was studied. The preferential substitution of Eu²⁺ into different Sr²⁺ cites at different reaction periods and the substitution rates under different atmospheres were discussed. Finally, green-emitting and red-emitting LEDs were fabricated by coating the phosphor onto near UV- or blue-emitting InGaN chips.     

Adsorption of hydrogen and carbon monoxide on platinum

TDS spectra and ESD ion energy distributions have been measured for coadsorption of H₂ and CO on recrystallized platinum. Sample exposure to a 90% H₂?10% CO gas mixture results in appearance of structurein both TDS spectra of H₂ and CO. Coadsorption also results in an O⁺ ion energy distribution which is much narrower compared to the distribution resulting from pure CO adsorption. These results are interpreted as evidence for the formation of an HCO surface complex.     

Femtosecond electron dynamics on solid surfaces probed by low energy ion scattering and stimulated desorption of secondary ions

The cations emission from condensed matter surfaces has been investigated on the basis of localization and delocalization of valence hole(s) in the femtosecond timescale. The yield of scattered H⁺ (E₀=100 eV), though negligibly small from the Pt(1 1 1) substrate, increases markedly when Ar is adsorbed on it, indicating the localization of a valence (H⁺ 1s) hole on the physisorbed Ar layer. However, the yield of H⁺ scattered from a thick H₂O layer is considerably small relative to that from Ar and CO layers. The delocalized nature of a valence hole in water ice is caused by some covalency in hydrogen bonds. Hydrated protons, H⁺(H₂O)_n, n=1,2,…,10, are emitted efficiently in electron stimulated desorption from water molecules adsorbed on the Ar layer; the ion yields are highest at the initial adsorption stage and decay steeply with increasing coverage. Coulombic repulsion between the hydrated protons confined in physisorbed nanoclusters is responsible for the explosive ion emission.     

Adsorption and coadsorption of carbon monoxide and hydrogen on Pd(111)

The adsorption and coadsorption of CO and H₂ have been studied by means of thermal desorption (TD) and electron stimulated desorption (ESD) at temperatures ranging from 250 to 400 K. Three CO TD states, labelled as β₂, β₁, and β₀ were detected after adsorption at 250 K. The population of β₂ and β₁ states which are the only ones observed upon adsorption at temperatures higher than 300 K was found to depend on adsorption temperature. The correlation between the binding states in the TD spectra and the ESD O⁺ and CO⁺ ions observed was discussed. Hydrogen is dissociatively adsorbed on Pd(111) and no ESD H⁺ signal was recorded following H₂ adsorption on a clean Pd surface. The presence of CO was found to cause an appearance of a H⁺ ESD signal, a decrease of hydrogen surface population and an arisement of a broad H₂ TD peak at about 450 K. An apparent influence of hydrogen on CO adsorption was detected at high hydrogen precoverages alone, leading to a decrease in the CO sticking coefficient and the relative population of CO β₂ state. The coadsorption results were interpreted assuming mutual interaction between CO and H at low and medium CO coverages, the “cooperative” species being responsible for the H⁺ ESD signal. Besides, the presence of CO was proved to favour hydrogen penetration into the bulk even at high CO coverage when H atoms were completely displaced from the surface.     

The use of low energy sims to study the chemisorption of CO on Ni(100) and polycrystalline nickel

Adsorption of CO on Ni(100) has been investigated using secondary ion mass spectrometry (SIMS) and Auger electron spectroscopy at 175 and 295 K. Interaction with polycrystalline nickel was examined at 295, 325 and 365 K. All the secondary ions, Ni⁺, Ni₂⁺, NiCO⁺ and Ni₂CO⁺ show large increases in intensity as CO is adsorbed but there is no simple correlation of the secondary ion species with the sequence of linear and bridge-bonded CO species expected from electron energy loss spectroscopy. Adsorption of CO at 175 K on a hydrogen saturated Ni(100) surface, which is thought to permit only bridge-bonded adsorbed CO, does not result in any enhancement of Ni₂CO⁺. The extent of increases in secondary ion yields after CO adsorption on the nickel surfaces are primarily related to the variations in the heat of adsorption as a function of surface coverage. The presence of more weakly-held species is important in enhancing secondary ion yields.     

SIMS,EID and flash-filament investigation of O2, H2, (O2 + H2) and H2O interaction with vanadium

Comparative investigations of secondary ion emission, electron induced ion emission and flash filament signals from polycrystalline vanadium surfaces exposed to well-defined O₂, H₂, H₂O and (O₂ + H₂) doses (<500 L) have been carried out. The vanadium target could be heated and bombarded by either electrons (300 eV) or ions (3 keV) under ultra high vacuum conditions (<10^?10 Torr). The investigations were carried out with a computer controlled ultra high vacuum mass spectrometer. The experimental results establish exact reproducible spectra of well defined surface layers. They give detailed insight into the reactions between H₂, O₂ H₂O and vanadium, and some interactions between these species. They further indicate the importance of bulk and surface diffusion as well as the influence of the probing ion and electron bombardment. A clear distinction between bulk oxygen, surface oxides, and adsorbed oxygen for the vanadium-oxygen interaction at room temperature could be established. For the interaction of hydrogen with clean and oxygen covered vanadium surfaces the formation of adsorbed hydrogen, bulk solution of hydrogen, and the formation of OH groups and H₂O could be demonstrated. A detection limit below 10^?5 of one single monolayer for metal bonded hydrogen could be established.     

CO on Pt(111): TDS and ESD study

Electron stimulated desorption of ionic species from CO adsorbed on Pt(111) has been studied and comparison made with EELS results. The “on-top” site which, according to EELS data, fills first is observed to yield O⁺ ion. The bridge adsorption site appears to release CO⁺ during electron bombardment. Coadsorption of H₂ and CO was also examined and compared with the polycrystalline platinum case. Only very weak coadsorption effects are seen on the Pt(111) surface, as evidenced by presence of a weak low energy component associated with the O⁺ ESD energy distribution.     

DRIFTS study of different gas adsorption for CO selective oxidation on Cu-Zr-Ce-O catalysts

The adsorptions of different gases (CO, H₂ and O₂) in the hydrogen-rich gas on the co-precipitated Cu-Zr-Ce-O catalyst were discussed and the active sites were ascertained with infrared spectroscopy technique. It was shown that the adsorption strength of CO was stronger than that of O₂ or H₂. Hydrogen and CO were competitive adsorption and the coexistence H₂ and CO on the surface accelerated the rate of CO desorption. Adsorbed H₂ could convert into geminal OH groups on the ceria surface at high temperatures in the absence of oxygen, while it was easy to form surface hydroxyl groups at low temperatures and condensed to physical water with increasing desorption temperature in the existence of oxygen. The adsorption of CO₂ was strong and it could transform into thermal stable carbonate species even in the reaction conditions. The active sites of the Cu-Zr-Ce-O catalyst were Cu²⁺ and Cu⁺, mainly the latter. The oxygen defect sites could be formed on the Cu-Zr-Ce-O catalyst surface through dehydration and decarboxylation.     

Associated and single iron ions in ion-exchanged faujasite zeolites

Different forms of extraframework ions present in faujasite zeolite prepared by Fe²⁺ ion exchange at different pH values and with subsequent reduction in hydrogen have been studied. “Low-coordination” Fe_tetr ²⁺ ions can be found either in the form of single ions accessible for chemisorption, or in the form of ion associations from which centers of the catalytic processes can be formed in the CO+H₂ reaction. “High-coordination” Fe_oct ²⁺ ions are not affected either by chemisorption or by CO+H₂ treatment.     

DC discharge experiment in an Ar/N2/CO2 ternary mixture: A laboratory simulation of the Martian ionosphere's plasma environment

A low-pressure DC plasma discharge sustained in a 1.6%Ar–2.7%N₂–95.3%CO₂ ternary mixture is studied. This plasma was generated in a total pressure range from 1.0 to 4.0 Torr, a power of 6.3 W and a 12 l/min flow rate of gases. The electron temperature was found to be 8.41 eV and the ion density, in the order of 10⁹ cm⁻³. The species observed in the plasma mixture were CO₂, CO₂⁺, CN, CO, CO⁺, O₂, O₂⁺, N₂, N₂⁺, NO, C⁺, Ar and Ar⁺. At the pressure range in the present study, the species observed do not change their intensity due to an increase in the pressure and they separate in two groups according to their emission intensity: the band of the first group (CO₂, CO₂⁺ and CN) is approximately a factor of 3 more intense than that of the second group (CO, CO⁺, O₂, O₂⁺, N₂, N₂⁺, NO, C⁺, Ar and Ar⁺). The behavior of the emission intensities may be correlated to the constant ion density and electron temperature measured. Also, we observed the same constant behavior in the ratios of the neutral and positive species intensities to that of the N₂ intensity, as a function of pressure. This may suggest that the different rate coefficients and cross sections of elastic collision, excitation and de-excitation of electronic or vibrational levels, inelastic and superelastic collisions of electrons with the gas phase and products, neutral–neutral interactions, resonant charged transfer processes, recombination, to mention some, to produce these species change in the same proportion, as a function of the pressure to keep the relative ratios of the species almost constant.     

The effect of oxygen islanding on Co and H2 oxidation on Pt(111)

A Pt(111) surface partially covered with ¹⁶O islands was postdosed with ¹⁸O₂ to increase the island size under conditions where oxygen atom mobility is limited. Subsequently, these islands were titrated with CO and H₂. Preferential production of species containing ¹⁸O was not observed during any stage of the reaction. Assuming there is no extensive mixing of ¹⁶O and ¹⁸O isotopes within the islands, the results indicate no preferential reaction at island perimeters. The data are consistent with a model in which reaction proceeds uniformly over the whole island but the concentration of the mobile species (CO, H) inside the island is controlled by the island structure. This model qualitatively accounts for several apparent rate anomalies reported for CO and H₂ oxidation.     

CuC3H-团簇阴离子与CO反应：H辅助的C-C偶联

本研究利用质谱和密度泛函理论计算研究了CuC₃H^-团簇阴离子与CO的反应. 实验结果指出CO与团簇CuC₃H^-中的C₃H^-部分偶联可生成唯一产物COC₃H^-. 此反应的活性和选择性远高于团簇CuC₃^-与CO的反应. 理论计算结果进一步明确了H辅助的C-C偶联反应.     

\mathrm{CO}_{2}^{*} chemiluminescence study at low and elevated pressures

Chemiluminescence experiments have been performed to assess the state of current $\mathrm{CO}_{2}^{*}$ kinetics modeling. The difficulty with modeling $\mathrm{CO}_{2}^{*}$ lies in its broad emission spectrum, making it a challenge to isolate it from background emission of species such as CH^? and CH₂O^?. Experiments were performed in a mixture of 0.0005H₂+0.01N₂O+0.03CO+0.9595Ar in an attempt to isolate $\mathrm{CO}_{2}^{*}$ emission. Temperatures ranged from 1654 K to 2221 K at two average pressures, 1.4 and 10.4 atm. The unique time histories of the various chemiluminescence species in the unconventional mixture employed at these conditions allow for easy identification of the $\mathrm{CO}_{2}^{*}$ concentration. Two different wavelengths to capture $\mathrm{CO}_{2}^{*}$ were used; one optical filter was centered at 415 nm and the other at 458 nm. The use of these two different wavelengths was done to verify that broadband $\mathrm{CO}_{2}^{*}$ was in fact being captured, and not emission from other species such as CH^? and CH₂O^?. As a baseline for time history and peak magnitude comparison, OH^? emission was captured at 307 nm simultaneously with the two $\mathrm{CO}_{2}^{*}$ filters. The results from the two $\mathrm{CO}_{2}^{*}$ filters were consistent with each other, implying that indeed the same species (i.e., $\mathrm{CO}_{2}^{*}$ ) was being measured at both wavelengths. A first-generation kinetics model for $\mathrm{CO}_{2}^{*}$ and CH₂O^? was developed, since no comprehensively validated one exists to date. CH₂O^? and CH^? were ruled out as being present in the experiments at any measurable level, based on calculations and comparisons with the data. Agreement with the $\mathrm{CO}_{2}^{*}$ model was only fair, which necessitates future improvements for a better understanding of $\mathrm{CO}_{2}^{*}$ chemiluminescence as well as the kinetics of the ground state species.     

Static sims studies of adsorbate structure: II. CO adsorption on Pd(111); adsorbate-adsorbate interactions on Ru(001), Ni(111) and Pd(111)

In a study of CO adsorption on Pd(111) it is shown that the secondary ion mass spectrum contains information on both adsorbate site geometry and adsorbate coverage. The fractional yields of PdCO⁺, Pd₂CO⁺ and Pd₃CO⁺, as a function of CO coverage are correlated with the changing site geometries suggested by reflection IR data. A relationship between secondary ion emission and the adsorbate-adsorbate interactions revealed by IR and EELS is also demonstrated for CO adsorption on Ru(001), Ni(111) and Pd(111).     

In situ auger electron spectroscopy applied to the study of chemisorption and diffusion during reactive implantation of titanium into iron

Auger electron spectroscopy (AES) has been used to monitor the composition of Fe and FeTi surfaces, in situ, during Ti, Fe and Ar ion implantation in the presence of CO, C₂H₂, CH₄, N₂ and NH₃ gases at pressures of approximately 10^-6 Torr. Implantation-induced subsurface carburization was observed for Ti⁺ implantation into Fe in CO and C₂H₂ and for Ar⁺ implantation into an FeTi alloy in CO. In these cases, Ti carbide-like bonding of carbon at the surface preceded the subsurface carburization. Carburization was not observed when CH₄ gas was present during Ti implantation of Fe nor was it observed when CO gas was present during Fe self-implantation. Subsurface nitridation, similar to but not exactly analogous to the carburization, occurred during Ti⁺ implantation of Fe with NH₃ gas present. Nitridation did not occur with N₂ gas present even though some nitrogen was adsorbed. The influences of surface chemical reactions are considered, along with other chemical and physical arguments, in proposing an interpretation of these results.     

Elucidation of mechanisms of ion—molecule reactions by ICR

The mechanisms of some positive and negative ion—molecule reactions have been determined by a quantitative ion cyclotron double-resonance technique with isotopically labelled reactants. Four types of mechanism were elucidated: charge transfer, ion transfer, atom abstraction and complex formation. Thus, charge transfer is shown to be the only major reaction channel in the systems CO⁺ + CO₂, SO⁻ + SO₂, and O⁻ + NO₂, while in the system Cl₂⁻ + Cl₂ CO ion transfer is the main mechanism, and complex formation with oxygen-atom scrambling is the major channel in O⁻ + N₂O.The experimental results also point out cases where the reaction proceeds by more than one mechanism as, for example, in the reaction system H₂O⁺ + H₂O.     

Luminescence properties of lanthanide(III) ions in concentrated carbonate solution

Luminescence properties of lanthanide(III) ions (Ln = Nd, Sm, Eu, Gd, Tb, Dy and Tm) were investigated by measuring the excitation and emission spectra, and emission lifetimes in H₂O and D₂O solutions of 3 moll^?1 K₂CO₃, where anionic tetra-carbonate complexes, [Ln(CO₃)₄]^5- were the predominant species.

Electronic transitions of the carbonato complex corresponding to both the excitation and emission spectra were assigned from the energy level diagrams of Ln(III) and compared with those of the aqua ion. Enhancement of emission intensity of the complex was observed at particular excitation transitions of Eu(III), Gd(III) and Tb(III), and at particular emission transitions of Sm(III), Eu(III), Dy(III) and Tm(III). The enhancement at the emission transition was estimated quantitatively as a branching ratio from the lowest emitting state of Ln(III), and discussed in terms of hypersensitivity.

Emission lifetimes of the carbonato complexes were all longer than those of aqua ions in H₂O solution, while the lifetimes of the complexes for Eu(III) and Tb(III) shorter than those in D₂O solution. The difference in non-radiative decay constants for the excited complex in H₂O and D₂O solutions was found to be proportional to an exponential of the energy gap of Ln(III). The lifetime ratio between the H₂O and D₂O solutions showed the order of Sm > Dy > Eu > Tb, corresponding to the opposite order of the energy gap. These were discussed in terms of an energy gap law, i.e. a relationship between the energy gap of Ln(III) and vibration energies of the ligand or water molecules.     

Ion induced secondary electron emission from single crystal surfaces

Yields of ion impact induced electrons from very pure Ni(110) and Ni(111) surfaces have been measured. In several tilt planes the angle of incidence of a 5 keV H⁺, H⁺₂ or H⁺₃ ion beam is varied from perpendicular to grazing incidence. Below = 75° the yield increases as sec but shows characteristic depressions when the beam is incident along crystallographically low indexed lattice directions. This is explained by kinetic electron emission with respect to the projectile transparency of the crystal lattice.     

In‐situ Raman spectroscopy study of Ru/TiO2 catalyst in the selective methanation of CO

Raman spectroscopic technique has been used to characterize a Ru/TiO₂ catalyst and to follow in situ their structural changes during the CO selective methanation reaction (S‐MET). For a better comprehension of the catalytic mechanism, the in‐situ Raman study of the catalysts activation (reduction) process, the isolated CO and CO₂ methanation reactions and the effect of the composition of the reactive stream (H₂O and CO₂ presence) have been carried out. Raman spectroscopy evidences that the catalyst is composed by islands of TiO₂–RuO₂ solid solutions, constituting Ru–TiO₂ interphases in the form of Ru_xTi_{1 − x}O₂ rutile type solid solutions. The activation procedure with H₂ at 300 °C promotes the reduction of the RuO₂–TiO₂ islands generating Ru^o–Ti³⁺ centers. The spectroscopic changes are in agreement with the strong increase in chemical reactivity as increasing the carbonaceous intermediates observed. The selective methanation of CO proceeds after their adsorption on these Ru^o–Ti³⁺ active centers and subsequent C―O dissociation throughout the formation of CH_x/C_nH_x/C_nH_xO/CH_x―CO species. These intermediates are transformed into CH₄ by a combination of hydrogenation reactions. The formation of carbonaceous species during the methanation of CO and CO₂ suggests that the CO presence is required to promote the CO₂ methanation. Similar carbonaceous species are detected when the selective CO methanation is carried out with water in the stream. However, the activation of the catalysts occurs at much lower temperatures, and the carbon oxidation is favored by the oxidative effect of water. Copyright © 2015 John Wiley & Sons, Ltd.