Adsorption of oxygen and reactivity with HCl on a barium-doped lead surface

X.p.s. studies on the adsorption of oxygen on a barium-covered Pb surface have shown the presence of two distinct types of oxygen species: oxidic, O2–, and the peroxo-like O2–2(ads), and the surface has been identified as a composite of PbO and BaPbO3. On a barium pre-covered surface, the sticking probability of oxygen on Pb is increased. The O2–(ads) species preferentially reacts with HCl forming PbCl2(ads)via proton abstraction, whereas O2–2(ads) is not reactive with HCl vapour. On the Pb surface, the PbCl2 overlayer reacts with excess HCl, forming a volatile compound believed to be Pb(ClHCl)2, while in the presence of coadsorbed barium, the stability of PbCl2 is increased and the activation energy for the reaction: PbCl2(ads)+ 2HCl(g) Pb(ClHCl)2(g) is increased. Stronger intermetallic interaction is suggested to be the reason for higher PbCl2 stability.

Surface modification of titania aerogel films by oxygen plasma treatment for enhanced dye adsorption

Titania aerogels were synthesized by sol-gel route followed by ambient pressure subcritical drying technique. The aerogels synthesized in the present work possess a maximum surface area of 252 m(2)/g. The pore size distribution is between 2 and 30 nm which confirms their mesoporosity. The oxygen plasma treatment on titania aerogel thin films improved the surface area up to 273 m(2)/g and produced additional hydrophilic groups on the surface. It is confirmed by BET surface area, XPS and thermal analysis in conjunction with dye adsorption studies. After plasma treatment the dye adsorption capacity was increased 2.5 times higher than that of untreated aerogel film. The increased surface area and the hydrophilic groups generated on the titania aerogel surface during plasma treatment are responsible for enhanced dye adsorption. The overall nanoporous morphology of titania aerogel is preserved after plasma treatment. (C) 2015 Elsevier B.V. All rights reserved.

Adsorption of oxygen on KxC（60） studied by photoelectron spectroscopy

国家自然科学基金

Adsorption of aqueous metal ions on oxygen and nitrogen functionalized nanoporous activated carbons

In this study, the adsorption characteristics of two series of oxygen and nitrogen functionalized activated carbons were investigated. These series were a low nitrogen content(similar to 1 wt % daf) carbon series derived from coconut shell and a high nitrogen content (similar to 8 wt % daf) carbon series derived from polyacrylonitrile. In both series, the oxygen contents were varied over the range similar to 2-22 wt % daf. The porous structures of the functionalized activated carbons were characterized using N-2 (77 K) and CO2 (273 K) adsorption. Only minor changes in the porous structure were observed in both series. This allowed the effect of changes in functional group concentrations on metal ion adsorption to be studied without major influences due to differences in porous structure characteristics. The surface group characteristics were examined by Fourier transform infrared (FTIR) spectroscopy, acid/base titrations, and measurement of the point of zero charge (pH(PZC)). The adsorption of aqueous metal ion species, M2+(aq), on acidic oxygen functional group sites mainly involves an ion exchange mechanism. The ratios of protons displaced to the amount of M2+(aq) metal species adsorbed have a linear relationship for the carbons with pH(PZC) <= 4.15. Hydrolysis of metal species in solution may affect the adsorption of metal ion species and displacement of protons. In the case of basic carbons, both protons and metal ions are adsorbed on the carbons. The complex nature of competitive adsorption between the proton and metal ion species and the amphoteric character of carbon surfaces are discussed in relation to the mechanism of adsorption.

Ultralow-temperature CO oxidation on an In2O3-Co3O4 catalyst: a strategy to tune CO adsorption strength and oxygen activation simultaneously

Highly efficient In2O3-Co3O4 catalysts were prepared for ultralow-temperature CO oxidation by simultaneously tuning the CO adsorption strength and oxygen activation over a Co3O4 surface, which could completely convert CO to CO2 at temperatures as low as -105 degrees C compared to -40 degrees C over pure Co3O4, with enhanced stability.

Modifying the adsorption characteristics of water on Ru{0001} with preadsorbed oxygen

The coadsorption of water and preadsorbed oxygen on Ru{0001) was studied by synchrotron-based high-resolution x-ray photoelectron spectroscopy. A dramatic change was observed in the interaction of water with oxygen between low and high oxygen precoverages. Low oxygen coverages below 0.18 ML induce partial dissociation, which leads to an adsorbed layer of H2O and OH. Around half the oxygen atoms take part in this reaction. All OH recombines upon heating to 200 K and desorbs together with H2O. Oxygen coverages between 0.20 and 0.50 ML inhibit dissociation, instead a highly stable intact water species is observed, which desorbs at 220 K. This species is significantly more stable than intact water on the clean surface. The stabilization is most likely due to the formation of hydrogen bonds with neighboring oxygen atoms. For intermediate oxygen coverages around 0.18 ML, the dissociation behavior depends on the preparation conditions, which points toward possible mechanisms and pathways for partial dissociation of water on Ru{0001}.

The influence of carbon surface oxygen groups on Dubinin–Astakhov equation parameters calculated from CO2 adsorption isotherm

We present the results of a systematic study of the influence of carbon surface oxidation on Dubinin–Astakhov isotherm parameters obtained from the fitting of CO2 adsorption data. Using GCMC simulations of adsorption on realistic VPC models differing in porosity and containing the most frequently occurring carbon surface functionalities (carboxyls, hydroxyls and carbonyls) and their mixtures, it is concluded that the maximum adsorption calculated from the DA model is not strongly affected by the presence of oxygen groups. Unfortunately, the same cannot be said of the remaining two parameters of this model i.e. the heterogeneity parameter (n) and the characteristic energy of adsorption (E0). Since from the latter the pore diameters of carbons are usually calculated, by inverse-type relationships, it is concluded that they are questionable for carbons containing surface oxides, especially carboxyls.

Oxygen photo-adsorption related quenching of photoluminescence in group-III nitride nanocolumns

GaN and InGaN nanocolumns of various compositions are studied by room-temperature photoluminescence (PL) under different ambient conditions. GaN nanocolumns exhibit a reversible quenching upon exposure to air under constant UV excitation, following a t−1/2 time dependence and resulting in a total reduction of intensity by 85–90%, as compared to PL measured in vacuum, with no spectral change. This effect is not observed when exposing the samples to pure nitrogen. We attribute this effect to photoabsorption and photodesorption of oxygen that modifies the surface potential bending. InGaN nanocolumns, under the same experimental conditions do not show the same quenching features: The high-energy part of the broad PL line is not modified by exposure to air, whereas a lower-energy part, which does quench by 80–90%, can now be distinguished. We discuss the different behaviors in terms of carrier localization and possible composition or strain gradients in the InGaN nanocolumns.

Impact of co-adsorbed oxygen on crotonaldehyde adsorption over gold nanoclusters:a computational study

Crotonaldehyde (2-butenal) adsorption over gold sub-nanometer particles, and the influence of co-adsorbed oxygen, has been systematically investigated by computational methods. Using density functional theory, the adsorption energetics of crotonaldehyde on bare and oxidised gold clusters (Au , d = 0.8 nm) were determined as a function of oxygen coverage and coordination geometry. At low oxygen coverage, sites are available for which crotonaldehyde adsorption is enhanced relative to bare Au clusters by 10 kJ mol. At higher oxygen coverage, crotonaldehyde is forced to adsorb in close proximity to oxygen weakening adsorption by up to 60 kJ mol relative to bare Au. Bonding geometries, density of states plots and Bader analysis, are used to elucidate crotonaldehyde bonding to gold nanoparticles in terms of partial electron transfer from Au to crotonaldehyde, and note that donation to gold from crotonaldehyde also becomes significant following metal oxidation. At high oxygen coverage we find that all molecular adsorption sites have a neighbouring, destabilising, oxygen adatom so that despite enhanced donation, crotonaldehyde adsorption is always weakened by steric interactions. For a larger cluster (Au, d = 1.1 nm) crotonaldehyde adsorption is destabilized in this way even at a low oxygen coverage. These findings provide a quantitative framework to underpin the experimentally observed influence of oxygen on the selective oxidation of crotyl alcohol to crotonaldehyde over gold and gold-palladium alloys. © 2014 the Partner Organisations.