气相中 H2O2与 N2O反应机理的探讨

采用RHF/AM1方法研究了H     

Anomalous magnetic behavior in the transition metal ions doped Cu2O flower-like nanostructures

Cuprous oxide (Cu₂O) flower-like nanostructures doped with various metal ions i.e. Fe, Co, Ni and Mn have been synthesized by an organic phase solution method. The powder X-ray diffraction study clearly reveals them as single phase simple cubic cuprite lattice. Study of their magnetic properties have shown that these doped samples are ferromagnetic in nature; however, no such property was observed for the undoped Cu₂O sample. The magnitude of the ferromagnetic behavior was found to be dependent on the dopant metal ions amount, which increased consistently with its increase. As total magnetic moment contribution of the doped metal ions calculated was insignificant, it is believed to have originated from the induced magnetic moments at cation deficiency sites in the material, created possibly due to the disturbance of the crystal lattice by the dopant ions. The existence of the defects has been supported by photoluminescence spectra of the doped samples.     

Theoretical study of N2 coordination in metal complexes with fullerene ligands

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Kinetic study of the reactions Sn+N2O→SnO+N2

The optical pumping method of alkali molecules by atom—molecule exchange collisions is applied to obtain the magnetic shielding difference σ(Na) — σ(Na₂) = (29 ± 16) × 10^?6 between Na atoms and Na₂ molecules and the scalar nuclear spin—spin coupling constants d_s = (306 ± 30)s^?1 of ²³Na³⁹K.     

Synthesis of meso-furyl porphyrins with N4, N3S, N2S2 and N3O porphyrin cores

A series of meso-furyl porphyrins with four different porphyrin cores (N₄, N₃S, N₂S₂ and N₃O) were synthesized and characterized. The comparison of NMR, optical and fluorescence properties of meso-furyl porphyrins with porphyrins with six-membered aryl groups indicates that electronic properties of porphyrins were changed drastically on the introduction of furyl groups at meso positions. The maximum shifts in spectral bands were observed for meso-furyl porphyrins with N₂S₂ core. On protonation, the absorption bands of meso-furyl porphyrins were further red shifted. All these changes were ascribed to the possibility of more planarity of the meso-furyl porphyrins due to the small size of the furyl groups which results in extending the π-delocalisation of the porphyrin ring in to the furyl groups.     

Ionization of N2O by low-energy electrons and near-thermal rare-gas ions

Emission spectra between 185 and 600 nm have been investigated following near-thermal charge exchange between He⁺ and N₂O and ≤ 100 eV electron impact on N₂O. The charge exchange produces N₂O⁺Ã→X?and N₂⁺ B → X emission, but the two band systems account for at most 5% of all charge transfer products. These results and literature data on Ar⁺/N₂O are discussed in the light of Franck—Condon and energy resonance criteria as applied to low-energy charge exchange. The electron-impact experiments revealed a weak (≈ 10^?3) long-lived (≈ 50 × 10^?6 s) component in the N₂O⁺Ã→X?emission.     

PVTx measurements for N2O + CH3F, N2O + CH2F2, and N2O + CHF3 binary systems

Isochoric PVTx measurements have been performed for the binary system of nitrous oxide + CH₃F (R41), +CH₂F₂ (R32), and +CHF₃ (R23) using a new experimental set-up. The experiments covered both the two-phase region and the superheated vapor region and were performed within the temperature range 214–358 K and within a pressure range from 270 to 5600 kPa. Data have been collected for not less than four compositions for each system. The vapor–liquid equilibrium data were derived correlating the experimental data by means of the Carnahan–Starling–De Santis equation of state. The studied systems show a positive deviation from the Raoult's law. The results obtained were compared with the Burnett PVTx data. The two methods showed a mutual consistency within an acceptable margin of error. No other experimental PVTx data were found in the literature for these binary systems.     

High-pressure Raman study of vibrational relaxation in N2O

The vibrational widths of the ν₁ and ν₃ Raman bands of N₂O were determined at pressures ranging from 8 bar to 2 kbar and temperatures varied from 25 to 150°C. The different dephasing theories including motional narrowing collisional models and resonant vibrational energy transfer theory were tested. A comparison of the theoretical predictions with the experimental data indicates the resonance VV transfer represents the dominant broadening mechanism. The observed frequency shifts between isotropic and anisotropic components of the bands were interpreted in terms of dipole-dipole interactions in dense N₂O.     

Synthesis,electrochemical and in situ spectroelectrochemical studies of new transition metal complexes with two new Schiff-bases containing N2O2/N2O4 donor groups

New Schiff-base copper and cobalt complexes, [Cu(L¹)], [Cu(L²)] and [Co(L¹)], [Co(L²)] (where L¹ = N-N′-bis(3,5-di-tert-butylsalicylaldimine)-1,4-cyclohexane bis(methylamine) and L² = N-N′-bis(3,5-di-tert-butylsalicylaldimine)-1,8-diamino-3,6-dioxaoctane), were synthesized and characterized using elemental analysis, IR spectra, UV–Vis spectra, magnetic susceptibility measurements, ¹H and ¹³C NMR spectroscopy, thermal analysis and molar conductance (Λ_M). Their electro-spectrochemical properties were investigated using cyclic voltammetric (CV) and thin-layer spectroelectrochemical techniques in a dichloromethane solution (CH₂Cl₂). The CV of [Cu(L²)] showed a lower oxidation potential than that of [Cu(L¹)] under the same experimental conditions. The oxidation wave (II) of [Cu(L²)] was accompanied by an EC process (II′), which was not observed for [Cu(L¹)]. Also, [Cu(L²)] exhibited a reduction process, but [Cu(L¹)] did not. These results indicate that the Cu(II) ion in [Cu(L²)] is coordinated by N₂O₄ donor sites while [Cu(L¹)] presents a square-planar structure with N₂O₂ donor sites. Both oxidation processes for [Co(L¹)] and [Co(L²)] are based on the cobalt center, and they are assigned to Co(II)/Co(III) couples. The spectroelectrochemical results indicate that the oxidized species of [Cu(L²)] is similar to that of [Cu(L¹)], the only difference being that the absorption bands of the oxidized species for [Cu(L²)] shift to lower energy compared with those of [Cu(L¹)] because of their different coordination environment. The geometry of [Cu(L²)] changed into square-planar after the complex was totally oxidized and the neutral complex was only recovered following the EC process, as observed from the CV of [Cu(L²)]. For the two cobalt complexes, the bands corresponding to the π → π^∗transitions disappeared and new bands with small red shifts and of lower intensity were observed during the oxidation process. These new bands are attributed to the LMCT transition as observed in the case of the oxidation processes of the cobalt complexes.     

Rate constants of the O(D) reactions with N2, O2, N2O, and H2O at 295 K

Using a technique of laser flash photolysis coupled with vacuum ultraviolet laser-induced fluorescence spectroscopy, the rate coefficients of O(¹D) reactions with N₂, O₂, N₂O, and H₂O at 295 ± 2 K have been determined to be , k_O2=(4.06±0.24)×10^-11, k_N2O=(1.35±0.08)×10^-10 and . The quoted uncertainties include estimated errors and are the 95% confidence level. The k_N2 and k_N2O values obtained are larger than the current NASA/JPL recommendations by 26% and 16%, respectively, although they are still within the error limits associated with the recommendations.     

Decomposition of N2O on Rh-loaded zeolites

N₂O was decomposed over Rh supported on NaY zeolite and ZSM5. With low Rh-loading (≤0.1 wt.%) the activity of Rh was much higher than that supported on SiO₂ and CeO₂. On the contrary, the activity of Rh-loaded zeolites (0.1 wt.%) was not so high or even lower than that on SiO₂ for the oxidation of toluene, which has a larger molecular size than N₂O. Thus the Rh present inside the zeolite cavity was especially effective in the decomposition of N₂O.     

Theoretical study of the singlet electronically excited states of N4

Vertical excitation energies for the lowest eleven singlet states of T_d N₄ were calculated using the TD-DFT method with the B3LYP functional, and at the EOM-CCSD level of theory. The vertical excitation energies for the five lowest-lying excited states were also obtained using the state-averaged CASSCF, CASPT2, CASPT3, and MRCI + Q methods. Our results show that the five lowest-lying states are of valence character. EOM-CCSD/d-aug-cc-pVTZ calculations predict that there are two weakly allowed optical transitions of T₂ symmetry at 10.44 and 10.82 eV. The transition to the third T₂ state, which is predicted to be at 10.89 eV, has an oscillator strength about one order of magnitude higher.     

Deactivation of vibrationally excited N2 by H2O

The VV exchange rate for the N₂H₂O system is determined using a hard-core repulsive potential. It is found that the rapid deactivation rate arises from near-resonant VR exchanges involving non-dipole changes in the rotational states. Furthermore, a classical-path approximation is used and the resulting rate found to be critically dependent on the path chosen.     

N2O emission in partial nitritation-anammox process

Nitrous oxide(N2O)is one of the significant greenhouse gases,and partial nitritation-anammox(PNA)process emits higher N2O than traditional nitrogen removal processes.N2O production in PNA mainly occurs in three different pathways,i.e.,the ammonia oxidizing bacteria(AOB)denitrification,the hydroxylamine(NH2 OH)oxidation and heterotrophic denitrifiers denitrification.N2O emission data vary significantly because of the different operational conditions,bioreactor configurations,monitoring systems and quantitative methods.Under the common operational parameter scopes of PNA,N2O emission via NH2 OH oxidation dominates at relatively low dissolved oxygen(DO),low inorganic carbon(IC),high pH or low N02-concentration,while N2O emission via AOB denitrification dominates at relative higher DO,higher IC.lower pH or higher N2O-concentration.AOB are highly enriched while nitriteoxidizing bacteria(NOB)are rarely found in partial nitritation process,and the order Nitrosomonadales of AOB is the dominant group and N2O producer.Anammox bacteria,AOB and certain amount of heterotrophic denitrifying bacteria are observed in the anammox process,the genus Denitratisoma and the heterotrophic denitrifying bacteria in the deep layer of anammox granules are the dominant N2O generation bacteria.In one-stage PNA reactors,anammox bacteria account for a large fraction of the biomass,AOB account for small portion,and NOB account for even less.The microbial community,diversity and N2O producers in one-stage PNA reactors are similar with those in two-stage PNA reactors.The dominant anammox bacteria,AOB and NOB in PNA are the species Candidatus Brocadia,the genera of Nitrotoga,Nitrospira and Nitrobacter,and the genus Nitrosomonas,respectively.The relations between N2O emission pathways and microbial communities need further study in the future.     

Theoretical study of the N20 molecule

In the study of the N₂₀ molecule with an I_h symmetry group, the following methods were applied: 6-31G, 3-21G and STO-3G ab initio and PM3 semiempirical MO methods. Both geometrical optimization and frequency calculations are reported. Results of optimized bond distances (d_N---N), first ionization potential, ΔH_a, ΔG_a and bond energy, for the cases of 6-31G, 3-21G, and PM3 showed that the N₂₀ molecule is a highly stable compound with a delocalized N---N single bonded cluster structure.     

High-Resolution Experimental Study on Photodissocaition of N2O

We study the photodissociation dynamics of nitrous oxide using the time-sliced ion velocity imaging technique at three photolysis wavelengths of 134.20, 135.30, and 136.43 nm. The O(¹S_J=0)+N₂(X¹∑_g⁺) product channels were investigated by measuring images of the O(¹S_J=0) products. Vibrational states of N₂(X¹∑_g⁺) products were fully resolved in the images. Product total kinetic energy releases (TKER) and the branching ratios of vibrational states of N₂ products were determined. It is found that the most populated vibrational states of N₂ products are v=2 and v=3. The angular anisotropy parameters (β values) were also derived. The β values are very close to 2 at low vibrational states of the correlated N₂(X¹∑_g⁺) products at all three photolysis wavelengths, and gradually decrease to about 1.4 at v=7. This indicates the dissociation is mainly through a parallel transition state to form products at lower vibrational states, and the highly vibrational exited products are from a more bent configuration. This is consistent with the observed shift of the most intense rotational structure in the TKER as the vibrational quantum number increases.     

Decomposition of N2O over CuxMg1?xAl2O4 catalysts

The results show that there is not difference between the catalytic activities of two series of Cu_xMg_1–xAl₂O₄ catalysts, despite a small but significant difference in cation distribution. The activity is mainly affected by the presence of CuO.

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Emission of secondary ions from osmium under oxygen and the nitrogen oxides N2O, NO and NO2

Summary Small briquettes compressed of high-purity Os powder were bombarded by primary Ar⁺ ions for moderate dynamic SIMS conditions. Secondary ion mass spectra were observed for positive ions which were produced under residual gas and under O₂, N₂O, NO, NO₂. For the different reactant gases these spectra were found rather similar, indicating that the nitrogen oxides mainly act as sources of reactive oxygen. But also some individual secondary ions containing nitrogen or NO are emitted from the target surface which, at least in the case of N₂O and NO₂, give some evidence of partial adsorptive fragmentation of the respective reactant gas molecules.