Calorimetric study of the adsorption of air pollutants on alumina-supported tin and gallium oxides

The differential enthalpies of adsorption of air pollutants such as SO₂, NO₂, NO on aluminasupported tin and gallium oxides were measured by calorimetry coupled with isothermal volumetry. Whatever the amount of tin or gallium on alumina, the enthalpies of adsorption of SO₂ at low coverage were of the same order of magnitude or up to 50 kJ/mol lower than those of the support. The amount of SO₂ adsorbed decreased with increasing SnO₂ loading and increased with increasing Ga₂O₃ loading on the alumina. The differential enthalpies of adsorption of NO₂ are close to those on the support whatever the amount of tin or gallium (around 120–130 kJ/mol). NO is only reversibly adsorbed on the samples. The calorimetric data of ammonia adsorption are given for comparison.     

Microcalorimetric Studies of the Surface Reactivity of Pollutant Gas Atmospheres on Supported SnO2 and Ga2O3 Catalysts

The surface properties of gallium oxide and tin dioxide supported on alumina or titania have been studied by adsorption microcalorimetry. The differential heats of adsorption of various pollutant adsorbates such as sulfur dioxide, nitrogen monoxide, nitrogen dioxide and also ammonia were measured on these catalytic surfaces. NH₃, SO₂, NO₂ are strongly adsorbed while NO is only physisorbed. The supported Ga₂O₃ samples show a slight decrease in acidity as probed by ammonia adsorption, compared to alumina or titania. The addition of SnO₂ decreases the number of strong acid sites but creates a few weak and medium strength acid sites on alumina and does not modify the acidity of titania. In all cases, the basicity, probed by SO₂ adsorption, is very strongly affected by the deposition of Ga₂O₃ or SnO₂. The differential heats of NO₂ adsorption remain nearly constant on all samples. The heats of adsorption are discussed as a function of the coverage and of the amount of guest oxide. This revised version was published online in August 2006 with corrections to the Cover Date.     

Adsorption study of micropore structure of tin dioxide

The micropore structure of xerogels of tin dioxide prepared by precipitation is studied by the physical adsorption of N₂, O₂, and H₂ at -195.6°C. The parameters of the microstructure as a whole depend on the adsorbate. The specific surface area of supermicropores measured by the oxygen adsorption exceeds that measured by nitrogen adsorption, and the extent of excess increases linearly with an increase in the supermicropore volume. The samples of tin dioxides have molecular-sieve properties, but they do not contain ultramicropores measurable by the adsorption of molecular hydrogen.     

Adsorption of Nitrogen,Oxygen, and Argon Vapors on Supermicroporous Oxides

The adsorption of N₂, O₂, and Ar vapors on a number of supermicroporous tin dioxide and zirconia xerogels at 77.4 K was studied. The micropore volumes calculated with the use of sorbate densities at the corresponding temperature were found to be in satisfactory agreement for all of the sorbates. At the same time, the volumes of larger pores measured using nitrogen were greater than the values found with other sorbates. The previously found behavior of oxygen and nitrogen molecules in the geometrically restricted space of supermicropores was substantiated. In particular, this behavior manifests itself in a change in the adsorption properties of a unit surface area of supermicropores as compared with the surface of mesopores. However, the effects of this kind were not found for the argon–nitrogen sorbate pair.     

Theoretical investigation of inhibition of the corrosion of A106 steel in NaCl solution by di-n-butyl bis(thiophene-2-carboxylato-O,O′)tin(IV)

This work reports results from potentiodynamic polarisation and impedance investigation, with a rotating disc electrode, of inhibition of corrosion of A106 steel in aerated, unstirred 3.0 % NaCl solutions using di-n-butyl bis(thiophene-2-carboxylato-O,O′)tin(IV) as inhibitor. These studies showed that it is a mixed-type inhibitor. Inhibition efficiency increased with increasing di-n-butyl bis(thiophene-2-carboxylato-O,O′)tin(IV) concentration and decreases with increasing solution temperature. Maximum efficiency of inhibition of the inhibitor of approximately 78 % is observed at a concentration at 10^?2 M. The inhibition process was attributed to formation of an adsorbed film on the metal surface that protects the metal against corrosive agents. The adsorption isotherm confirms the applicability of Langmuir equation to describe the adsorption process. Thermodynamic functions for the adsorption process were determined. The efficiency of corrosion inhibitors and global chemical reactivity depend on such properties as energy of the highest occupied molecular orbital (E _HOMO), energy of the lowest unoccupied molecular orbital (E _LUMO), energy gap (ΔE), which were calculated. All calculation was been performed by density functional theory (DFT) using the Gaussian03W suite of software. Calculated results were usually in agreement with the experimental data.     

Adsorption,Thermodynamic, and Experimental Studies of Corrosion Inhibitor of Tin in 0.2 M Maleic Acid by Hydrogen Phosphate Ions (HPO42−)

The inhibition efficiency of H₂PO₄²⁻ ions against tin corrosion in 0.2 M maleic acid is studied using electrochemical methods, surface analytical methods, and thermodynamic analysis. The potentiodynamic polarization plots showed the presence of an active/passive transition state of the tin electrode. The EIS measurements confirmed that the inhibition efficiency of H₂PO₄²⁻ increased by increasing the concentration (η=81 % at C_inh=2.10⁻² M) and decreased by rising the temperature. The polarization tests demonstrated that the inhibitor performs as a cathodic-type. The adsorption of the inhibitor was spontaneous and followed the Langmuir adsorption isotherm. A model of the inhibition mechanism was suggested.     

New catalysts and adsorbents on the basis of the InSb-CdTe semiconducting system

The acid-base properties of solid solutions and binary components of the InSb-CdTe system were studied by IR spectroscopy, pH isoelectric point measurements, and conductometric titration; adsorption properties with respect to CO, O₂, NO₂, NH₃, CO + O₂, and NO₂ + NH₃, by piezoquartz microweighing; and catalytic properties in the oxidation of carbon(II) oxide and reduction of nitrogen(IV) oxide with ammonia, by the pulsed and circulation flow methods. The nature, strength, and concentration of acid centers were determined. Changes in the concentration of acid centers under the action of gases (NO₂ and NH₃), gamma irradiation, and composition variations were estimated. The experimental dependences, thermodynamic and kinetic adsorption characteristics, the electrophysical, acid-base, and other physicochemical characteristics of the adsorbents, and adsorption characteristic-composition phase diagrams were analyzed taking into account the electronic nature of adsorbate molecules to determine the mechanism and characteristics of adsorption processes depending on the conditions of adsorption and the composition of the system. The results of adsorption studies were used to preliminarily determine the temperature regions of the occurrence and the mechanism of the reactions studied. A shock mechanism was suggested. Separate components (predominantly, solid solutions) of the InSb-CdTe system showed high catalytic activity at comparatively low temperatures. Along with behavior common to the system and its binary compounds (InSb and CdTe), solid solutions exhibited features characteristic of multi-component systems. These were the presence of extrema in the pH_iso-composition, adsorption characteristic-composition, and catalytic activity-composition diagrams. The use of these diagrams allowed us to discover system components most active with respect to the gases and reactions studied and create high-sensitivity and selective sensors and high-activity and selective catalysts on the basis of these components.     

Removal of radiocobalt from aqueous solution by Mg2Al layered double hydroxide

The adsorption behavior of radiocobalt by Mg₂Al layered double hydroxide (Mg₂Al LDH) was studied as a function of contact time, pH, ionic strength, foreign ions, FA and temperature under ambient conditions. The results showed that the kinetic adsorption could be described by a pseudo-second order model very well. The adsorption of Co(II) on Mg₂Al LDH was strongly dependent on pH and ionic strength. The presence of FA enhanced the adsorption of Co(II) on Mg₂Al LDH at low pH, whereas reduced Co(II) adsorption at high pH. The Langmuir model fitted the adsorption isotherms of Co(II) better than the Freundlich and D–R model at three different temperatures of 303, 323 and 343 K. The thermodynamic parameters (ΔH°, ΔS° and ΔG°) calculated from the temperature dependent adsorption isotherms indicated that the adsorption process of Co(II) on Mg₂Al LDH was endothermic and spontaneous. The results show that Mg₂Al LDH is a promising material for the preconcentration and separation of pollutants from large volumes of aqueous solutions.     

Enhanced adsorption of roxarsone onto humic acid modified goethite from aqueous solution

The adsorption of roxarsone (ROX) on the humic acid modified goethite (HA-α-FeOOH) was evaluated for several potential environmental factors. Results showed that 1) ROX had a higher adsorption capacity onto HA-α-FeOOH than unmodified α-FeOOH; 2) the adsorption of ROX increased with a decrease in pH; 3) the high ionic strength significantly inhibited the adsorption capacity of HA-α-FeOOH; and 4) a higher temperature yielded greater adsorption, since the process for ROX to be adsorbed by HA-α-FeOOH was a spontaneous endothermic reaction. The maximum adsorption capacity of ROX was found to be 80.71?mg?·?g^?1, when the temperature was 308?K. Meanwhile, the inhibitory effects of ionic strength and PO₄^3? on the adsorption of ROX onto HA-α-FeOOH were enhanced with an increase in concentration. In addition, the adsorption equilibrium data obeyed Langmuir isotherm model and the kinetic data were well described by the pseudo-second-order kinetic model. From the infrared spectra of HA-α-FeOOH, it could be deduced that the ROX adsorption onto HA-α-FeOOH was achieved via the ion exchange between the arsenic acid and the carboxyl group on adsorbent, as well as the formation of As-O-Fe bond between Fe-O and arsenic acid ions.     

Adsorption and desorption of small molecules for the characterization of solid acids

The relative acid strength and acid amount of solid acids has been determined from the adsorption and desorption of small molecules, such as argon. The order of activation energy for desorption of Ar from a solid acid, determined using temperature-programmed desorption (TPD), is sulfated zirconia > Cs_2.5H_0.5PW₁₂O₄₀ > proton-type zeolites > silica–alumina. The adsorption isotherms were analyzed using Langmuir and Henry equations. The Henry-type adsorption isotherms were also analyzed using the theory of Cremer and Flügge. The heat of Ar adsorption was 22 kJ mol⁻¹ for sulfated zirconia and ca. 17 kJ mol⁻¹ for mordenite, ZSM-5, and beta-zeolite. Molybdenum oxides reduced at 623 and 773 K exhibited a large heat of adsorption (19.3 and 19.7 kJ mol⁻¹, respectively), and these materials are classified as superacids. W-Nb mixed-oxides and tungstated tin oxide (calcined at 1373 K), which are newly developed solid acids, had a heat of adsorption of 18.1 and 16.9 kJ mol⁻¹, respectively. The type of acid site could be distinguished by comparing the heat of adsorption of Ar and N₂. Our data indicate that Ar is useful for the characterization of solid acids.     

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.     

Effect of environmental parameters on the sequestration of radionickel by Mg2Al layered double hydroxide

In this work, sequestration of Ni(II) from aqueous solution to Mg₂Al layered double hydroxide (Mg₂Al LDH) by adsorption process as a function of various water quality parameters and temperature was investigated. The results showed that the kinetic adsorption could be described by a pseudo-second order model very well. The adsorption of Ni(II) on Mg₂Al LDH was strongly dependent on pH and ionic strength. The presence of humic acid (HA)/fulvic acid (FA) enhanced the adsorption of Ni(II) on Mg₂Al LDH at low pH, whereas reduced Ni(II) adsorption at high pH. The Langmuir model fitted the adsorption isotherms of Ni(II) better than the Freundlich model at three different temperatures of 298, 318 and 338 K. The thermodynamic parameters (ΔH^o, ΔS^o and ΔG^o) calculated from the temperature dependent adsorption isotherms indicated that the adsorption process of Ni(II) on Mg₂Al LDH was endothermic and spontaneous. The results show that Mg₂Al LDH is a promising material for the preconcentration and separation of pollutants from large volumes of aqueous solutions.     

Removal of Th(IV), Ni(II)and Fe(II) from aqueous solutions by a novel PAN–TiO<Subscript>2</Subscript> nanofiber adsorbent modified with aminopropyltriethoxysilane

A novel polyacrylonitrile (PAN)–titanium oxide (TiO₂) nanofiber adsorbent functionalized with aminopropyltriethoxysilane (APTES) was fabricated by electrospinning. The adsorbent was characterized by SEM, FTIR, TEG and BET analyses. The pore diameter and surface area of the adsorbent were 3.1 nm and 10.8 m² g^?1, respectively. The effects of several variables, such as TiO₂ and amine contents, pH, interaction time, initial concentration of metal ions, ionic strength and temperature, were studied in batch experiments. The kinetic data were analyzed by pseudo-first-order, pseudo-second-order and double-exponential models. Two isotherm models, namely Freundlich and Langmuir, were used for analysis of equilibrium data. The maximum adsorption capacities of Th(IV), Ni(II) and Fe(II) by Langmuir isotherm were found to be 250, 147 and 80 mg g^?1 at 45 °C with pH of 5, 6 and 5, respectively, and greater adsorption of Th(IV) could be justified with the concept of covalent index and free energy of hydration. Calculation of ΔG°, ΔH° and ΔS° demonstrated that the nature of the Th(IV), Ni(II) and Fe(II) metal ions adsorption onto the PAN–TiO₂–APTES nanofiber was endothermic and favorable at a higher temperature. The negative values of ΔG° for Th(IV) showed that the adsorption process was spontaneous, but these values for Ni(II)and Fe(II) were positive and so the adsorption process was unspontaneous. Increasing of ionic strength improved the adsorption of Ni(II) and Fe(II) on nanofiber adsorbent but decreased the adsorption capacity of Th(IV). The adsorption capacity was reduced slightly after six cycles of adsorption–desorption, so the nanofiber adsorbent could be used on an industrial scale. The inhibitory effect of Ni(II) and Fe(II) on the adsorption of Th(IV) was increased with an increase in the concentration of inhibitor metal ions.     

Kinetics and equilibrium of adsorption on 4A zeolite

Adsorption isotherms for Ar, 0₂, N₂, CO, CO₂, CH₄, and C₂H₆ on 4A zeolite at three or more temperatures were determined. An adsorption equation based on a 2-dimensional virial equation in terms of integer powers of the reciprocal of (A - σ) was shown to fit the equilibrium data accurately with three constants for C₂H₆ and two constants for other gases. Here A is the area per molecule and σ is the area of the molecule in a close-packed situation.Rates of adsorption and desorption of Ar, N₂, CO, CH₄, and C₂H₆ on 4A zeolite were determined over ranges of temperature in which the rate was moderately fast. Electron microscopy showed that the particles were cubes, and their size-distribution was determined. The conventional Fick's law rate equation for cubes was used to produce a generalized rate curve for the particle size distribution of the adsorbent. This curve was applied to the last 20% of the rate curve to obtain a diffusivity that could be related to the final amount adsorbed. This procedure also avoids the initial rapid portion of the adsorption, in which large variations of adsorbent temperature from that of the bath often occur.The diffusivities increased with amount adsorbed by a small extent for Ar and CH₄ and by larger amounts for N₂, CO, and C₂H₆. The activation energy for diffusion, as well as the heat of adsorption, were nearly independent of amount adsorbed for Ar and CH₄, but these quantities decreased substantially with coverage for N₂, CO, and C₂H₆. The dependence upon amount adsorbed of diffusivity and activation energy seemed related to the shape of the adsorption isotherm; those for Ar and CH₄ were nearly linear, whereas isotherms for the other gases had large curvatures. The activation energy for diffusion varied with coverage in the same way as heat of adsorption.     

Synthesis, characterization, and application of titanate nanotubes for Th(IV) adsorption

Titanate nanotubes (TNTs) have been synthesized by a hydrothermal method using rutile TiO₂ powder as titanium source. The determination of the structure and morphology was characterized by XRD, FTIR, SEM and TEM. The results indicate that the TNTs successfully synthesized under hydrothermal conditions of 150 °C. The adsorption of Th(IV) on TNTs was studied as a function of contact time, pH values, ionic strength, initial Th(IV) concentration and temperature under ambient conditions by using batch technique. The results indicate that adsorption of Th(IV) on TNTs is strongly dependent on pH values, but weakly dependent on ionic strength; Adsorption kinetics was better described by the pseudo-second-order model. The adsorption isotherms are simulated by Langmuir and Freundlich models well. ΔG°, ΔH° and ΔS° free energy were calculated from experimental data, The results indicate that the adsorption of Th(IV) on TNTs is an endothermic and a spontaneous process, and increases with increasing temperature. The adsorption of Th(IV) on TNTs is mainly dominated by chemical sorption or surface complexation.     

Gas-Sensing Property of TM-MoTe2 Monolayer towards SO2, SOF2, and HF Gases

Detecting the characteristic decomposition products (SO₂, SOF₂, and HF) of SF₆ is an effective way to diagnose the electric discharge in SF₆-insulated equipment. Based on first-principles calculations, Au, Ag, and Cu were chosen as the surface modification transition metal to improve the adsorption and gas-sensing properties of MoTe₂ monolayer towards SO₂, SOF₂, and HF gases. The results show that Au, Ag, and Cu atoms tend to be trapped by T_H sites on the MoTe₂ monolayer, and the binding strength increases in the order of Ag < Au < Cu. In gas adsorption, the moderate adsorption energy provides the basis that the TM-MoTe₂ monolayer can be used as gas-sensing material for SO₂, SOF₂, and HF. The conductivity of the adsorption system changes significantly. The conductivity decreases upon gases adsorption on TM-MoTe₂ monolayer, except the conductivity of Ag-MoTe₂ monolayer increases after interacting with SOF₂ gas.     

Adsorption isotherms of CO2, CO,N2, CH4, Ar and H2 on activated carbon and zeolite LiX up to 1.0 MPa

The adsorption isotherms of CO₂, CO, N₂, CH₄, Ar, and H₂ on activated carbon and zeolite LiX were measured using a volumetric method. Equilibrium experiments were conducted at 293, 308, and 323 K and pressures up to 1.0 MPa. The adsorption isotherm and heat of adsorption were analyzed for two pressure regions of experimental data: pressures up to 0.1 MPa and up to 1.0 MPa. Each experimental isotherm was correlated by the Langmuir, Sips, Toth and temperature dependent Sips isotherm models, and the deviation of each model was evaluated. The Sips and Toth models showed smaller deviation from the experimental data of adsorbents than the Langmuir model. Isosteric heats of adsorption were calculated by the temperature dependent Sips model and are presented along with surface loading. From deviation analysis, it is recommended that the isotherm in the proper pressure range be used to appropriately design adsorptive processes.     

Adsorption characteristics of Titan yellow and Congo red on CoFe2O4 magnetic nanoparticles

This paper assesses the adsorption characteristics of Titan yellow and Congo red on CoFe₂O₄ magnetic nanoparticles. The adsorption behavior of Titan yellow and Congo red from aqueous solution onto CoFe₂O₄ magnetic nanoparticles has been determined by investigating the effects of pH, concentration of the dye, amount of adsorbent, contact time, ionic strength and temperature. Experimental results indicated that CoFe₂O₄ nanoparticles can remove more than 98 % of each dye under optimum operational conditions of a dosage of 15.0 mg CoFe₂O₄, pH 3.0, initial dye concentration of 22–140 mg L^?1, and contact times of 2.0 and 15.0 min for Congo red and Titan yellow, respectively. Langmuir and Freundlich isotherm models have been used to evaluate the ongoing adsorption kinetic equations. Regeneration of the saturated adsorbent was possible by NaCl/acetone solution as eluent. The maximum adsorption capacities were 200.0 and 212.8 mg dye per gram adsorbent for Congo red and Titan yellow, respectively. With the help of adsorption isotherm, thermodynamic parameters such as free energy, enthalpy and entropy have been calculated. On the basis of pseudo-first-order and pseudo-second-order kinetic equations, different kinetic parameters have been obtained.     

Specific features of the adsorption of chlorinated methanes and water on carbon nanotubes and alumina

The adsorption of CH₂Cl₂, CH₃Cl, CCl₄, and H₂O vapors on the surface of multi-walled carbon nanotubes and alumina in the temperature range of 10—25 °C was studied. Dependences of the isosteric heat of adsorption on the surface coverage were plotted. The initial heat of adsorption of dichloromethane, chloroform, and CCl₄ on Al₂O₃ was found to be equal to 71, 28, and 31 kJ mol^–1, respectively. In most cases, adsorption on the oxide adsorbent was characterized by a higher heat of adsorption compared to that found on the carbon material, which is apparently related to chemical interaction of sorbed molecules with the OH groups of the alumina surface.     

Tin Acetylacetonate as a Precursor for Producing Gas-Sensing SnO<Subscript>2</Subscript> Thin Films

To expand the range of precursors used in the sol–gel technology for applying nanostructured SnO₂ thin films promising as components of semiconductor chemical gas sensors, the efficiency of using tin acetylacetonate solutions with various precursor concentrations was demonstrated. It was determined that finely divided SnO₂ with a crystallite size of 3–4 nm (cassiterite) can be obtained by hydrolysis by atmospheric moisture in the course of solvent evaporation at room temperature. Using tin acetylacetonate solutions with various precursor concentrations for applying SnO₂ thin films by dip coating to the surface of rough ceramic Al₂O₃-based substrates with platinum interdigital electrodes and a microheater resulted in significant differences in microstructure, continuity, thickness, and porosity of the produced coatings. In a lower-concentration (0.13 mol/L) tin acetylacetonate solution, a multilayer dense continuous SnO₂ coating was applied, whereas in a higher-concentration (0.25 mol/L) solution, the formed layer comprised aggregated nanoparticles 30–60 nm in size and had much more defects and higher porosity. The sensitivity of the obtained thin-film nanostructures to the most practically important gaseous analytes: CO, H₂, CH₄, CO₂, and NO₂. The produced two-dimensional nanomaterials were shown to be promising for detecting carbon monoxide at 200–300°C in dry air.