Green synthesis of BiVO4/Eco-graphene nanostructures for the elimination of sulfamethoxazole by adsorption and photo-degradation using blue LED light.

Photo-catalysts based on BiVO4 (BV) and Eco-graphene (EG) were synthesized and obtained in a single step with high-quality properties. These nanostructures (NEs) were obtained through a green chemistry route and by adding 2, 3, and 5 wt% of a homemade EG. The BV/X EG NEs (where X = corresponds to the weight % of EG) demonstrated high photocatalytic activity, obtaining Sulfamethoxazole degradation percentages of 40, 45, 52, and 57 for BV, BV/2 EG, BV/3 EG, and BV/5 EG respectively, using a blue LED light. In addition, it was observed that the presence of EG slightly affected the surface area and porosity of BV. Moreover, it was observed that the presence of EG stabilized the scheelite monoclinic phase (m-s), and decreased the crystal size and band-gap values of BV-based samples. It was detected that EG contents increased the BV reduction, creating oxygen vacancies and V4+ states, which favored electron transfer, enhanced the photo-catalytic activity, and decreased the recombination rate. The adsorption influence of the BV/EG system was also studied. Finally, the stability tests of these materials after four cycles of reuse allowed keeping practically the full degradation capacity, demonstrating that these NEs represent a promising material driven by visible light that can be used for wastewater decontamination in the presence of drugs.

Influence of the physicochemical properties of inorganic supports on the activity of immobilized bacteria for water denitrification.

The denitrification of polluted water was studied by using supported E-coli bacteria. The physicochemical characteristics of supports and the influence of these properties on the bacteria performance were analyzed. Inorganic supports oxides and zeolites were selected in order to cover a wide range of porosity and surface chemical properties and the denitrification process systematically studied. Consecutive denitrification cycles in batch experiments and the toxicity of supports were also analyzed. The acidity of supports provokes a slower reduction processes, favoring also a high concentration of intermediate nitrites in solution for longer periods. The NO3(-) reduction is faster than the NO2(-) one, being also less influenced by the support characteristics. Anyway, the total denitrification is reached in all cases. The best performance was obtained with bacteria supported on mesoporous and non-acid silica support.

Application of ammonia intermittent temperature-programmed desorption to evaluate surface acidity of tungsten oxide supported on activated carbon.

Intermittent temperature-programmed desorption of ammonia was used to study the strength and population of surface acid sites of tungsten oxide supported on activated carbon pretreated at 350 and 700 degrees C. Catalysts pretreated at 350 degrees C showed two types of surface acid sites and desorption occurred with free readsorption until a temperature of around 300 degrees C was reached. Pretreatment at 700 degrees C produced three different states of ammonia adsorbed on the catalysts and desorption occurred with free readsorption.

Tailoring activated carbons for the development of specific adsorbents of gasoline vapors.

The specific adsorption of oxygenated and aliphatic gasoline components onto activated carbons (ACs) was studied under static and dynamic conditions. Ethanol and n-octane were selected as target molecules. A highly porous activated carbon (CA) was prepared by means of two processes: carbonization and chemical activation of olive stone residues. Different types of oxygenated groups, identified and quantified by TPD and XPS, were generated on the CA surface using an oxidation treatment with ammonium peroxydisulfate and then selectively removed by thermal treatments, as confirmed by TPD results. Chemical and porous transformations were carefully analyzed throughout these processes and related to their VOC removal performance. The analysis of the adsorption process under static conditions and the thermal desorption of VOCs enabled us to determine the total adsorption capacity and regeneration possibilities. Breakthrough curves obtained for the adsorption process carried out under dynamic conditions provided information about the mass transfer zone in each adsorption bed. While n-octane adsorption is mainly determined by the porosity of activated carbons, ethanol adsorption is related to their surface chemistry, and in particular is enhanced by the presence of carboxylic acid groups.

Design of low-temperature Pt-carbon combustion catalysts for VOC's treatments.

Two series of Pt/C-catalysts were prepared using pure carbon aerogels as supports. The influence of porosity, surface chemistry and Pt dispersion on the activity of Pt/C combustion catalysts was analyzed. The synthesis of the supports was fitted to have a monomodal pore size distribution in the meso and macropore range respectively. Both supports were functionalized by oxidation treatment with H(2)O(2) or (NH(4))(2)S(2)O(8). These treatments did not modify the porosity significantly, but the surface chemistry changed from basic to acid as oxygen content increased. In this way, Pt-dispersion decreased as a result of the low thermal stability of surface carboxylic acid groups. Benzene was selected as target VOCs and the catalytic combustion performance depended mainly on the porous texture and Pt-dispersion, while the variations in the surface chemistry of carbon supports due to oxidation treatments seemed to have a weak influence on this kind of reaction.

Inter- and intra-primary-particle structure of monolithic carbon aerogels obtained with varying solvents.

Different carbon aerogels were obtained by carbonization of organic aerogels prepared from the polymerization of resorcinol and formaldehyde using potassium carbonate as catalyst. Various solvents were added to the initial mixture to study their effects on the inter- and intra-primary-particle structure of the carbon aerogels. To carry out this study, various techniques were used, including high-resolution transmission and scanning electron microscopy, mercury porosimetry, mechanical tests, N2 and CO2 adsorption at -196 and 0 degrees C, respectively, and immersion calorimetry into benzene. Variation of the solvent used produced changes in the gelation time of the organic aerogels, which gave rise to variations in the inter- and intra-primary-particle structure of the carbon aerogels obtained. The monolith density of the carbon aerogels ranged from 0.37 to 0.87 g/cm3. Samples with a density higher than 0.61 g/cm3 had micropores and mesopores but no macropores. Macro- and mesoporosity had a monomodal pore size distribution. The elastic modulus showed a scaling relationship with density. In all samples studied, which had a mean micropore width of 0.62-1.06 nm, the surface area obtained by enthalpy of immersion into benzene yielded a realistic value of their total surface area.

Adsorption of benzene, toluene, and xylenes on monolithic carbon aerogels from dry air flows.

Monolithic carbon aerogels were obtained by carbonization of organic aerogels prepared by polymerization of resorcinol and formaldehyde under different conditions. Some carbon aerogels obtained were further CO2-activated. Samples were characterized by gas adsorption, scanning electron microscopy, high-resolution transmission electron microscopy, and mechanical tests. Benzene, toluene and xylenes were adsorbed from dry air by using carbon bed columns, obtaining the breakthrough curves. There was no correlation between the amount adsorbed at the breakthrough point and the volume of micropores narrower than 0.7 nm. Conversely, a good linear relationship between the amount adsorbed at the breakthrough point and the total micropore volume up to a mean micropore width of around 1.05 nm was found. In addition, the height of the mass transfer zone decreased with the mean width of the total micropores up to a value of around 1.05-1.10 nm. One of the best adsorbents obtained showed the lowest height of the mass transfer zone and one of the highest amounts adsorbed at the breakthrough point, either per mass or volume unit. However, it had a lower elastic modulus and compressive strength than other monolithic carbon aerogels, although its compressive strength (3 MPa) was still high enough to use it in carbon bed columns. The sample with the best mechanical properties was a poorer adsorbent. Regeneration of the exhausted adsorbents allowed the recovery of the hydrocarbons adsorbed without any appreciable loss of adsorption capacity of the carbon bed.

Ligand adsorption on an activated carbon for the removal of chromate ions from aqueous solutions.

The results presented in this work are related to the design of a guideline to develop specific properties at the surface of an activated carbon (AC). For this, two model aromatic compounds have been synthesized and their electrolytic behavior in aqueous solutions was studied by a potentiometric method. The textural characteristics of the activated carbon were determined by porosimetry methods. The nature of oxygen-carrying functions and the acid-base behavior of the AC surface were characterized by TPD and potentiometric titration methods, respectively. The adsorption and desorption equilibria of the aromatic compounds on activated carbon were measured in aqueous solutions, and the hysteresis between adsorption and desorption, which reveals irreversible adsorption, was discussed on the basis of the frontier orbital theory. HOMO and LUMO orbitals of the adsorbent and adsorbates were calculated, and irreversible adsorption was attributed to the small energy difference between HOMO and LUMO of the aromatic adsorbates and the adsorbent. Adsorption equilibria of K2CrO4 in aqueous solution on the AC alone and on the AC-aromatic ligand adsorbents, respectively, prove the efficient development of specific chemical functions at the carbon surface provided by the adsorbed aromatic compounds.

Activated carbon and tungsten oxide supported on activated carbon catalysts for toluene catalytic combustion.

We have used activated carbon (AC) prepared from almond shells as a support for tungsten oxide to develop a series of WOx/AC catalysts for the catalytic combustion of toluene. We conducted the reaction between 300 and 350 degrees C, using a flow of 500 ppm of toluene in air and space velocity (GHSV) in the range 4000-7000 h(-1). Results show that AC used as a support is an appropriate material for removing toluene from dilute streams. By decreasing the GHSV and increasing the reaction temperature AC becomes a specific catalyst for the total toluene oxidation (SCO2 = 100%), but in less favorable conditions CO appears as reaction product and toluene-derivative compounds are retained inside the pores. WOx/AC catalysts are more selective to CO2 than AC due to the strong acidity of this oxide; this behavior improves with increased metal loading and reaction temperature and contact time. The catalytic performance depends on the nonstoichiometric tungsten oxide obtained during the pretreatment. In comparison with other supports the WOx/AC catalysts present, at low reaction temperatures, higher activity and selectivity than WO, supported on SiO2, TiO2, Al2O3, or Y zeolite. This is due to the hydrophobic character of the AC surface which prevents the adsorption of water produced from toluene combustion thus avoiding the deactivation of the active centers. However, the use of WOx/AC system is always restricted by its gasification temperature (around 400 degrees C), which limits the ability to increase the conversion values by increasing reaction temperatures.