Oxygen Atom Exchange Mechanism in Reaction of OH Radical with AsO

Oxygen atom exchange reaction mechanism in the reaction of OH radicals with AsO was investigated by means of the density functional theory (DFT) with 6 311++G( 3df,3pd ) and 6 311++G( d,p ) basis sets. The calculated results suggest that the reaction between OH and AsO should make the oxygen atoms exchange rapidly because the barrier to isomerization is significantly less than the HO-AsO bond dissociation energy.

Oxygen Atom Transfer Reaction of Manganese-oxo Corrole toward Dimethyl Sulfide: a Density Functional Study

The effects of axial ligand on the oxygen atom transfer(OAT)reaction from 5,10,15-tris(pentafluorophenyl)corrole((tpfc)MnVO)to dimethyl sulfide(DMS)have been investigated by density functional theory(DFT)calculations.Imidazole(Im),4-methylimidazole(4-MI)and pyridine(Py)were selected as the axial ligands.The results revealed that the axial ligand can form coordinate bond with(tpfc)MnVO in the transition state(TS)of the OAT reaction.The axial coordination favored charge transferring from(tpfc)MnVO to DMS,and weakened the Mn≡O bond in both singlet and triplet states.Furthermore,axial coordination can reduce the energy barrier of neutral(tpfc)MnVO from 23.62 kJ·mol^-1 to less than 3 kJ·mol^-1 in the triplet state,which is significantly lower than in the singlet state.This makes(tpfc)MnVO tend to direct the OAT reaction via triplet state pathway.On the other hand,the energy barriers of[(tpfc)MnVIO]+species from disproportionation pathway increased from 1.26 to 33.95 kJ·mol^-1 in a doublet state.This suggests axial ligands were conducive for direct(tpfc)MnVO OAT reaction pathway.

Oxygen Atom Transfer Mechanism for Vanadium-Oxo Porphyrin Complexes Mediated Aerobic Olefin Epoxidation

The development of catalytic aerobic epoxidation by numerous metal complexes in the presence of aldehyde as a sacrificial reductant(Mukaiyama epoxidation)has been reported,however,comprehensive examination of oxygen atom transfer mechanism involving free radical and highly reactive intermediates has yet to be presented.Herein,meso-tetrakis(pentafluorophenyl)porphyrinatooxidovanadium(Ⅳ)(VOTPFPP)was prepared and proved to be efficient toward aerobic olefin epoxidation in the presence of isobutyraldehyde.In situ electron paramagnetic resonance spectroscopy(in situ EPR)showed the generation,transfer pathways and ascription of free radicals in the epoxidation.According to the spectral and computational studies,the side-on vanadium-peroxo complexes are considered as the active intermediate species in the reaction process.In the cyclohexene epoxidation catalyzed by VOTPFPP,the kinetic isotope effect value of 1.0 was obtained,indicating that epoxidation occurred via oxygen atom transfer mechanism.The mechanism was further elucidated using isotopically labeled dioxygen experiments and density functional theory(DFT)calculations.

Solvent effects on oxygen atom transfer reaction between manganese(V)-oxo corrole and alkene

Pseudo-first order reaction rate constants of 5,10,15-tris（pentafluorophenyl）corrole Mn（V）-oxo （F_（15）CMn（V）-oxo）,5,15-bis（pentafluorophenyl）-10-（phenyl）corrole Mn（V）-oxo（F_（10）CMn（V）-oxo）,5,15- bis（phenyl）-10-（pentafluorophenyl）corrole Mn（V）-oxo（F_5CMn（V）-oxo） and 5,10,15-tris（phenyl）corrole Mn（V）-oxo（F_0CMn（V）-oxo） with a series of alkene substrates in different solvents were determined by UV-vis spectroscopy.The results indicated that the oxygen atom transfer pathway between Mn（V）-oxo corrole and alkene is solvent-dependent.

The vacancy defects and oxygen atoms occupation effects on mechanical and electronic properties of Mo_(5)Si_(3) silicides

Improving brittle behavior and mechanical properties is still a big challenge for high-temperature structural materials.By means of first-principles calculations,in this paper,we systematically investigate the effect of vacancy and oxygen occupation on the elastic properties and brittle-or-ductile behavior on Mo_(5)Si_(3).Four vacancies(Si_(-Va1),Si_(-Va2),Mo_(-Va1),Mo_(-Va2))and oxygen occupation models(O_(Mo1),O_(Mo2),O_(-Si1),O_(-Si2))are selected for research.It is found that Mo_(-Va2) vacancy has the stronger structural stability in the ground state in comparison with other vacancies.Besides,the deformation resistance and hardness of the parent Mo_(5)Si_(3) are weakened due to the introduction of different vacancy defects and oxygen occupation.The ratio of B/G indicates that oxygen atoms occupation and vacancy defects result in brittle-to-ductile transition for Mo_(5)Si_(3).These vacancies and the oxygen atoms occupation change the localized hybridization between Mo-Si and Mo-Mo atoms.The weaker O-Mo bond is a contributing factor for the excellent ductile behavior in the O_(-Si2) model for Mo_(5)Si_(3).

A Simulator for Producing of High Flux Atomic Oxygen Beam by Using ECR Plasma Source

In order to study the atomic oxygen corrosion of spacecraft materials in low earth orbit environment, an atomic oxygen simulator was established. In the simulator, a 2.45 GHz microwave source with maximum power of 600 W was launched into the circular cavity to generate ECR (electron cyclotron resonance) plasma. The oxygen ion beam moved onto a negatively biased Mo plate under the condition of symmetry magnetic mirror field confine, then was neutralized and reflected to form oxygen atom beam. The properties of plasma density, electron temperature, plasma space potential and ion incident energy were characterized. The atomic oxygen beam flux was calibrated by measuring the mass loss rate of Kapton during the atomic oxygen exposure. The test results show that the atomic oxygen beam with flux of 1016-1017 atoms-cm-2·s-1 and energy of 5-30 eV and a cross section of φ80 mm could be obtained under the operating pressure of 10-1-10-3 Pa. Such a high flux source can provide accelerated simulation tests of materials and coatings for space applications.

Molecular intrinsic characteristic contours of small organic molecules containing oxygen atom

By utilizing the classical turning point of the electron movement, we have defined and computed the mo-lecular intrinsic characteristic contour (MICC) via the com-bination of the ab initio quantum chemistry computational method with the ionization potential measured by photo-electron spectroscopy experiment. In this paper, we calcu-lated the MICCs of several small organic molecules contain-ing oxygen atom for the first time. The three-dimensional pictures have been drawn, by performing a large number of calculations. The analysis on some characterized cross-sec-tions of the MICC can provide atomic spatial changing information in the process of forming a molecule.

Preparation and anti atomic oxygen erosion properties of OPPOSS/PI composites

Atomic oxygen （AO） found in low earth orbit can cause serious erosion to polyimide （PI） materials, which greatly limits their lifetime. 8-phenyl silsesquioxane （OPPOSS） was synthesized, and OPPOSS/PI composites were pre- pared by physical blending, followed by thermal imidization to enhance the AO erosion resistance of PI materials. The morphology, composition, and structure of the composites were analyzed before and after AO exposure in a ground sim- ulated facility of atomic oxygen. After 16 h AO exposure, the OPPOSS/PI composite with 5wt% OPPOSS addition shows an erosion rate of about 1.4×10-24 cm3/atom with only 48% mass loss of that of PI without OPPOSS addition. The mixture of OPPOSS nano molecules is assembled into a kind of regular square structure and distributed evenly in OPPOSS/PI composites. Some SiO2 particles are formed in the composites during AO exposure, which can act as ＂inert points＂ to reduce the AO erosion rate of OPPOSS/PI composites.

Ground-based Investigations of Atomic Oxygen Erosion Behaviors of Silver and Ion-implanted Silver

Silver foils and ion-implanted silver foils exposed to atomic oxygen （AO） generated in a ground simulation facility were investigated by the quartz crystal microbalance （QCM）, the scanning electron microscopy （SEM） and the X-ray photoelectron spectroscopy （XPS）. The experimental results show the presence of Ag2O and AgO in an oxidation process of the silver foil having exposure to AO. As soon as silver comes under the bombardment of atomic oxygen, the oxidation process starts with a thick film forming on the silver surface. Because of the development of stresses, the oxide layer gets cracked and spalled, which leads to appearance of a new silver surface intensifying further oxidation. At last, AgO begins to form on the outer surface of the oxide film. The analytical results of the XPS and the AES attest to formation of a continuous high-quality protective oxide-based layer on the surface of ion-implanted silver films after exposure to AO. This layer can well protect materials in question from erosion.

Effects of Vacuum Ultraviolet Radiation on Atomic Oxygen Erosion of Polysiloxane/SiO_2 Hybrid Coatings

Polysiloxane/SiO2 hybrid coatings have been prepared on Kapton films by a sol-gel process. The erosion resistance of polysiloxane/Si02 （20 wt pct） coating was evaluated by exposure tests of vacuum ultraviolet radiation （VUV） and atomic oxygen beam （AO） in a ground-based simulation facility. The experimental results indicate that this coating exhibits better AO resistance than pure polysiloxane coating. The erosion yield （Ey） of the polysiloxane/Si02 （20 wt pct） hybrid coating is about 10-27 cm3/atom, being one or two orders of magnitude lower than that of polysiloxane. VUV radiation can affect the erosion process greatly. Under simultaneous AO and VUV exposure, the value of Ey of the polysiloxane/5iO2 （20 wt pct） hybrid coating increases by 3g% compared with that under single AO exposure.

The Erosion Effect of Kapton Film in a Ground-based Atomic Oxygen Irradiation Simulator

In order to investigate the effect of space environmental factors on spacecraft materials, a ground-based simulation facility for space atomic oxygen（AO） irradiation was developed in our laboratory. Some Kapton film samples were subjected to AO beam generated by this facility. The Kapton films before and after AO exposure were analyzed comparatively using optical microscopy, scanning electronic microscopy, atomic force microscopy, high-precision microbalance, and X-ray photoelectron spectroscopy. The experimental results indicate that the transmittance of Kapton film will be reduced by AO irradiation notably, and its color deepens from pale yellow to brown. Surface roughness of the AO-treated sample is already increased obviously after AO irradiation for 5 hours, and exhibits a flannel-like appearance after 15 hours’ exposure in AO beam. The imide rings and benzene rings in kapton molecule are partially decomposed, and some new bonds form during AO irradiation. The mass loss of kapton film increases linearly with the increase of AO fluence, which is resulted from the formation of volatile products, such as CO, CO2 and NOx. The breakage in structure and degradation in properties of AO-treated Kapton film can be attributed to the integrated effect ofimpaction and oxidization of AO beam. The test results agree well with the space flight experimental data.

Quantitative Determination of Density of Ground State Atomic Oxygen from Both TALIF and Emission Spectroscopy in Hot Air Plasma Generated by Microwave Resonant Cavity

Two experimental techniques have been used to quantify the atomic oxygen density in the case of hot air plasma generated by a microwave （MW） resonant cavity. The latter operates at a frequency of 2.45 GHz inside a cell of gas conditioning at a pressure of 600 mbar, an injected air flow of 12 L/min and an input MW power of 1 kW. The first technique is based on the standard two photon absorption laser induced fluorescence （TALIF） using xenon for calibration but applied for the first time in the present post discharge hot air plasma column having a temperature of about 4500 K near the axis of the nozzle. The second diagnostic technique is an actinometry method based on optical emission spectroscopy （OES）. In this case, we compared the spectra intensities of a specific atomic oxygen line （844 nm） and the closest wavelength xenon line （823 nm）. The two lines need to be collected under absolutely the same spectroscopic parameters. The xenon emission is due to the addition of a small proportion of xenon （1% Xe） of this chemically inert gas inside the air while a further small quantity of H2 （2~） is also added in the mixture in order to collect OH（A- X） and NH（A-X） spectra without noise. The latter molecular spectra are required to estimate gas and excitation temperatures. Optical emission spectroscopy measurements, at for instance the position z=12 mm on the axis plasma column that leads to a gas measured temperature equal to 3500 K, an excitation temperature of about 9500 K and an atomic oxygen density 2.09× 1017＋ 0.2×1017 cm-3. This is in very good agreement with the TALIF measurement, which is equal to 2.0×101T cm-3.

Roll-to-roll fabrication of large-scale polyorgansiloxane thin film with high flexibility and ultra-efficient atomic oxygen resistance

One of the most widely used and well-established atomic oxygen(AO)protection solutions for low Earth orbit(LEO)satellites is the deposition of protective coatings on polymeric materials.However,manufacturing extensive expanses of these coating materials with good transparency,flexibility,smoothness,ultra-thinness,and exceptional AO resistance remains a critical issue.Herein,we successfully deposited a 400 nm thick polyorgansiloxane(SiO_(x)C_(y)H_(z))coating with high optical transparency and uniform good adherence on to a 1.2 m wide polyimide surface,by optimizing the distribution of hexamethyldisiloxane and oxygen as precursors in the roll-to-roll compatible plasmaenhanced chemical vapor deposition process.After AO irradiation with the fluence of 7.9×10^(20)atoms·cm^(–2),the erosion yield of the SiO_(x)C_(y)H_(z)-coated Kapton was less than 2.30×10^(–26)cm^3·atom^(–1),which was less than 0.77%of that of the Kapton.It indicates that the SiO_(x)C_(y)H_(z)coating can well prevent the erosion of Kapton by AO.In addition,it was also clarified that a SiO_(2) passivation layer was formed on the surface of the SiO_(x)C_(y)H_(z)coating during AO irradiation,which exhibited a‘self-reinforcing’defense mechanism.The entire preparation process of the SiO_(x)C_(y)H_(z)coating was highly efficient and low-cost,and it has shown great potential for applications in LEO.

A Method of Inversing the Peak Density of Atomic Oxygen Vertical Distribution in the MLT Region From the OI (557.7 nm)Night Airglow Intensity

In this paper, using the MSISE-90 model as the reference atmosphere, we discuss the feasibility and method of deducing the peak densities of the undisturbed atomic oxygen profiles in the MLT region (the mesosphere and lower thermosphere region) from OI (557.7 nm) night airglow intersities. The peak densities for different seasons, latitudes and longitudes are deduced from OI (557.7nm) airglow intensities through this expression. We analyze the features of inversion relative errors and discuss the influence of the variations in temperature on inversion errors. The results indicate that all inversion errors are less than 5% except for those at high altitudes in the summer hemisphere. And the impact of the variations in temperature on errors is not significant.

Resistance of Nanoclay Reinforced Epoxy Composites to Hyperthermal Atomic Oxygen Attack

Due to outstanding mechanical properties, heat resistance, and relatively facile production, nanoclay reinforced epoxy composites (NCRE composites) have been suggested as candi- date materials for use on external surfaces of spacecraft residing in the low Earth orbit (LEO) environment. The resistance of the NCRE composites to bombardment by atomic oxygen (AO), a dominant component of the LEO environment, has been investigated. Four types of samples were used in this study. They were pure epoxy (0 wt% nanoclay con- tent), and NCRE composites with di erent loadings of nanoclay|1 wt%, 2 wt%, and 4 wt%. Etch depths decreased with increasing nanoclay content, and for the 4 wt% samples it ranged from 28% to 37% compared to that of pure epoxy. X-ray photoelectron spectroscopy (XPS) indicates that after AO bombardment, relative area of C-C/C-H peak decreased, while the area of the C-O, ketones peaks increased, and the oxidation degree of surfaces increased. New carbon-related component carbonates were detected on nanoclay contain- ing composite surfaces. Scanning electron microscopy indicates that aggregates formed on nanoclay-containing surfaces after AO bombardment. The sizes and densities of aggregates increased with nanoclay content. The combined erosion depths, XPS and SEM results indi- cate that although all the studied surfaces got eroded and oxidized after AO bombardment, the nanoclay containing composites showed better AO resistance compared to pure epoxy, because the produced aggregates on surface potentially act as a physical “shield”, e ectively retarding parts of the surface from further AO etching.

A general bimetal-ion adsorption strategy to prepare nickel single atom catalysts anchored on graphene for efficient oxygen evolution reaction

Single-atom catalysts (SACs) supported on two-dimensional (2D) materials are highly attractive for maximizing their catalytic activity.However,graphene based SACs are primarily bonded with nitrogen and carbon sites,resulting in poor performance for the oxygen evolution reaction (OER).Herein,we develop a general bimetal-ion adsorption strategy for the synthesis of individually dispersed Ni SACs anchored on the oxygenated sites of ultrathin reduced graphene oxide as efficient OER electrocatalysts.The resultant Ni SACs for OER in alkaline electrolyte exhibit a highly stable overpotential of 328 mV at the current density of 10 mA cm^-2,and Tafel slope of 84 mV dec^-1 together with long-term durability and negligible degradation for 50 h,which is greatly outperform its counterparts of nitrogen bonded Ni SACs (564 mV,364 mV dec^-1) and Ni(OH)2 nanoparticles anchored on graphene (450 mV,142 mV dec^-1),and most reported Ni based OER electrocatalysts.Furthermore,the extended X-ray absorption fine structure at the Ni K-edge and theoretical simulation reveal that the nickel-oxygen coordination significantly boost OER performance.Therefore,this work will open numerous opportunities for creating novel-type 2D SACs via oxygen-metal bonding as highly robust OER catalysts.

Inactivation of Bacillus Subtilis by Atomic Oxygen Radical Anion

UAtomic oxygen radical anion （O-） is one of the most active oxygen species, and has extremely high oxidation ability toward small-molecules of hydrocarbons. However, to our knowledge, little is known about the effects of O- on cells of micro-organisms. This work showed that O- could quickly react with the Bacillus subtilis cells and seriously damage the cell walls a s well as their other contents, leading to a fast and irreversible inactivation. SEM micrographs revealed that the cell structures were dramatically destroyed by their exposure to O-. The inactivation efficiencies of B. subtilis depend on the O- intensity, the initial population of cells and the treatment temperature, but not on the pH in the range of our investigation. For a cell concentration of 10^6 cfu/ml, the number of survived cells dropped from 10^6 cfu/ml to 10^3 cfu/ml after about five-minute irradiation by an O- flux in an intensity of 233 nA/cm^2 under a dry argon environment （30 ℃, 1 atm, exposed size： 1.8 cm^2）. The inactivation mechanism of micro-organisms induced by O- is also discussed.

Behavior of pure and modified carbon/carbon composites in atomic oxygen environment

Atomic oxygen （AO） is considered the most erosive particle to spacecraft materials in low earth orbit （LEO）. Carbon fiber, car-bon/carbon （C/C）, and some modified C/C composites were exposed to a simulated AO environment to investigate their behaviors in LEO. Scanning electron microscopy （SEM）, AO erosion rate calculation, and mechanical property testing were used to characterize the material properties. Results show that the carbon fiber and C/C specimens undergo significant degradation under the AO bombing. According to the effects of AO on C/C-SiC and CVD-SiC-coated C/C, a condensed CVD-SiC coat is a feasible approach to protect C/C composites from AO degradation.

Atomic-Oxygen Beam Source with Compact ECR Plasma

An atomic-oxygen beam source with compact ECR plasma was successfully investigated. The microwave was produced and transmitted in a coaxial mode, and coupled with the loop. The plasma was produced at a higher asymmetry magnetic mirror field, and neutralized with the molybdenum target at a lower asymmetry magnetic mirror field. The magnetic field was constituted with permanent magnets. This source has a higher flux density of atom beam, a lower operating pressure, a smaller power consumption and low-cost. When it was installed at the equipment to study the interaction of the beam with the surface, the operation was carried out very easily and with a good stability.