Investigation of chemisorption properties of the PbO surface

Chemisorption of O₂, Cl₂, and SO₂on the orthorhombic and tetragonal PbO samples was studied in the 225—550 °C temperature range. The main features of chemisorption are independent of the crystal modification of the sample. The change in the type of conductivity of PbO during chemisorption of O₂was found.     

The effect of platinum on the SnO<Subscript>2</Subscript> sorption properties

Chemisorption of SO₂ and O₂ at Pt-modified SnO₂ is studied by using the vacuum static method, with simultaneous recording of electrical conductivity, over the 22 to 300°C temperature range. The SnO₂ surface modification results in the increasing of SO₂ adsorption and weakening of the gas-surface bonding. The chemisorption enhances the samples’ electrical conductivity. The surface pretreatment with oxygen leads to the decreasing of the successive SO₂ chemisorption.     

Effect of lithium oxide dopants on electrophysical and sorption properties of zinc oxide

The effects of lithium oxide dopants (0.5–0.8 at. % Li) on the electrophysical and sorption properties of ZnO were studied in the temperature range from 150 °C to 410 °C. The introduction of lithium increases the activation energy of the conductivity of ZnO, decreases its conductivity, and increases the amount of S0₂ sorbed. Two forms of chemisorbed SO₂ (donor and acceptor) are observed on the surface.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1096–1100, May, 1996.     

Chemisorption of SO<Subscript>2</Subscript> on the Zn-modified In<Subscript>2</Subscript>O<Subscript>3</Subscript> surface

Chemisorption of SO₂ and O₂ on the In₂O₃ surface containing a zinc additive (0.4–2.7 at.%) was studied in a temperature range of 22–200 °C. At least three forms of sorbed SO₂ exist on the modified In₂O₃ surface. The temperature affects the contribution of single forms of SO₂ sorption and, hence, the change in the electric conductivity. The preliminary sorption of O₂ favors the formation of a donor form of chemisorbed SO₂. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2228–2232, October, 2005.     

Effect of gallium oxide dopants on electrophysical and sorption properties of zinc oxide

The effect of gallium oxide dopants (0.1–0.3 at.% Ga) on the electrophysical and sorption properties of ZnO was studied in the temperature range from 19 to 350 °C. The introduction of the dopant increasing the conductivity of ZnO is accompanied by a change in the amounts of SO₂ and Cl₂ sorbed and the reactivity of zinc oxide. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 266–270, February, 1999.     

Fast chemisorption of NO and SO2 on FeOOH crystals

The electrical conductivity changes of α-, β- and γ-FeOOH by adsorption of NO and SO₂ during 1 ms-1 min were determined. The conductivity change consists of fast and slow processes which are presumably caused by fast chemisorption on the oxygen vacancies and by slow one on the surface anions. The rate constants of fast and slow chemisorption were determined from the conductivity changes. The correlations of the rate constants with the compression pressure of specimen, adsorption temperature and original electrical conductivity are given. The order of magnitude of the fast chemisorption rate constants of the three polymorphs is related to the difference in the surface structure.     

Combined electrochemical and radiotracer study of anion sorption from aqueous solutions into polypyrrole films

The sorption of SO²⁻₄ and Cl⁻ ions into polypyrrole films has been studied by the radiotracer method under potential cycling and steady state conditions using labelled H₂SO₄ and HCl. Although a potential dependent migration and penetration of anions in the film can be detected, no strong correlation was found between the amount of charge consumed in the oxidation and reduction processes and the number of sorbed anions. The number of positively charged sites attracting anions into the film seems to be significantly lower than that expected from the amount of charge involved in the electrochemical transformations.     

Molecular Beam Studies on the Laser-Enhanced Surface Reaction of GaAs(100) with Chlorine

A cw supersonic Cl₂ molecular beam coupled with an angle-resolved time-of-flight (TOF) technique has been used to investigate the laser-enhanced surface reaction of GaAs(100) with chlorine. The mass and velocity distributions of the major reaction products under 1064 nm laser irradiation have been measured as a function of laser fluence, detection angle, surface temperature and normal component of the translational energy of the incident chlorine molecules. It has been found that increasing both laser fluence and the translational energy of incident chlorine molecules markedly enhance mis surface reaction. The measured flux angular distributions of major reaction products can be fit satisfactorily with a bi-cosine function. Measurements of the mass and angular distributions of reaction products by a modulated molecular beam mass spectrometry show that the surface temperature effect is obvious for the Cl₂/GaAs(100) “dark” thermal reaction. A direct activated dissociative chemisorption is proposed for the mechanism of Cl₂ chemisorption on the GaAs(100) surface.     

The non-covalent bindings of CF2Cl2 with NO and SO2

Ab initio calculations have been performed on the complexes of CF₂Cl₂ with NO and SO₂, and a set of stable configurations for CF₂Cl₂–NO and CF₂Cl₂–SO₂ were found with no imaginary frequencies by the MP2 method. In addition, the binding energy and the NBO analysis were used to evaluate the relative stability of the complexes. The calculated results indicate that the weak interactions in the CF₂Cl₂–NO and CF₂Cl₂–SO₂ systems involved are enhanced with the increase of the number of non-covalent bonds. Further studies predict that the CF₂Cl₂–SO₂ system may play a more important role than the CF₂Cl₂–NO system in environmental problem because the former offers a stronger interaction than the latter. Furthermore, the non-covalent binding interactions of Cl···N and Cl···O for CF₂Cl₂–NO system, Cl···O, Cl···S and F···S for CF₂Cl₂–SO₂ system, are the dominant forces, which seem to be very significant as a driving force influencing the arrangement of molecules, especially in CF₂Cl₂–SO₂ system.     

Kinetics and mechanism of nitration of cellulose with the HNO3-CH2Cl2 mixture

Complexing in the HNO₃-CH₂Cl₂ system was confirmed tensimetrically. The kinetics of nitration of wood cellulose by the HNO₃-CH₂Cl₂ mixture were investigated. A large part of the cellulose is nitrated in a first fast reaction in comparison to the HNO₃-H₂SO₄ mixture with the same concentration of HNO₃. The rate of the process is determined by the rate of diffusion of the HNO₃, the rate of the process decreases more rapidly in the case of HNO₃-CH₂Cl₂ than in the HNO₃-H₂SO₄ mixture, which is probably due to the effect of CH₂Cl₂ on the diffusion coefficient of HNO₃.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2445–2450, November, 1989.     

Adsorption of SO2 by typical carbonaceous material: a comparative study of carbon nanotubes and activated carbons

Applying activated carbons for SO₂ adsorption and conversion to H₂SO₄, as a dry process, has been considered the development direction of desulfurization technology. Coal-based activated carbon, coconut shell activated carbon, single wall carbon nanotube and multi-wall carbon nanotubes were used as typical carbonaceous materials to study the SO₂ adsorption mechanism. SEM, N₂ adsorption, XPS and fixed-bed reaction system were employed to study the morphology, pore structure, surface functional groups and SO₂ adsorption behaviors of the four adsorbents. The fixed-bed experiment was carried out at normal pressure and SO₂ concentration was set 1,000 ppm. According to SEM and N₂ adsorption results, hierarchical pore structure was an important characteristic of activated carbon. Aggregation was an important characteristic of CNTs. Mesopores and macropores took the dominance of pore structure in CNTs. According the SO₂ adsorption data and correlation analysis, it can be concluded that the dominant adsorption type on activated carbons does not alter with adsorption temperature changing. However, the adsorption type of SO₂ adsorption on CNTs changes with adsorption temperature varying. With adsorption temperature increasing, the dominant adsorption type transforms to chemisorption by physisorption. Higher-density π–π* in carbon nanotubes may be the active sites for the SO₂ chemical adsorption. Micropores with the diameter smaller than 0.7 nm were the best SO₂ adsorption place for both activated carbons and carbon nanotubes. The results provided a profound insight into the microstructure and SO₂ adsorption mechanism of the two kinds of carbonaceous materials.     

Dissolution of oxygen in polycrystalline palladium at $${P_{{O_2}}}$$= 100 Pa and temperatures of 500 to 950 K

The dissolution of oxygen in polycrystalline palladium Pd(poly) at an O₂ pressure of 100 Pa and temperatures of 500–950 K has been investigated by temperature-programmed desorption. At 500 K, the process yields a surface palladium film that includes an oxide-like reconstructed structure on a rarefied metal surface layer. At this temperature, palladium sorbs ~2 monolayers (ML) of oxygen. At 600–800 K, palladium dissolves up to ~140 ML of oxygen as a result of O₂ chemisorption on the surface of the oxide film, penetration of O_ads atoms under the oxide film, and their diffusion into the metal bulk. The dependence of the amount of oxygen sorbed by Pd(poly) (n) on the time of exposure to an O₂ atmosphere is described by a nearparabolic function, n = at^b, indicating that oxygen atoms diffuse in the metal lattice. The activation energy of this diffusion, Е _dif, is ~83.5 kJ/mol. At high temperatures (800–950 K), palladium sorbs much less oxygen (≤10 ML). This is due to the complete decomposition of the surface oxide film, a process that markedly hampers the insertion of Oads atoms under the surface layer of the metal.     

Aqueous extract of Acacia cyanophylla leaves as environmentally friendly inhibitor for mild steel corrosion in 1 M H2SO4 solution

The efficiency of Acacia cyanophylla leaves extract as an environmentally friendly inhibitor for mild steel in aerated aqueous 1 M H₂SO₄ solution has been investigated by potentiodynamic polarization measurements and electrochemical impedance spectroscopy techniques. Addition of inhibitor decreases the corrosion current whereas the corrosion potential values show slight shifts in positive directions. Inhibition efficiency was found to be about 93% (the maximum value was determined from the polarization curve). Efficiencies obtained from both electrochemical techniques are in good agreement. Adsorption of Acacia cyanophylla leaves extract on mild steel surface in 1 M H₂SO₄ solution obeys Langmuir adsorption isotherm. Polarization curves were also obtained at different temperatures in order to measure changes of corrosion rate. Corrosion current increases and inhibition efficiency decreases with temperature increasing in H₂SO₄ solutions with and without Acacia cyanophylla extract. Corrosion parameters also changed with exposure time. Copyright © 2010 John Wiley & Sons, Ltd.     

Room temperature ppb level Cl2 sensing using sulphonated copper phthalocyanine films

We present room temperature chemiresistive gas sensing characteristics of drop casted sulphonated copper phthalocyanine (CuTsPc) films. It has been demonstrated that these films are highly selective to Cl₂ and the sensitivity in the 5-2000 ppb range varies linearly between 65 and 625%. However, for concentrations ≥2000 ppb, the response becomes irreversible, which is found to be due to the chemical bond formation between Cl₂ and SO₃Na group of CuTsPc films. The X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) data confirms the oxidation of SO₃Na group by Cl₂ gas.     

On the open-circuit interaction between methanol and oxidized platinum electrodes

In the present work, results of the interaction between methanol and oxidized platinum surfaces as studied via transients of open-circuit potentials are presented. The surface oxidation before the exposure to interaction with 0.5 M methanol was performed at different polarization times at 1.4 V vs reversible hydrogen electrode (RHE). In spite of the small changes in the initial oxide content, the increase of the pre-polarization time induces a considerable increase of the time needed for the oxide consumption during its interaction with methanol. The influence of the identity of the chemisorbing anion on the transients was also investigated in the following media: 0.1 M HClO₄, 0.5 M H₂SO₄, and 0.5 M H₂SO₄ + 0.1 mM Cl⁻. It was observed that the transient time increases with the energy of anion chemisorption and, more importantly, without a change in the shape of the transient, meaning that free platinum sites are available at the topmost layer all over the transient and not only in the potential region of small oxide ‘coverage’. The impact of the pre-polarization time and the effect of anion chemisorption on the transients are rationalized in terms of the presence of surface and subsurface oxygen driven by place exchange.

Sulfur and chlorine K-shell x-ray absorption spectra of SCl2, S2Cl2, SOCl2, and SO2Cl2

The X-ray absorption spectra of dichlorosulfide (SCl₂), dichlorodisulfide (S₂Cl₂), thionyl chloride (SOCl₂) and sulfuryl chloride (SO₂Cl₂) have been recorded with synchrotron radiation in the regions of S 1s and Cl 1s excitation and ionization. Ionization current spectra of SOCl₂ and SO₂Cl₂ in the Cl 1s regions are also presented. The main spectral features are assigned to K-shell excitations to σ^* orbitals associated with the SCl, SS and SO bonds in these molecules.     

Polycations Stabilised by Borosulfates: [Au3Cl4][B(S2O7)2] and the One-Dimensional Metal [Au2Cl4][B(S2O7)2](SO3)

(SO₄)-rich silicate analogue borosulfates are able to stabilise cationic cluster-like and chain-like aggregates. Single crystals of [Au₃Cl₄][B(S₂O₇)₂] and [Au₂Cl₄][B(S₂O₇)₂](SO₃) were obtained by solvothermal reaction with SO₃, and the electronic properties were investigated by means of density functional theory–based calculations. [Au₃Cl₄][B(S₂O₇)₂] exhibits a cluster-like cation, and the cationic gold-chloride strands in [Au₂Cl₄][B(S₂O₇)₂](SO₃) are found to resemble one-dimensional metallic wires. This is confirmed by polarisation microscopy.     

Regioselective bromination of aromatic compounds with Br2/SO2Cl2 over microporous catalysts

A new selective brominating system Br₂/SO₂Cl₂/zeolite, has been discovered. Partially cation-exchanged Ca²⁺-Y zeolite efficiently catalyzes the selective para-bromination of neat chlorobenzene (CB) by Br₂/SO₂Cl₂ affording a CB conversion of ∼89% and a para-selectivity of ∼97%. During the bromination reaction, SO₂Cl₂ oxidizes HBr, prevents its accumulation within the zeolite pores and yields a more active brominating species. The Ca²⁺-Y catalyst was found to be stable under the bromination conditions, and can easily be regenerated by calcination. The Br₂/SO₂Cl₂/Ca²⁺-Y brominating system could be applicable to other activated aromatic compounds such as o-xylene, toluene and fluorobenzene.     

Platinum Nanoparticles on Silica Obtained Under Mild Conditions Using cis-PtCl2(CO)2 as Precursor

Physi-/chemisorption of cis-PtCl₂(CO)₂ on partially dehydroxylated amorphous silica followed by exposure to water vapor at room temperature or at 210°C produces platinum nanoparticles, through a reductive process involving both coordinated carbon monoxide and water. Incomplete removal of hydrogen-bonded water from the silica surface increases the implantation yield. XPS and TEM measurements are reported. The silica-supported platinum is catalytically active towards the hydrogenation of cyclohexene.     

Adsorption of H3PW12O40 by porous carbon materials

Adsorption of H₃PW₁₂O₄₀ from water and organic oxygen-containing solvents (AcOH, Me₂CO, MeOH) by carbon mesoporous materials, viz., Sibunit and catalytic filamentous carbons (CFC), was studied. The amount of irreversibly sorbed heteropolyacid is 50—100 mg g^–1 of support and decreases in the series of solvents: H₂O > Me₂CO > AcOH > MeOH. The adsorption capacity of CFC depends on the specific surface, total pore volume, and microstructure of the CFC fiber.