An investigation of vibrational exciton bands in solid nitrous oxide

Infrared spectra of N₂O crystals containing dilute to isotopic impurities are reported. Information on the second moments and other properties of the vibrational exciton bands has been determined from an analysis of the impurity modes, the LOTO splittings, and a comparison of the transition dipole moments of N₂O with those of CO₂. The effect of the random sense of the molecules on the spectra is discussed.     

Theoretical investigation on the reaction of N2O and CO catalyzed by Fe(C6H6)

The reaction of N₂O with CO, catalyzed by Fe⁺(C₆H₆) and producing N₂ and CO₂, has been investigated at the UB3LYP/6-311+G(d) level. The computation results revealed that the reaction of Fe⁺(C₆H₆), N₂O and CO, is an O-atom abstraction mechanism. For the reaction channels, the geometries and the vibrational frequencies of all species have been calculated and the frequency modes analysis also have been given to elucidate the reaction mechanism. On the basis for geometry optimizations, the thermodynamic data of these reactions channels have been calculated using the statistical theory at 295.15 K and pressure of 0.35 Torr. Using Eyring transition state theory with Wigner correction, the activation thermodynamic data, rate constant and frequency factors for the these reaction channels also have been given. The results showed that CO and N₂O do not react without catalyst and Fe⁺(C₆H₆) can excellently mediate the reaction of N₂O and CO.     

Vibrational relaxation of CO2(00°1) and N2O(00°1) by NO

The far-from-resonance transfers and the de-excitation processes in CO₂-NO and N₂O-NO systems have been studied by measuring fluorescence decay rate constants of CO₂ or N₂O excited to the (00°1) level by laser radiation. The diagrams giving the variations of these rate constants versus the molar fraction of CO₂ or N₂O have been set out. From these diagrams, the relative importance of the V-V transfer and V-T de-excitation rate constants is discussed. The transfer rate constants have been calculated from a semiclassical theory in which the interaction potential is a sum of four atom-atom Morse potentials. The disagreement observed between calculated and experimental values probably results from the attractive multipolar forces which the theory does not take into account.     

Rotational structure in the infrared spectra of carbon dioxide and nitrous oxide dimers

High-resolution infrared predissociation spectra have been measured for dilute mixtures of CO₂ and N₂O in helium. Rotational fine structure is clearly resolved for both (CO₂)₂ and (N₂O)₂, the linewidths being instrument-limited. This establishes that predissociation lifetimes are longer than approximately 50 ns.     

Modeling gas separation in metal-organic frameworks

The gas adsorption and CO₂ separation properties of 9 different metal-organic frameworks (MOFs) have been modelled with grand canonical Monte Carlo (GCMC) adsorption simulations. Adsorption of both pure gases and gas mixtures has been studied. MOFs are shown to have high selectivity for polar gases such as CO₂ over non-polar gases such as N₂. Selectivity of one polar gas from another can be altered by changing the polarity of the framework, pore geometry and also temperature. Often features that lead to good selectivity of CO₂ from N₂ also lead to poor selectivity of CO₂ from H₂O.     

The solubility of CO2 and N2O in olive oil

The solubility of CO₂ and N₂O in olive oil has been measured at temperatures of about 298, 310, and 323 K with a gravimetric microbalance under pressures up to 2 MPa. The molecular weight of olive oil has been analyzed and found to be about 882 g mol⁻¹ as a mixed oil compound. The observed solubility data have been correlated with a cubic equation of state (EOS) model. N₂O has a larger solubility than CO₂ in olive oil based on either the mole or mass fraction. The present results clarify some ambiguities from the previous N₂O solubility data in the literature.     

Photon Energy Dependence of the Vibrational Fine Structure in Core Level Photoemission Spectra Near Threshold

The C 1s and N 1s main lines in the photoelectron spectra of CO, CO₂, CH₄, C₂H₂, C₂H₄, C₂H₆, N₂, and N₂O have been measured with high resolution in the threshold region, revealing in each case the extent of the rich vibrational fine structure. Using a simple line shape analysis which allows for the effect of post-collision interaction, the vibrational energies and approximate lifetimes of the core-excited ions are determined. The relative intensities of the vibrational lines change dramatically with photon energy due to the influence of shape resonances and double excitations.     

Recent Advances in Catalytic Decomposition of N<Subscript>2</Subscript>O on Noble Metal and Metal Oxide Catalysts

Catalytic decomposition of nitrous oxide (N₂O) is one of the most efficient methods for the removal of N₂O which is of high greenhouse potential and ozone-depleting property. Recent progress in the decomposition of N₂O has been reviewed with the focus on noble meal and metal oxide catalysts. The influence factors, such as catalyst support, preparation method, alkali metal additives and the reaction conditions (including O₂, H₂O, SO₂, NO and CO₂), on the performance of deN₂O catalysts have been discussed. Finally, future research direction for the catalytic decomposition of N₂O is proposed.     

Rapid interspecies energy flow between vibrationally excited SF6 and the asymmetric stretch of N2O

Rapid, selective collision-dependent excitation of N₂O following pumping of SF₆ with a CO₂ laser is reported. The N₂O fluorescence rise depends on the pressure of each component and is dominated by the SF₆-dependent contribution of 2290 ms^?1 Torr^?1. The subsequent fall is governed by V→V processes among SF₆ vibrational modes.     

Tuning of Microenvironment in Covalent Organic Framework via Fluorination Strategy promotes Selective CO2 Capture

Herein, we have designed and synthesized two heteroatom (N, O) rich covalent organic frameworks (COF), PD-COF and TF-COF , respectively, to demonstrate their relative effect on CO₂ adsorption capacity and also CO₂/N₂ selectivity. Compared to the non-fluorinated PD-COF (BET surface area 805 m² g⁻¹, total pore volume 0.3647 ccg⁻¹), a decrease in BET surface area and also pore volume have been observed for fluorinated TF-COF due to the incorporation of fluorine to the porous framework (BET surface area 451 m² g⁻¹, total pore volume 0.2978 ccg⁻¹). This fact leads to an enormous decrease in the CO₂ adsorption capacity and CO₂/N₂ selectivity of TF-COF , though it shows stronger affinity towards CO₂ with a Qst of 37.76 KJ/mol. The more CO₂ adsorption capacity by PD-COF can be attributed to the large specific surface area with considerable amount of micropore volume compared to the TF-COF . Further, PD-COF exhibited CO₂/N₂ selectivity of 16.8, higher than that of TF-COF (CO₂/N₂ selectivity 13.4).     

Negative ion chemical ionization mass spectrometry of some isocyanates

Summary Negative ion mass spectra for 3 aliphatic and 4 aromatic isocyanates have been obtained by low pressure chemical ionization, using CH₄, CO₂ and N₂O as reagent gases. All compounds furnished intense anions at m/z 42. With CH₄, quasi-molecular anions were observed at m/z M+1 for aliphatic and m/z M+1 and M–1 for aromatic isocyanates. With N₂O, anionic substitution products at m/z M+15 and M+30 were observed, and with CO₂ and N₂O, peaks at m/z M–12 could be detected for all aromatic isocyanates. Studies with ¹³CO₂ and C¹⁸O₂ as reagent gases showed that the anions at m/z M–12 and M+15 correspond to [M–CO+O]^– and [M–H+O]^–, respectively.

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Negativionen-Massenspektrometrie mit chemischer Ionisierung von einigen Isocyanaten

Zusammenfassung Die Negativionen-Massenspektren von 3 aliphatischen und 4 aromatischen Isocyanaten wurden mittels chemischer Ionisation bei tiefem Quellendruck aufgenommen, und zwar mit den Reagensgasen CH₄, CO₄ und N₂O. Alle Verbindungen lieferten intensive Anionen mit m/z 42. Mit CH₄ erhielten wir die quasi-molekularen Anionen M+1 für aliphatische sowie M+1 und M–1 für aromatische Isocyanate. Das Reagens N₂O ergab die anionischen Substitutionsprodukte M+15 und M+30. Sowohl CO₂ als auch N₂O führten mit aromatischen Isocyanaten zur Bildung von M–12 Anionen. Versuche mit ¹³CO₂ und mit C¹⁸O₂ als Reagensgase zeigten, daß die Anionen M–12 und M+15 den Ionen [M–CO+O]^– und [M–H+O]^– entsprechen.

     

Vibrational kinetics in HeCO reacting discharges

Combined measurements of vibrational distributions (N_υ) of CO and CO₂ yields (β) in HeCO discharges have been performed at different residence times in radiofrequency discharges. The experimental results on N_υ have been obtained by IR emission spectroscopy and on β by gas-chromatographic and mass-spectrometric techniques. A theoretical model including the most important relaxation channels of the vibrational energy has been set up and coupled to the plasma chemistry describing the rate of formation of species such as CO₂, C, and O. Theoretical and experimental results are in good agreement, emphasizing the role of a vibrational mechanism in dissociating CO in HeCO mixtures.     

Chemically pumped N2O laser

Optical gain and laser oscillation has been achieved in N₂O through selective excitation of the (001) state by vibrational energy transfer from CO². The CO² is produced by the flash photolysis initiated chemical reaction: O + CS → CO² + S.     

Raman spectroscopic study of CO2 sorption process in poly methyl methacrylate

Raman spectra of poly methyl methacrylate (PMMA) in contact with compressed CO₂ were measured, to investigate effects of CO₂ sorption on structure of the PMMA chain. The solubility and diffusivity of CO₂ in PMMA were estimated from temporal variations of intensities of CO₂ peaks. The PMMA structure was analyzed from temporal variations of vibrational energies of PMMA peaks. The results show that the vibration energies of C H stretching modes of PMMA increase with CO₂ sorption, whereas those for skeletal vibration modes decrease. These energy shifts are attributed to elongational deformation of PMMA. The PMMA structure is deformed with stretching of the chains as a bundle. From energy shifts of the CO₂ peaks, the size of the CO₂ accommodated space between the bundles is estimated to be 1.6–1.9 nm. Furthermore, it was observed that the vibrational energies of the PMMA modes in foamed glassy PMMA differ from the values in glassy PMMA without foams. This result suggests that the local structure of the PMMA chain changes with the process of the CO₂ sorption and/or foaming. The local structure of the PMMA chain might be one of the dominant factors governing the properties of cellular materials. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 831–842, 2008     

The behavior of molecules in microwave-induced plasmas studied by optical emission spectroscopy. 1. Plasmas at atmospheric pressure

The behavior of molecules in different atmospheric microwave-induced plasmas (MIPs) has been studied by means of optical emission spectroscopy. This is in order to obtain more insight into molecular processes in plasmas and to investigate the feasibility of emission spectroscopy for the analysis of molecular compounds in gases, e.g. flue gases. Various molecular species (i.e. N₂, CO₂, H₂O, SF₆ and SO₂) have been introduced into discharges in argon or in molecular gases such as carbon dioxide or nitrogen. The plasmas were created and sustained by a guide-surfatron or a torch in the power range of 150 W to 2 kW. Only nitrogen sometimes yielded observable emission from the non-dissociated molecule (first and second positive system). Using other molecular gases, only dissociation and association products were observed (i.e. atomic species and diatomic molecules such as CN, C₂, CO, OH, NH and N₂⁺). The intensities of these products have been studied as a function of the concentration of introduced molecules, the position in the plasma and the composition of the plasma environment. Since in most cases the same diatomic association products are seen, observed associated molecules can only to some extend be related to the molecules originally present in the plasma gas. Therefore, it will be difficult to use atmospheric microwave discharges for the analysis of gas mixtures under the experimental conditions studied.     

Photoelectron spectroscopy of N2 and CO with dispersed Nel radiation

High resolution photoelectron spectra have been recorded from N₂ and CO with a fully calibrated energy analyzer at both the 736 and 744 A Nel lines. Observation of electrons from transitions to the υ = 11 level of the CO⁺ X²Σ⁺ ground state is reported for the first time. Relative intensities of all vibrational peaks appearing in each spectrum are given.     

Intermediates-induced CO2 Reduction Reaction Activity at Single-Atom M−N2 (M=Fe,Co, Ni) Sites

Single-atom M−N₂ (M=Fe, Co, Ni) catalysts exhibit high activity for CO₂ reduction reaction (CO₂RR). However, the CO₂RR mechanism and the origin of activity at the single-atom sites remain unclear, which hinders the development of single-atom M−N₂ catalysts. Here, using density functional theory calculations, we reveal intermediates-induced CO₂RR activity at the single-atom M−N₂ sites. At the M−N₂ sites, the asymmetric *O*CO configuration tends to split into *CO and *OH intermediates. Intermediates become part of the active moiety to form M−(CO)N₂ or M-(OH)N₂ sites, which optimizes the adsorption of intermediates on the M sites. The maximum free energy differences along the optimal CO₂RR pathway are 0.30, 0.54, and 0.28 eV for Fe−(OH)N₂, Co−(CO)N₂, and Ni−(OH)N₂ sites respectively, which is lower than those of Fe−N₂ (1.03 eV), Co−N₂ (1.24 eV) and Ni−N₂ (0.73 eV) sites. The intermediate modification can shift the d-band center of the spin-up (minority) state downward by regulating the charge distribution at the M sites, leading to less charge being accepted by the intermediates from the M sites. This work provides new insights into the understanding of the activity of single-atom M−N₂ sites.     

The plasma emission detector (PED) as an element-selective detector for supercritical fluid chromatography

The plasma emission detector (PED) has been shown to be an element specific detector for supercritical fluid chromatography (SFC). The commonly used eluents (CO₂ and N₂O) tend to disturb the He plasma; two different discharge tubes were tested in an attempt to overcome this problem. Promising results were obtained with a concentric dual flow torch design for the element specific detection of Cl, H, and C containing analytes using N₂O as SFC mobile phase.     

Computational Exploration of Mechanistic Avenues in Metal-Free CO2 Reduction to CO by Disilyne Bisphosphine Adduct and Phosphonium Silaylide

Recent years have seen a growing interest in metal-free CO₂ activation by silylenes, silylones, and silanones. However, compared to mononuclear silicon species, CO₂ reduction mediated by dinuclear silicon compounds, especially disilynes, has been less explored. We have carried out extensive computational investigations to explore the mechanistic avenues in CO₂ reduction to CO by donor-stabilized disilyne bisphosphine adduct ( R1^M ) and phosphonium silaylide ( R2 ) using density functional theory calculations. Theoretical calculations suggest that R1^M exhibits donor-stabilized bis(silylene) bonding features with unusual Si−Si multiple bonding. Various modes of CO₂ coordination to R1^M have been investigated and the coordination of CO₂ by the carbon center to R1^M is found to be kinetically more facile than that by oxygen involving only one or both the silicon centers. Both the theoretically predicted reaction mechanisms of R1^M and R2 -mediated CO₂ reduction reveal the crucial role of silicon-centered lone pairs in CO₂ activations and generation of key intermediates possessing enormous strain in the Si−C−O ring, which plays the pivotal role in CO extrusion.     

Copper–Carbene Intermediates in the Copper‐Catalyzed Functionalization of OH Bonds

Copper–carbene [Tp^xCu?C(Ph)(CO₂Et)] and copper–diazo adducts [Tp^xCu{η¹‐N₂C(Ph)(CO₂Et)}] have been detected and characterized in the context of the catalytic functionalization of O?H bonds through carbene insertion by using N₂?C(Ph)(CO₂Et) as the carbene source. These are the first examples of these type of complexes in which the copper center bears a tridentate ligand and displays a tetrahedral geometry. The relevance of these complexes in the catalytic cycle has been assessed by NMR spectroscopy, and kinetic studies have demonstrated that the N‐bound diazo adduct is a dormant species and is not en route to the formation of the copper–carbene intermediate.