Adsorption of fluorinated ethers and alcohols on fresh and oxidized carbon overcoats for magnetic data storage

Temperature programmed desorption has been used to study the desorption kinetics and desorption energies of perfluorodiethylether, (CF3CF2)2O, and 2,2,2-trifluoroethanol, CF3CH2OH, adsorbed on fresh and oxidized hydrogenated amorphous carbon (a-CHx) films. (CF3CF2)2O and CF3CH2OH serve as models for the ether backbone and hydroxyl end-groups of Fomblin Zdol, the lubricant most commonly used to lubricate the surfaces of amorphous carbon overcoats on magnetic data storage hard disks. Our measurements clearly reveal, for the first time, the effects of surface oxidation on the adsorption of fluorocarbon lubricants such as Fomblin Zdol on a-CHx films. Oxidation of the a-CHx surface increases the desorption energy of CF3CH2OH but has no observable impact on the desorption energy of (CF3CF2)2O. These results support the suggestion that the alcohols interact with the surface via hydrogen bonding. From a practical perspective, these results imply that the oxidation of the fresh a-CHx film may serve as a means to control or tailor the a-CHx surface to optimize the properties of the lubricant-overcoat interface in hard disks.     

Adsorption of sulfur dioxide on hematite and goethite particle surfaces

The adsorption of sulfur dioxide (SO(2)) on iron oxide particle surfaces at 296 K has been investigated using X-ray photoelectron spectroscopy (XPS). A custom-designed XPS ultra-high vacuum chamber was coupled to an environmental reaction chamber so that the effects of adsorbed water and molecular oxygen on the reaction of SO(2) with iron oxide surfaces could be followed at atmospherically relevant pressures. In the absence of H(2)O and O(2), exposure of hematite (alpha-Fe(2)O(3)) and goethite (alpha-FeOOH) to SO(2) resulted predominantly in the formation of adsorbed sulfite (SO(3)(2-)), although evidence for adsorbed sulfate (SO(4)(2-)) was also found. At saturation, the coverage of adsorbed sulfur species was the same on both alpha-Fe(2)O(3) and alpha-FeOOH as determined from the S2p : Fe2p ratio. Equivalent saturation coverages and product ratios of sulfite to sulfate were observed on these oxide surfaces in the presence of water vapor at pressures between 6 and 18 Torr, corresponding to 28 to 85% relative humidity (RH), suggesting that water had no effect on the adsorption of SO(2). In contrast, molecular oxygen substantially influenced the interactions of SO(2) with iron oxide surfaces, albeit to a much larger extent on alpha-Fe(2)O(3) relative to alpha-FeOOH. For alpha-Fe(2)O(3), adsorption of SO(2) in the presence of molecular oxygen resulted in the quantitative formation of SO(4)(2-) with no detectable SO(3)(2-). Furthermore, molecular oxygen significantly enhanced the extent of SO(2) uptake on alpha-Fe(2)O(3), as indicated by the greater than two-fold increase in the S2p : Fe2p ratio. Although SO(2) uptake is still enhanced on alpha-Fe(2)O(3) in the presence of molecular oxygen and water, the enhancement factor decreases with increasing RH. In the case of alpha-FeOOH, there is an increase in the amount of SO(4)(2-) in the presence of molecular oxygen, however, the predominant surface species remained SO(3)(2-) and there is no enhancement in SO(2) uptake as measured by the S2p : Fe2p ratio. A mechanism involving molecular oxygen activation on oxygen vacancy sites is proposed as a possible explanation for the non-photochemical oxidation of sulfur dioxide on iron oxide surfaces. The concentration of these sites depends on the exact environmental conditions of RH.     

Gas adsorption and storage in metal-organic framework MOF-177

Gas adsorption experiments have been carried out on a zinc benzenetribenzoate metal-organic framework material, MOF-177. Hydrogen adsorption on MOF-177 at 298 K and 10 MPa gives an adsorption capacity of approximately 0.62 wt %, which is among the highest hydrogen storage capacities reported in porous materials at ambient temperatures. The heats of adsorption for H2 on MOF-177 were -11.3 to -5.8 kJ/mol. By adding a H2 dissociating catalyst and using our bridge building technique to build carbon bridges for hydrogen spillover, the hydrogen adsorption capacity in MOF-177 was enhanced by a factor of approximately 2.5, to 1.5 wt % at 298 K and 10 MPa, and the adsorption was reversible. N2 and O2 adsorption measurements showed that O2 was adsorbed more favorably than N2 on MOF-177 with a selectivity of approximately 1.8 at 1 atm and 298 K, which makes MOF-177 a promising candidate for air separation. The isotherm was linear for O2 while being concave for N2. Water vapor adsorption studies indicated that MOF-177 adsorbed up to approximately 10 wt % H2O at 298 K. The framework structure of MOF-177 was not stable upon H2O adsorption, which decomposed after exposure to ambient air in 3 days. All the results suggested that MOF-177 could be a potentially promising material for gas separation and storage applications at ambient temperature (under dry conditions or with predrying).     

Inhibition of CO oxidation on RuO2(110) by adsorbed H2O molecules

Catalytic CO oxidation on the RuO(2)(110) surface was studied at 300 K by scanning tunneling microscopy (STM), high-resolution electron-energy-loss spectroscopy (HREELS), and thermal desorption spectroscopy (TDS). Upon repeatedly exposing the surface to several 10 L of CO and O(2) at 300 K, STM shows that unreactive features accumulate with each CO and O(2) titration run. HREELS and TDS show formation of increasing amounts of H(2)O, retarded formation of O-cus atoms and incomplete removal of CO-bridge molecules during O(2) dosing, and a changing ratio of single- and double-bonded CO-bridge molecules. It is concluded that H(2)O (presumably from the residual gas) is accumulating at the Ru-cus sites thus blocking them, so that the dissociative adsorption of oxygen is prevented and the CO oxidation reaction is suppressed. Some 10% CO- bridge remains on the surface even during oxygen exposure. Consistent with this interpretation, deactivation of the surface is suppressed at 350 K, at the onset of H(2)O desorption.     

High-resolution soft X-ray photoelectron spectroscopic studies and scanning auger microscopy studies of the air oxidation of alkylated silicon(111) surfaces

High-resolution soft X-ray photoelectron spectroscopy was used to investigate the oxidation of alkylated silicon(111) surfaces under ambient conditions. Silicon(111) surfaces were functionalized through a two-step route involving radical chlorination of the H-terminated surface followed by alkylation with alkylmagnesium halide reagents. After 24 h in air, surface species representing Si(+), Si(2+), Si(3+), and Si(4+) were detected on the Cl-terminated surface, with the highest oxidation state (Si(4+)) oxide signal appearing at +3.79 eV higher in energy than the bulk Si 2p(3/2) peak. The growth of silicon oxide was accompanied by a reduction in the surface-bound Cl signal. After 48 h of exposure to air, the Cl-terminated Si(111) surface exhibited 3.63 equivalent monoleyers (ML) of silicon oxides. In contrast, after exposure to air for 48 h, CH(3)-, C(2)H(5)-, or C(6)H(5)CH(2)-terminated Si surfaces displayed <0.4 ML of surface oxide, and in most cases only displayed approximately 0.20 ML of oxide. This oxide was principally composed of Si(+) and Si(3+) species with peaks centered at +0.8 and +3.2 eV above the bulk Si 2p(3/2) peak, respectively. The silicon 2p SXPS peaks that have previously been assigned to surface Si-C bonds did not change significantly, either in binding energy or in relative intensity, during such air exposure. Use of a high miscut-angle surface (7 degrees vs < or =0.5 degrees off of the (111) surface orientation) yielded no increase in the rate of oxidation nor change in binding energy of the resultant oxide that formed on the alkylated Si surfaces. Scanning Auger microscopy indicated that the alkylated surfaces formed oxide in isolated, inhomogeneous patches on the surface.     

Thermal and photochemical oxidation of self-assembled monolayers on alumina particles exposed to nitrogen dioxide

Alumina is an important component of airborne dust particles as well as of building materials and soils found in the tropospheric boundary layer. While the uptake and reactions of oxides of nitrogen and their photochemistry on alumina have been reported in the past, little is known about the chemistry when organics are also present. Fourier transform infrared (FTIR) spectroscopy at ～23 °C was used to study reactions of NO(2) on γ-Al(2)O(3) particles that had been derivatized using 7-octenyltrichlorosilane to form a self-assembled monolayer (SAM). For comparison, the reactions with untreated γ-Al(2)O(3) were also studied. In both cases, the particles were exposed to water vapor prior to NO(2) to provide adsorbed water for reaction. As expected, surface-bound HONO, NO(2)(-), and NO(3)(-) were formed. Surprisingly, oxidation of the organic by surface-bound nitrogen oxides was observed in the dark, forming organo-nitrogen products identified as nitronates (R(2)C[double bond, length as m-dash]NO(2)(-)). Oxidation was more rapid under irradiation (λ > 290 nm) and formed organic nitrates and carbonyl compounds and/or peroxy nitrates in addition to the products observed in the dark. Mass spectrometry of the gas phase during irradiation revealed the production of NO, CO(2), and CO. These studies provide evidence for oxidation of organic compounds on particles and boundary layer surfaces that are exposed to air containing oxides of nitrogen, as well as new pathways for the formation of nitrogen-containing compounds on these surfaces.     

Imaging water dissociation on TiO2(110): Evidence for inequivalent geminate OH groups

Identical regions of partially reduced TiO2(110) surfaces with bridge-bonded oxygen vacancy (BBO(V)) concentrations of approximately 10% ML (1 ML = 5.2 x 10(14) cm(-2)) were imaged using scanning tunneling microscopy (STM) before and after dosing H2O at ambient temperature (approximately 300 K). Atomically resolved images confirm that H2O adsorbs dissociatively on the BBO(V) sites, producing two hydroxyl species, one positioned at BBO(V) and denoted OH(V) and the other, denoted OH(B), formed by protonation at either of the two nearest-neighbor bridge-bonded oxygen atoms. Hydrogen hopping along the [001] direction is observed at ambient temperature, with a strong preference for OH(B) (approximately 10x) hydrogen motion. This powerful imbalance demonstrates the inequality of OH(V) and OH(B) and suggests differences in their charge and/or binding configuration.     

Computational study on the reactions of H2O2 on TiO2 anatase (101) and rutile (110) surfaces

This study investigates the adsorption and reactions of H(2)O(2) on TiO(2) anatase (101) and rutile (110) surfaces by first-principles calculations based on the density functional theory in conjunction with the projected augmented wave approach, using PW91, PBE, and revPBE functionals. Adsorption mechanisms of H(2)O(2) and its fragments on both surfaces are analyzed. It is found that H(2)O(2) , H(2)O, and HO preferentially adsorb at the Ti(5c) site, meanwhile HOO, O, and H preferentially adsorb at the (O(2c))(Ti(5c)), (Ti(5c))(2), and O(2c) sites, respectively. Potential energy profiles of the adsorption processes on both surfaces have been constructed using the nudged elastic band method. The two restructured surfaces, the 1/3 ML oxygen covered TiO(2) and the hydroxylated TiO(2), are produced with the H(2)O(2) dehydration and deoxidation, respectively. The formation of main products, H(2)O(g) and the 1/3 ML oxygen covered TiO(2) surface, is exothermic by 2.8 and 5.0 kcal/mol, requiring energy barriers of 0.8 and 1.1 kcal/mol on the rutile (110) and anatase (101) surface, respectively. The rate constants for the H(2)O(2) dehydration processes have been predicted to be 6.65 × 10(-27) T(4.38) exp(-0.14 kcal mol(-1)/RT) and 3.18 × 10(-23) T(5.60) exp(-2.92 kcal mol(-1)/RT) respectively, in units of cm(3) molecule(-1) s(-1).     

Chemical alteration of poly(tetrafluoroethylene) TFE teflon induced by exposure to electrons and inert-gas ions

In this study the chemical alterations of poly(tetrafluoroethylene) (TFE Teflon) by approximately 1.0-keV electrons and 1.0-keV He and Ar ions have been examined using X-ray photoelectron spectroscopy (XPS). The initial F/C atom ratio of 1.99 decreases to a steady-state value of 1.48 after 48 h of electron exposure. Exposure to either He+ or Ar+ decreases the initial F/C atom ratio from approximately 2 to a steady-state value of 1.12. The high-resolution XPS C 1s data indicate that new chemical states of carbon form as the F is removed and that the relative amounts of these states depend on the F content of the near-surface region. These states are most likely due to C bonded only to one F atom, C bonded only to other C atoms and C that have lost a pair of electrons through emission of F-. Exposures of the electron-damaged and He+- or Ar+-damaged surfaces to research-grade O2 result in chemisorption of very small amounts of O indicating that large quantities of reactive sites are not formed during the chemical erosion. Further exposure to the electron or ion fluxes quickly removes this chemisorbed oxygen. Exposure of the He+-damaged surface to air at room temperature results in the chemisorption of a larger amount of O than the O2 exposure but no N is adsorbed. The chemical alterations due to electrons and ions are compared with those caused by hyperthermal (approximately 5 eV) atomic oxygen (AO) and vacuum ultraviolet (VUV) radiation. The largest amount of damage is caused by AO followed by VUV, inert-gas ions, and then electrons.     

Water exchange rates in the diruthenium mu-oxo ion cis,cis-[(bpy)(2)Ru(OH(2))](2)O(4+).

Addition of 2 equiv of Ce(4+) to the dimeric ruthenium mu-oxo ion cis,cis-[(bpy)(2)Ru(OH(2))](2)O(4+) (formal oxidation state III-III, subsequently denoted [3,3]) or addition of 1 equiv of Ce(4+) to the corresponding [3,4] ion gave near-quantitative conversion to the [4,4] ion, confirming our recent assignment of this oxidation state as an accumulating intermediate during water oxidation by the cis,cis-[(bpy)(2)Ru(O)](2)O(4+) ([5,5]) ion. The rates of water exchange at the cis-aqua positions in the [3,3] and [3,4] ions were investigated by incubating H(2)(18)O-enriched samples in normal water for predetermined times, then oxidizing them to the [5,5] state and measuring by resonance Raman (RR) spectroscopy changes in the magnitudes of the O-isotope sensitive bands at 780 and 818 cm(-1). These bands have been assigned to Ru=(18)O and Ru=(16)O stretching modes, respectively, for ruthenyl bonds formed by deprotonation of the aqua ligands upon oxidation to the [5,5] state. An intermediate accumulated during the course of the isotope exchange reaction that gave a [5,5] ion possessing both approximately 782 and approximately 812 cm(-1) bands; this spectrum was assigned to the mixed-isotope species, (bpy)(2)Ru((16)O)(16)ORu((18)O)(bpy)(2)(4+). Kinetic analysis of solutions at various levels of oxidation indicated that only the [3,3] ion underwent substitution; the exchange rate constant obtained in 0.5 M trifluoromethanesulfonic acid, 23 degrees C, was 7 x 10(-3) s(-1), which is (10(3)-10(5))-fold larger than rate constants measured for anation of monomeric (bpy)(2)Ru(III)X(H(2)O)(3+) ions bearing simple sigma-donor ligands (X).     

Methane oxidation over mixed-conducting SrFe(Al)O3-delta-SrAl2O4 composite

The steady-state CH4 conversion by oxygen permeating through mixed-conducting (SrFe)0.7(SrAl2)0.3Oz composite membranes, comprising strontium-deficient SrFe(Al)O3-delta perovskite and monoclinic SrAl2O4-based phases, occurs via different mechanisms in comparison to the dry methane interaction with the lattice oxygen. The catalytic behavior of powdered (SrFe)0.7(SrAl2)0.3Oz, studied by temperature-programmed reduction in dry CH4 at 523-1073 K, is governed by the level of oxygen nonstoichiometry in the crystal lattice of the perovskite component and is qualitatively similar to that of other perovskite-related ferrites, such as Sr0.7La0.3Fe0.8Al0.2O3-delta. While extensive oxygen release from the ferrite lattice at 700-900 K leads to predominant total oxidation of methane, significant selectivity to synthesis gas formation, with H2/CO ratios close to 2, is observed above 1000 K, when a critical value of oxygen deficiency is achieved. The steady-state oxidation over dense membranes at 1123-1223 K results, however, in prevailing total combustion, particularly due to excessive oxygen chemical potential at the membrane surface. In combination with surface-limited oxygen permeability, mass transport limitations in a porous layer at the membrane permeate side prevent reduction and enable stable operation of (SrFe)0.7(SrAl2)0.3Oz membranes under air/methane gradient. Taking into account the catalytic activity of SrFeO3-delta-based phases for the partial oxidation of methane to synthesis gas and the important role of mass transport-related effects, one promising approach for membrane development is the fabrication of thick layer of porous ferrite-based catalyst at the surface of dense (SrFe)0.7(SrAl2)0.3Oz composite.     

CeO2 as the Oxygen Carrier for Partial Oxidation of Methane to Synthesis Gas in Molten Salts： Thermodynamic Analysis and Experimental Investigation

A new technique -- the direct partial oxidation of methane to synthesis gas using lattice oxygen in molten salts medium has been introduced. Using CeO2 as the oxygen carrier, thermodynamic data were calculated in the reaction process, and the results indicated that direct partial oxidation of methane to synthesis gas using lattice oxygen of cerium oxide is feasible in theory. In a stainless steel reactor, the effects of temperature and varying amounts of γ-Al2O3 supported CeO2 on cn4 conversion, H2 and CO selectivity, were investigated, respectively. The results show that 10% CeO2/γ-Al2O3 has the maximal reaction activity at a temperature of 865 ℃ and above, the H2/CO ratio in the gas that has been produced reaches 2 and the CH4 conversion, H2 and CO selectivity reached the following percentages： i.e. 61%, 89%, and 91% at 870 ℃, respectively. In addition, increase of reaction temperature is favorable for the partial oxidation of methane.     

In situ ATR-IR spectroscopic and reaction kinetics studies of water-gas shift and methanol reforming on Pt/Al2O3 catalysts in vapor and liquid phases

Reaction kinetics measurements of the water-gas shift reaction were carried out at 373 K on Pt/Al2O3 in vapor phase to investigate the effects of CO, H2, and H2O partial pressures. Results of in situ ATR-IR studies conducted in vapor phase under similar conditions suggest that the Pt surface coverage by adsorbed CO is high (approximately 90% of the saturation coverage), leading to a negligible effect of the CO pressures on the rate of reaction. The negative reaction order with respect to the H2 pressure is caused by the increased coverage of adsorbed H atoms, and the fractional positive order with respect to the water pressure is consistent with non-equilibrated H2O dissociation on Pt. Results of in situ ATR-IR studies carried out at 373 K show that the presence of liquid water leads to a slight decrease in the Pt surface coverage by adsorbed CO (approximately 80% of the saturation coverage) when the CO partial pressure is the same as in the vapor-phase studies. The rate of the WGS reaction in the presence of liquid water is comparable to the rate under complete vaporization conditions when other factors (such as CO partial pressure) are held constant. Reaction kinetics measurements of methanol reforming were carried out at 423 K over a total pressure range of 1.36-5.84 bar. In situ ATR-IR studies were conducted at 423 K to determine the Pt surface coverage by adsorbed CO in completely vaporized methanol feeds and in aqueous methanol solutions. The decomposition of methanol is found to be slower during the reforming of methanol in liquid phase than in vapor phase, which leads to a lower rate of hydrogen production in liquid phase (0.08 min(-1) at 4.88 bar) than in vapor phase (0.23 min(-1) at 4.46 bar). The lower reaction order with respect to methanol concentration observed for vapor-phase versus liquid-phase methanol reforming (0.2 versus 0.8, respectively) is due to the higher extent of CO poisoning on Pt for reforming in vapor phase than in liquid phase, based on the higher coverage by adsorbed CO observed in completely vaporized methanol feeds (55-60% of the saturation coverage) than in aqueous methanol feed solutions (29-40% of the saturation coverage).     

Heterogeneous Interaction of H(2)O(2) with TiO(2) Surface under Dark and UV Light Irradiation Conditions

The heterogeneous interaction of H(2)O(2) with TiO(2) surface was investigated under dark conditions and in the presence of UV light using a low pressure flow tube reactor coupled with a quadrupole mass spectrometer. The uptake coefficients were measured as a function of the initial concentration of gaseous H(2)O(2) ([H(2)O(2)](0) = (0.17-120) × 10(12) molecules cm(-3)), irradiance intensity (J(NO(2)) = 0.002-0.012 s(-1)), relative humidity (RH = 0.003-82%), and temperature (T = 275-320 K). Under dark conditions, a deactivation of TiO(2) surface upon exposure to H(2)O(2) was observed, and only initial uptake coefficient of H(2)O(2) was measured, given by the following expression: γ(0)(dark) = 4.1 × 10(-3)/(1 + RH(0.65)) (calculated using BET surface area, estimated conservative uncertainty of 30%) at T = 300 K. The steady-state uptake coefficient measured on UV irradiated TiO(2) surface, γ(ss)(UV), was found to be independent of RH and showed a strong inverse dependence on [H(2)O(2)] and linear dependence on photon flux. In addition, slight negative temperature dependence, γ(ss)(UV) = 7.2 × 10(-4) exp[(460 ± 80)/T], was observed in the temperature range (275-320) K (with [H(2)O(2)] ≈ 5 × 10(11) molecules cm(-3) and J(NO(2)) = 0.012 s(-1)). Experiments with NO addition into the reactive system provided indirect evidence for HO(2) radical formation upon H(2)O(2) uptake, and the possible reaction mechanism is proposed. Finally, the atmospheric lifetime of H(2)O(2) with respect to the heterogeneous loss on mineral dust was estimated (using the uptake data for TiO(2)) to be in the range of hours during daytime, i.e., comparable to H(2)O(2) photolysis lifetime (～1 day), which is the major removal process of hydrogen peroxide in the atmosphere. These data indicate a strong potential impact of H(2)O(2) uptake on mineral aerosol on the HO(x) chemistry in the troposphere.     

Ultralow energy ion beam surface modification of low density polyethylene

Ultralow energy Ar+ and O+ ion beam irradiation of low density polyethylene has been carried out under controlled dose and monoenergetic conditions. XPS of Ar+-treated surfaces exposed to ambient atmosphere show that the bombardment of 50 eV Ar+ ions at a total dose of 10(16) cm(-2) gives rise to very reactive surfaces with oxygen incorporation at about 50% of the species present in the upper surface layer. Using pure O+ beam irradiation, comparatively low O incorporation is achieved without exposure to atmosphere (approximately 13% O in the upper surface). However, if the surface is activated by Ar+ pretreatment, then large oxygen contents can be achieved under subsequent O+ irradiation (up to 48% O). The results show that for very low energy (20 eV) oxygen ions there is a dose threshold of about 5 x 10(15) cm(-2) before surface oxygen incorporation is observed. It appears that, for both Ar+ and O+ ions in this regime, the degree of surface modification is only very weakly dependent on the ion energy. The results suggest that in the nonequilibrium plasma treatment of polymers, where the ion flux is typically 10(18) m(-2) s(-1), low energy ions (<50 eV) may be responsible for surface chemical modification.     

Effect of oxidation on the wettability of poly(dimethylsiloxane) surfaces

The wetting of amorphous poly(dimethylsiloxane) (PDMS) surfaces by water has been studied using molecular dynamics simulations. PDMS surfaces were generated by compressing a long PDMS chain between two elastic boundaries at atmospheric pressure. Oxidation of the PDMS surface, achieved in real systems by exposure to air plasma or corona discharge, was modeled by replacing methyl groups on the PDMS chain with hydroxyl groups. Three surfaces of varying degrees of oxidation were characterized by measuring the water contact angle and the roughness. The dependence of the microscopic contact angle on drop size was measured from time averaged density profiles. The macroscopic contact angle was measured directly using a cylindrical drop of infinite length with zero contact line curvature. The measured macroscopic contact angle ranged from approximately 125 degrees on the untreated surface to 75 degrees on the most oxidized surface studied. The line tension was found to increase with increasing degree of oxidation, from a negligible value on the untreated surface to approximately 5x10(-11) J m(-1) on the most heavily oxidized surface.     

Burial of gas-phase HNO(3) by growing ice surfaces under tropospheric conditions

The uptake of gas-phase nitric acid by ice surfaces undergoing growth by vapor deposition has been performed for the first time under conditions of the free troposphere. The investigation was performed using a coated-wall flow tube coupled to a chemical ionization mass spectrometer, at nitric acid partial pressures between 10(-7) and 10(-6) hPa, at 214, 229 and 239 K. Ice surfaces were prepared as smooth ice films from ultra-pure water. During the experiments an excess flow of water vapor was added to the carrier gas flow and the existing ice surfaces grew by depositing water vapor. The average growth rates ranged from 0.7-5 microm min(-1), values similar to those which prevail in some portions of the atmosphere. With growing ice the long term uptake of nitric acid is significantly enhanced compared to an experiment performed at equilibrium, i.e. at 100% relative humidity (RH) with respect to ice. The fraction of HNO(3) that is deposited onto the growing ice surface is independent of the growth rate and may be driven by the solubility of the nitric acid in the growing ice film rather than by condensation kinetics alone.     

水汽对TiO_2上CO光催化氧化反应的影响

在室温、杀菌灯照射下 ,对“氧化的”TiO2 催化剂上CO光催化氧化反应进行了研究 ,发现当原料气中加入分压为 3.36kPa水汽时 ,光催化氧化CO的活性明显降低 .这可能是由于杀菌灯照射下TiO2 表面生成的O-(a) 或O(a) 与H2 O反应生成·OH ,降低了表面的O-(a) 和O(a) 的浓度 ,而生成的·OH不能使CO氧化 ,从而降低了氧化CO的能力     

Plasma-assisted oxidation of Cu(100) and Cu(111)

Oxidized copper surfaces have attracted significant attention in recent years due to their unique catalytic properties, including their enhanced hydrocarbon selectivity during the electrochemical reduction of CO₂. Although oxygen plasma has been used to create highly active copper oxide electrodes for CO₂RR, how such treatment alters the copper surface is still poorly understood. Here, we study the oxidation of Cu(100) and Cu(111) surfaces by sequential exposure to a low-pressure oxygen plasma at room temperature. We used scanning tunnelling microscopy (STM), low energy electron microscopy (LEEM), X-ray photoelectron spectroscopy (XPS), near edge X-ray absorption fine structure spectroscopy (NEXAFS) and low energy electron diffraction (LEED) for the comprehensive characterization of the resulting oxide films. O₂-plasma exposure initially induces the growth of 3-dimensional oxide islands surrounded by an O-covered Cu surface. With ongoing plasma exposure, the islands coalesce and form a closed oxide film. Utilizing spectroscopy, we traced the evolution of metallic Cu, Cu₂O and CuO species upon oxygen plasma exposure and found a dependence of the surface structure and chemical state on the substrate''s orientation. On Cu(100) the oxide islands grow with a lower rate than on the (111) surface. Furthermore, while on Cu(100) only Cu₂O is formed during the initial growth phase, both Cu₂O and CuO species are simultaneously generated on Cu(111). Finally, prolonged oxygen plasma exposure results in a sandwiched film structure with CuO at the surface and Cu₂O at the interface to the metallic support. A stable CuO(111) surface orientation is identified in both cases, aligned to the Cu(111) support, but with two coexisting rotational domains on Cu(100). These findings illustrate the possibility of tailoring the oxidation state, structure and morphology of metallic surfaces for a wide range of applications through oxygen plasma treatments.

A low-pressure oxygen plasma oxidized Cu(100) and Cu(111) surfaces at room temperature. The time-dependent evolution of surface structure and chemical composition is reported in detail for a range of exposure times up to 30 min.     

Exploration of the potential energy surfaces, prediction of atmospheric concentrations, and prediction of vibrational spectra for the HO2...(H2O)n (n = 1-2) hydrogen bonded complexes

The hydroperoxy radical (HO2) plays a critical role in Earth's atmospheric chemistry as a component of many important reactions. The self-reaction of hydroperoxy radicals in the gas phase is strongly affected by the presence of water vapor. In this work, we explore the potential energy surfaces of hydroperoxy radicals hydrogen bonded to one or two water molecules, and predict atmospheric concentrations and vibrational spectra of these complexes. We predict that when the HO2 concentration is on the order of 10(8) molecules x cm(-3) at 298 K, that the number of HO2...H2O complexes is on the order of 10(7) molecules x cm(-3) and the number of HO2...(H2O)2 complexes is on the order of 10(6) molecules x cm(-3). Using the computed abundance of HO2...H2O, we predict that, at 298 K, the bimolecular rate constant for HO2...H2O + HO2 is about 10 times that for HO2 + HO2.