Further study of continuous-wave CO flame chemical laser of the CS2/O2/N2O type

This report describes an experimental examination of the output characteristics of the continuous-wave (cw) carbon monoxide flame chemical laser (FCL) of the CS₂/O₂/N₂O type in case of small CS₂/O₂ reactants ratios (tipically CS₂/O₂≦1/10). A linear burner which gives a homogeneous and stable flame was used during the experimental study. The measurements of temperature distribution in CS₂/O₂ as well as CS₂/O₂/N₂O flames show maximum temperatures of 1040 and 890 K, respectively. The addition of nitrous oxide (N₂O) leads to dramatically enhanced output laser power caused primarily by V?V transfer processes. A chemical efficiency, based on the reaction O+CS→CO^*+S, of 3% was achieved. The spectral composition of the CO FCL of the CS₂/O₂/N₂O type shows lasing in the region from 5.130 to 5.586 μm. Experimental results were obtained with a nondispersive optical cavity.     

Reactivity of anionic gold oxide clusters towards CO: experiment and theory

In this paper, we present results from our joint experimental and theoretical study of the reactivity of anionic gold oxide clusters Au_2,3O_1-4 ^- towards CO. We provide clear evidence that, although O–O bond weakening/dissociation is important to enable CO oxidation, the presence of atomic oxygen can be favorable but is not always sufficient. Furthermore, we show that with the addition of a single gold atom the reactivity channels can be changed. As a consequence, in contrast to CO oxidation in the case of anionic gold dimer oxides, association of CO or replacement of O₂ by CO become the dominant reaction channels for Au₃O_n ^-. This demonstrates the nonscalable properties of gold clusters in the size regime in which each atom counts.     

Simultaneous determination of the ground level abundances of N2O,CO2, CO and H2O

The AFCRL atmospheric line-parameter listing has been used with a non-linear, least-squares method of analysis to obtain the abundances of N₂O and CO in a sample of ground level air with a precision of about 1%. Absorption coefficients calculated for N₂O agree satisfactory with laboratory measurements but an error of 0.0267 cm^-1 in the listed position of an H₂O line at 2205.250 cm^-1 has been corrected and errors in the positions and intensities of CO₂ lines between 2230 and 2250 cm^-1 have been observed.     

The interaction of CO and O2 with the (111) surface of Pt3Ti

The electronic properties of clean and partly oxidized Pt₃Ti(111) surfaces have been studied utilizing carbon monoxide both as a probe and as a reducing agent. Vibrational frequencies and desorption profiles of chemisorbed CO as well as ion scattering and angular resolved X-ray photoelectron spectroscopy (XPS) suggest that the first atomic layer of annealed Pt₃Ti(111) is quasi-pure platinum. Scarcely any (θ ≈ 0.01) dissociation of CO was observed. Minor shifts of vibrational frequencies and desorption temperatures compared to Pt(111) and a p(2 × 2) “reconstruction” of the clean surface reveal some influence of the bulk. Auger spectroscopy, XPS, and ion scattering all show an increased titanium signal as a result of oxidation. Surface bound atomic oxygen gives a vibrational band around 650 cm⁻¹ which coincides with infrared absorption spectra of TiO₂. Flashing with CO shifts the band to 500 cm⁻¹. Correlated with this shift we observe (i) CO₂ desorption at a temperature well above that observed for Pt(111)/O, (ii) an altered Ti XPS signal, and (iii) a reduced oxygen concentration. Subsequently adsorbed CO molecules vibrate at the same frequencies as on the bare surface, give the same c(4 × 2) LEED pattern, and desorb at the same temperatures but with reduced intensity, in all proving that the surface oxide only acts as a site-blocker with respect to the metal surface. Our current understanding of these observations is that oxygen creates “islands of TiO₂”, segregated to the surface but with no electronic influence on remaining areas of the platinum enriched metal surface. The hexacoordinated Ti⁴⁺ ions on the surface of these islands are reduced by CO to pentacoordinated Ti³⁺ species. The vibrational shift, 650 to 500 cm⁻¹, can be understood by the dipole active bands of a triatomic O−Ti⁴⁺ −O vibrator compared to a diatomic Ti³⁺−O vibrator.     

Conversion of nitrogen oxides in N2:O2:CO2 and N2:O2:CO2:NO2 mixtures subjected to a dc corona discharge

This paper concerns the influence of a direct current (dc) corona discharge on production and reduction of NO, NO₂ and N₂O in N₂:O₂:CO₂ and N₂:O₂:CO₂:NO₂ mixtures. The corona discharge was generated in a needle-to-plate reactor. The positively polarized electrode consisted of 7 needles. The grounded electrode was a stainless steel plate. The gas flow rate through the reactor was varied from 28 to 110 cm³/s. The time-averaged discharge current ranged from 0 to 6 mA. It was found that in the N₂:O₂:CO₂ mixture the corona discharge produced NO, NO₂ and N₂O. In the N₂:O₂:CO₂:NO₂ mixture the reduction of NO₂ was between 6–56%, depending on the concentration of O₂, gas flow rate and corona discharge current. The NO₂ reduction was accompanied by production of NO and N₂O. The results show that efficient reduction of nitrogen oxides by a corona discharge cannot be expected in the mixtures containing N₂ and O₂ if reducing additives are not employed.     

The absorption cross sections of N2, O2, CO,NO, CO2, N2O,CH4, C2H4, C2H6 and C4H10 from 180 to 700Å

The absorption cross sections of N₂, O₂, CO, NO, CO₂, N₂O, CH₄, C₂H₄, C₂H₆, C₄H₁₀ have been measured photoelectrically in the 180–700 Å region using synchrotron radiation. The absorption cross sections in the region λ ≥ 500 Å was found to be structureless and to increase monotonically with wavelength for all gases. The positions of the structure observed in the 520–720 Å region for N₂, O₂, CO₂ and N₂O are consistent with the various Rydberg series reported by previous authors.     

Reactivity and XAFS study on (1−x)CeO2-xNiO (x=0.025-0.3) system in the two-step water-splitting reaction for solar H2 production

The redox reaction of Ce⁴⁺-Ce³⁺ promoted by the catalytic function of nickel ions in a (1−x)CeO₂-xNiO solid solution was investigated for solar H₂ production by the two-step water-splitting reaction. By irradiation using an infrared imaging lamp as a solar simulator, the O₂-releasing reaction with (1−x)CeO₂-xNiO solid solution proceeded at 1673-1873 K, and its reduced form was produced. The amounts of H₂ gas evolved by the reduced form were 1.2-2.5 cm³/g and the evolved gases amounts ratio of H₂/O₂ was nearly 2, which is equal to the stoichiometric value of the water-splitting reaction (H₂O=H₂+1/2O₂). The maximum amounts of evolved H₂ and O₂ gases were obtained at the Ce:Ni mole ratio of 0.95:0.05 (x=0.05) in the (1−x)CeO₂-xNiO system. The X-ray absorption fine structure (XAFS) measurement showed that the O₂-releasing and H₂-generation reactions with (1−x)CeO₂-xNiO solid solution were repeatable with the redox system of Ce⁴⁺-Ce³⁺, which was enhanced by the catalytic function of Ni²⁺-Ni⁰.     

Molecular photoelectron spectroscopy at 132.3 eV: N2, CO,C2H4 and O2

The molecular photoelectron spectra of gaseous N₂, CO, C₂H₄ and O₂ were obtained using yttrium Mζ X-rays (132.3 eV). Comparison with spectra taken with MgKα₁₂ X-rays (1253.6 eV) showed the molecular orbitals derived from atomic 2p orbitals to be emphasized in the YMζ spectra. Orbital compositions were confirmed in N₂ and CO, and the presence of several peaks was either better established or detected for the first time (e.g., a ²Π_u state at 23.5 eV in O₂⁺) in C₂H₄ and O₂. The relative cross-section predictions of Rabalais et al. were tested by these spectra. The theoretical values, which were based on ground-state wavefunctions and plane-wave (PW) or OPW continuum states, were found to agree qualitatively with experiment, establishing that this level of theory has diagnostic value. Quantitative agreement is lacking, however. The potential application of 132.3 eV X-rays to the study of photoemission from adsorbed molecules on surfaces is emphasized.     

Infrared diode laser absorption features of N2O and CO2 in a laval nozzle

Design and operation of a pulsed Laval nozzle and the characterization of molecular flow through such a nozzle using IR tunable diode laser (TDL) is the central theme of this work. The results here deal with He diluted N₂O and CO₂ gaseous systems. Boltzmann type plots of the spectral intensity data of both N₂O and CO₂ show non-linear behaviour. We have attempted to understand this non-linear behaviour of Boltzmann plots in terms of (1) instability in the jet and (2) a two-temperature model for the flowing gas, a cold central core and a hot boundary layer close to the nozzle walls. The model based on jet instability represents the data somewhat poorer than the two-temperature model. The parameters derived from fitting our experimental data to the former model could be used to calculate the thermodynamic parameters only through further approximations. Measured absorption line profile of the P(15) line of the v ₂ band of N₂O as a function of axial distance from the nozzle exit gradually shifts from a Lorentzian to a Gaussian type. Velocity distribution of N₂O molecules in a Laval nozzle is determined by differentiating the absorption line profile of the P(15) line (v ₀=576.235 cm^–1) of the v ₂ band of N₂O. Translational temperature of N₂O molecules is determined from the observed spectral profiles.     

Determination of N and O – Atom and N2(A) Metastable Molecule Densities in the Afterglows of N2 and N2‐O2 Microwave Discharges

Early afterglows of N₂ and N₂‐O₂ flowing microwave discharges are characterized by optical emission spectroscopy. The N and O atom and N₂(A) metastable molecule densities are determined by optical emission spectroscopy after calibration by NO titration for N‐atoms and measurements of NO and N₂ band intensities for O‐atoms and N₂(A) metastable molecules. By using N₂ tanks with 50 and 10 ppm impurity, it is determined in the afterglow an O‐ atom impurity of 150‐200 ppm. Variations of the N and O‐atom and N₂(A) metastable molecule densities are obtained in the early afterglow of N₂–(9·10^–5–3·10^–3)O₂ gas mixtures. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dynamical aspects and the role of IVR for the reactivity of noble metal clusters towards molecular oxygen

Here, we present the dynamical aspects and the role of internal energy redistribution (IVR) in the reactivity of noble metal clusters towards O₂. We show on the example of Ag₃O₂ ^- / Ag₃O₂ / Ag₃O₂ ⁺ that NeNePo spectroscopy carried out under zero electron kinetic energy (ZEKE) conditions can be a powerful tool to investigate the geometry relaxation and IVR induced by photodetachment in real time. Furthermore, we demonstrate that difference in the reactivity of Ag₆ ^- and Au₆ ^- towards O₂ can be attributed to different nature of the IVR process. Dissipative IVR in Ag₆ ^- favors fast complex stabilization, whereas resonant IVR found for Au₆ ^- might be an important factor determining the catalytic activity of Au₆ ^- cluster in the CO oxidation.     

Characterisation of the Ru/MgF2 catalyst with adsorbed O2, NO, CO probe molecules by EPR and IR spectroscopy

Electron paramagnetic resonance (EPR) and infrared (IR) spectroscopy were used to study the formation of ruthenium and adsorbed species appearing on the catalyst during O₂, NO, and CO adsorption at room temperature on 1 wt% Ru/MgF₂ catalysts prepared from Ru₃(CO)₁₂ . Both EPR and IR results provided clear evidence for the interaction between surface ruthenium and probe molecules. No EPR signals due to ruthenium (Ru) species were recorded at 300 and 77 K after H₂-reduction of the catalyst at 673 K. However, at 4.2 K a very weak EPR spectrum due to low-spin (4d⁵) Ru³⁺ complexes was detected. A weak anisotropic O₂^- radicals signal with g_∣∣=2.017 and g_⊥=2.003 superimposed on a broad (ΔB_pp=120 mT), slightly asymmetric line at g=2.45(1) was identified after O₂ admission to the reduced sample. Adsorption of NO gives only a broad, Gaussian-shaped EPR line at g=2.43(1) indicating that the admission of NO, similarly to O₂ adsorption, brings about an oxidation of Ru species in the course of the NO decomposition reaction. Introduction of NO over the CO preadsorbed catalyst leads to EPR spectrum with parameters g_⊥=1.996, g_∣∣=1.895, and A_⊥^N=2.9 mT assigned to surface NO species associated with Ru ions. The IR spectra recorded after adsorption of NO or CO probe molecules showed the bands in the range of frequency characteristic of ruthenium nitrosyl, nitro, and nitrate/nitrite species and the bands characteristic of ruthenium mono-and multicarbonyls, respectively. Addition of CO after NO admission to the catalyst leads to appearance in the IR spectrum, beside the ones characteristic of NO adsorption, the bands which can be attributed to Ru-CO₂ and Ru-NCO species, indicating that the reaction between NO and CO occurs. These species were also detected after CO adsorption followed by NO adsorption, additionally to the band at 1850 cm⁻¹ being due to cis-type species.     

Si-doped C3N monolayers as efficient single-atom catalysts for the reduction of N2O: a computational study

Density functional theory calculations are performed to probe reaction pathways of N₂O reduction by CO molecule catalysed over Si-doped C₃N (Si-C₃N) nanosheets. According to our results, a single Si atom can be stabilised above the C- or N-vacancy site of C₃N due to the formation of strong Si-N or Si-C covalent bonds. The reduction of N₂O over Si-C₃N is characterised as a two-step process. First, N₂O is dissociated to N₂ and an activated oxygen atom (O_ads) without an energy barrier. Then, the O_ads moiety is removed by CO molecule by overcoming negligible activation energy.     

Reasons for the deactivation of Pt/TiO2 photocatalyst treated by inert gas N2

The effect of N₂ treatment on the photocatalytic activity of Pt⁰/TiO₂ was investigated. The results showed that after treatment at 500 °C in N₂, 70% of the photocatalytic activity of 1.0 wt.% Pt⁰/TiO₂ was lost by the evaluation of photocatalytic oxidation reaction of C₃H₆. Transmission electron microscopy (TEM) and Ar⁺ ion sputtering tests revealed that in the course of high-temperature N₂ treatment, the size of Pt⁰ particles on TiO₂ increases and a strong interaction between metal and support, i.e. Pt⁰ particles encapsulated by Ti_xO_y, happens, which are the reasons for the deactivation of Pt⁰/TiO₂ photocatalyst treated by high-temperature N₂.     

Determination of N and O‐atoms and N2 (A) Metastable Molecule Densities in the Afterglows of N2‐H2, Ar‐N2‐H2 and Ar‐N2‐O2 Microwave Discharges

Early afterglows of N₂‐H₂, Ar‐N₂‐H₂ and Ar‐N₂‐O₂ flowing microwave discharges are characterized by optical emission spectroscopy. The N and O atoms and the N₂ (A) metastable molecule densities are determined by optical emission spectroscopy after calibration by NO titration for N and O‐atoms and measurements of NO and N₂ band intensities. If an uncertainty of 30% is estimated on N‐atomic density, an inaccuracy of one order of magnitude is obtained on the O and N₂ (A) densities. In N₂‐(0.05‐2.5%)H₂ and Ar‐(1‐50%)N₂‐(0.05‐2.5%) H₂ gas mixtures, the O‐atoms are coming from O₂ impurities in the discharge. Concentrations of N and O‐atoms and of N₂ (A) densities are compared to the ones obtained in Ar‐(5‐50%)N₂‐(0.2‐2.5%) O₂ gas mixtures in which a controlled amount of O₂ is added. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A quadratic configuration interaction study of N2O and N2O·−

The geometries and vibrational frequencies of both N₂O and N₂O^·– were calculated at the QCISD and QCISD(T) levels of theory using aug-cc-pVDZ and aug-cc-pVTZ basis sets. The electron affinity of N₂O was determined to be ?0.15 eV. This work corroborates an earlier G2 study and suggests that the currently accepted value for the electron affinity, 0.22eV, is in error. This study represents the best calculation to date for the geometry and vibrational frequencies of N₂O^·?     

Study of flowerlike CeO2 microspheres used as catalyst supports for CO oxidation reaction

Porous flowerlike CeO₂ microspheres were synthesized via a novel hydrothermal method and were used as supports for the oxidation of CO. After loaded with Au or CuO, it exhibited an excellent low-temperature catalytic activity toward CO oxidation reaction. Especially, for the Au-loaded flowerlike CeO₂ microsphere catalyst, CO gas started its conversion into CO₂ above 80% at room temperature. The possible reasons for the superior catalytic activity of flowerlike CeO₂ microsphere catalysts were discussed.     

Real-gas properties of n-alkanes, O2, N2, H2O, CO, CO2, and H2 for diesel engine operation conditions

The objective of the research outlined in this paper was to develop the analytical approximations for calculating real-gas properties (p-v-T data, thermodynamic functions: internal energy, enthalpy, and entropy, and specific heats) of vapor-phase n-alkanes from C₁ (methane) to C₁₄ (normal tetradecane), O₂, N₂, H₂O, CO, CO₂, and H₂ within the range of pressure 0.05 MPa ≤ p ≤ 20 MPa and temperature 280 K ≤ T ≤ 3000 K aimed for implementation into computational fluid dynamics (CFD)-codes simulating the operation process in modern Diesel engines. The analytical approximations have been developed based on available literature data and on the new equation of state for moderately dense gases. The approximations reported are rather simple and therefore can be used directly in CFD codes. Approximations for mixing rules are also provided.     

Laser schlieren measurement of vibrational relaxation times for N2O in mixtures containing CO,N2, and Ar behind a shock wave

The laser schlieren method has been used behind shock waves where the temperatures are 410–2400°K to measure the vibrational relaxation times for N₂O and also for mixtures of N₂O with CO, N₂, and Ar. The vibrational relaxational times of N₂O have been measured for collisions with these partners, and it has been found that the effectiveness of N₂ in relaxation is close to that of N₂O, whereas CO results in accelerated vibrational relaxation of N₂O. A comparison is made with the available published data.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 3–8, November, 1984.We are indebted to V. V. Savkin for performing the mass spectral analyses.