Particle size distribution and morphological changes in activated carbon-metal oxide hybrid catalysts prepared under different heating conditions.

In catalysis processes, activated carbon (AC) and metal oxides (MOs) are widely used either as catalysts or as catalyst supports because of their unique properties. A combination of AC and a MO in a single hybrid material entails changes not only in the composition, microstructure and texture but also in the morphology, which may largely influence the catalytic behaviour of the resulting product. This work is aimed at investigating the modifications in the morphology and particle size distribution (PSD) for AC-MO hybrid catalysts as a result of their preparation under markedly different heating conditions. From a commercial AC and six MO (Al2O3, Fe2O3, ZnO, SnO2, TiO2 and WO3) precursors, two series of such catalysts are prepared by wet impregnation, oven-drying at 120 ºC, and subsequent heat treatment at 200 ºC or 850 ºC in inert atmosphere. The resulting samples are characterized in terms of their morphology and PSD by scanning electron microscopy and ImageJ processing program. Obtained results indicate that the morphology, PSD and degree of dispersion of the supported catalysts are strongly dependent both on the MO precursor and the heat treatment temperature. With the temperature rise, trends are towards the improvement of crystallinity, the broadening of the PSD and the increase in the average particle size, thus suggesting the involvement of sintering mechanisms. Such effects are more pronounced for the Fe, Sn and W catalysts due to the reduction of the corresponding MOs by AC during the heat treatment at 850 ºC.

Electrical conductivity of activated carbon-metal oxide nanocomposites under compression: a comparison study.

From a granular commercial activated carbon (AC) and six metal oxide (Al2O3, Fe2O3, SnO2, TiO2, WO3 and ZnO) precursors, two series of AC-metal oxide nanocomposites were prepared by wet impregnation, oven-drying at 120 °C, and subsequent heat treatment at 200 or 850 °C in an inert atmosphere. Here, the electrical conductivity of the resulting products was studied under moderate compression. The influence of the applied pressure, sample volume, mechanical work, and density of the hybrid materials was thoroughly investigated. The DC electrical conductivity of the compressed samples was measured at room temperature by the four-probe method. Compaction assays suggest that the mechanical properties of the nanocomposites are largely determined by the carbon matrix. Both the decrease in volume and the increase in density were relatively small and only significant at pressures lower than 100 kPa for AC and most nanocomposites. In contrast, the bulk electrical conductivity of the hybrid materials was strongly influenced by the intrinsic conductivity, mean crystallite size, content and chemical nature of the supported phases, which ultimately depend on the metal oxide precursor and heat treatment temperature. The supported nanoparticles may be considered to act as electrical switches either hindering or favouring the effective electron transport between the AC cores of neighbouring composite particles in contact under compression. Conductivity values as a rule were lower for the nanocomposites than for the raw AC, all of them falling in the range of semiconductor materials. With the increase in heat treatment temperature, the trend is toward the improvement of conductivity due to the increase in the crystallite size and, in some cases, to the formation of metals in the elemental state and even metal carbides. The patterns of variation of the electrical conductivity with pressure and mechanical work were slightly similar, thus suggesting the predominance of the pressure effects rather than the volume ones.

Activated carbon modifications to enhance its water treatment applications. An overview.

The main objective of this study was to list and compare the advantages and disadvantages of different methodologies to modify the surface of activated carbons (ACs) for their application as adsorbents to remove organic and inorganic pollutants from aqueous phase. These methodologies have been categorized into four broad groups: oxidation, sulfuration, ammonification, and coordinated ligand anchorage. Numerous investigations into the removal of metals from water have modified carbon surfaces to increase their content of acidic surface functional groups by using H(2)O(2), O(3) and HNO(3). Because these treatments can reduce the AC surface area, researchers are seeking alternative methods to modify and/or create surface functional groups without the undesirable effect of pore blockage. The nitrogenation or sulfuration of the AC surface can increase its basicity favoring the adsorption of organic compounds. The introduction of nitrogen or sulfur complexes on the carbon surface increases the surface polarity and, therefore, the specific interaction with polar pollutants. Different coordinated ligands have also been used to modify ACs, showing that coordinated ligand anchorage on the AC surface modifies its textural and chemical properties, but research to date has largely focused on the use of these modified materials to remove heavy metals from water by complexes formation.

Enhanced adsorption of metal ions onto functionalized granular activated carbons prepared from cherry stones.

Some granular activated carbons (GACs) were prepared from cherry stones (CS), an agricultural waste, by thermal methods following pyrolysis in nitrogen and subsequent activation (with air, carbon dioxide and steam) or single-step activation in steam. A GAC prepared by activation with carbon dioxide was further treated with several oxidizing agents (air, air-ozone mixture, nitric acid and hydrogen peroxide). The non-oxidized GACs produced have surface areas ranged from 508 to 901m(2)/g and show a predominantly micro- and macropores structure. Oxidation treatments, especially with nitric acid and ozone, led to the fixation of high amounts of acidic surface oxygen complexes (SOCs), thus making the carbon surface more hydrophilic. Contrary to oxidation with the other agents, the ozone treatment, at the conditions applied in this work, does not decrease the GAC surface area. Both, the non-oxidized and the oxidized GACs were used as adsorbent to study the adsorption of Cu(II) from aqueous solution. Adsorption isotherms were obtained at 25 degrees C and data were well fitted to the Langmuir equation. The results show that the Cu(II) uptake of the non-oxidized GACs is not great, but similar to that of the commercial grade Filtrasorb 400. The adsorption capacity for Cu(II) could be greatly enhanced by GAC oxidation, especially with nitric acid and ozone treatments. The larger adsorption capacity of the oxidized GACs has been attributed to oxygen functionalities (mainly carboxylic) fixed on the GAC surface, which can remove Cu(II) species from water by both ion-exchange and surface complexation mechanisms. The ozonated GAC was also evaluated for the adsorption of Co(II) species from single solute and Cu(II)-Co(II) binary mixture solutions. The functionalization of GAC by the ozone treatment improved the adsorption of both Cu(II) and Co(II) regardless of the fact that they were in single solute or binary systems.

Adsorption of mercury by carbonaceous adsorbents prepared from rubber of tyre wastes.

Rubber from tyre wastes has been used to prepare carbonaceous adsorbents and the products obtained have been tested as adsorbents for mercury in aqueous solution. The adsorbents have been prepared by applying thermal, chemical and combined (thermal and chemical or vice versa) treatments. Tyre rubber has been: heated at 400 or 900 degrees C for 2 h in N2, chemically-treated with H2SO4, HNO3 or H2SO4/HNO3 solution for 24 h, and in two successive steps first heated at 400 degrees C for 2h in N2 and then treated with a H2SO4/HNO3 solution for 24 h, or vice versa. Resultant products have been characterised in terms of elementary composition and textural properties. The adsorption of mercury has been studied from kinetic and equilibrium standpoints. The treatments effected to tyre rubber decrease the carbon content and the hydrogen content. The oxygen content and the nitrogen content increase for the chemically-treated products. The heat treatment of tyre rubber results in a larger development of surface area, microporosity, and mesoporosity than the chemical treatments. These treatments, however, produce a great creation of macropores. In comparison to the starting rubber, the adsorption process of mercury is faster when the material is heated or treated with the H2SO4, HNO3 or 1:3 H2SO4/HNO3 solution. These adsorbents are either a non-porous solid or possess a high mesopore volume or a wide pore size distribution in the macropore range. The adsorption capacity is larger for products prepared by heat, chemical and combined treatments of the rubber. A common textural characteristic of these adsorbents is their better developed microporosity. The ability to adsorb mercury is higher for the heated products than for the chemically-treated ones. The maximum adsorption of mercury is 211 mg g(-1). The constant Kf of the Freundlich equation is as high as 108.9 mg g(-1).

Development of activated carbon using vine shoots (Vitis vinifera) and its use for wine treatment.

An abundant and low-cost agricultural waste such as vine shoots (Vitis vinifera) (VS), which is generated by the annual pruning of vineyards, has been used as raw material in the preparation of powder activated carbon (AC) with a view to develop a new fining agent for white wines. A commercial activated carbon, S5X-Agrovin, was used for comparison purposes. From VS size-reduced pieces, AC was prepared using phosphoric acid as activating agent. The concentration of the H(3)PO(4) solution, the impregnation temperature, and the carbonization conditions were controlled. The carbons were texturally characterized by gas adsorption (N(2), -196 degrees C), mercury porosimetry, and density measurements. FT-IR spectroscopy was used in the analysis of the surface functional groups and structures of the carbons. Three varieties of white wine (i.e., cv. Cayetana, cv. Macabeo, and cv. Sauvignon Blanc) were treated with the activated carbons. Color changes were monitored by UV-vis spectrometry. Significant differences in the degree of uptake of polyphenols were observed depending on the wine variety and on the method of preparation of activated carbon. The carbon prepared by first impregnation of VS with the 60 vol% H(3)PO(4) solution at 50 degrees C and by then carbonization of the resultant product at 400 degrees C for 2 h presents a higher ability to discolor the white wines. The action of this carbon is comparable to that shown by the commercial product. Both carbons possess a well-developed porosity in the macropore range.

Adsorption kinetics of zinc in multicomponent ionic systems.

Using commercial activated carbon as an adsorbent, the kinetics of adsorption of zinc from multicomponent ionic systems having cadmium and mercury has been studied and reported. The variables investigated have been the chemical nature, ionic strength, and pH of the adsorptive (Zn2+) solution. The adsorption of Zn2+ is speeded up by the presence of Cd2+ and Hg2+ ions provided that the concentration of these two ions is high as compared to the concentration of Zn2+. When the ionic strength of the solution in relative terms is high (i.e., > 3 x 10(-4) M), however, the adsorption of Zn2+ decelerates. Also, the adsorption process is greatly accelerated at pH 12, whereas at pH 2 it does not occur at all.

Comparison between thermal and ozone regenerations of spent activated carbon exhausted with phenol.

Thermal and ozone regenerations of granular activated carbons (GAC) used in the removal of phenol from aqueous solution have been studied. The phenol isotherms for virgin GAC could be well represented by the Langmuir equation. Direct ozonation of GAC introduced large amounts of acidic surface oxygen groups, which caused a decrease in the phenol uptake. Thermogravimetric methods were used to investigate the mechanism of phenol adsorption onto virgin and ozonated carbons. Thermal regeneration was carried out at 1123K using nitrogen (pyrolysis alone) or nitrogen and carbon dioxide (pyrolysis plus oxidation). Results showed that spent carbons do not recover their adsorption characteristics when heated under inert conditions whereas carbon dioxide regeneration was effective at about 15% wt burn-off. Regeneration of GAC was also carried out with ozone as oxidizing gas at room temperature. Ozone dose and the nature of GAC have much influence on the regeneration performance. For an individual GAC there exits an optimum ozone dose for which phenol is eliminated together with most of its oxidation by-products without incurring in carbon surface chemical alterations. However, if excessive ozone is applied some acidic surface groups are formed on the GAC, thereby decreasing the adsorption capacity for phenol. Results showed that spent carbons can recover most of their adsorption characteristics and specific surface areas when regenerated through a number of adsorption-ozone regeneration cycles.

Adsorption of cadmium by sulphur dioxide treated activated carbon.

Merck carbon (1.5 mm) was treated in three ways: heating from ambient temperature to 900 degrees C in SO(2); treatment at ambient temperature in SO(2); or successive treatments in SO(2) and H(2)S at ambient temperature. All samples were then characterised and tested as adsorbents of Cd(2+) from aqueous solution. The characterisation was in terms of composition by effecting ultimate and proximate analyses and also of textural properties by N(2) adsorption at -196 degrees C. Kinetics and extent of the adsorption process of Cd(2+) were studied at 25 and 45 degrees C at pH of the Cd(2+) solution (i.e., 6.2) and at 25 degrees C also at pH 2.0. The various treatments of the starting carbon had no significant effect on the kinetics of the adsorption of Cd(2+), but increased its adsorption capacity. The most effective treatment was heating to 900 degrees C, the adsorption in this case being 70.3% more than that of the starting carbon. The adsorption increased at 45 degrees C but decreased at pH 2.0 when compared to adsorption at 25 degrees C and pH 6.2, respectively.

Free energy of interaction of sodium dodecyl sulfate in aqueous solution with carbon black surfaces.

The free energy of the adsorption process of an ionic surfactant from aqueous solutions onto a set of carbon blacks in the range of low concentrations was evaluated using the model proposed by van Oss and co-workers. The obtained results indicated that the free energy of interaction between adsorbent and adsorbate through water results mainly from Lifshitz-van der Waals and electrostatic interactions, and its value showed a good correspondence with that previously found from a combination of the classical measurements of adsorption isotherms and the Langmuir model.