Optimizing filters of activated carbons obtained from biomass residues for ethylene removal in agro-food industry devices.

A series of adsorbents (activated carbons, ACs) were synthesized by physical and chemical activation of olive stones (OS) and their textural and chemical characteristics determined by complementary techniques such as N2 and CO2 physisorption, pH of the point zero of charge (pHPZC), HRSEM or XPS. Samples with a wide range of physicochemical properties were obtained by fitting the activation procedure. The performance of these adsorbents in filters working under dynamic conditions was studied by determining the corresponding breakthrough curves for the ethylene removal. The physicochemical transformations of OS during activation were related with the adsorptive performance of derivative ACs. Results were compared to those obtained using commercial carbons, in particular ACs, carbon black or carbon fibers, in order to identify the properties of these materials on influencing the adsorptive performance. In general, ACs from OS perform better than the commercial samples, being also easily regenerated and properly used during consecutive adsorption cycles. CO2-activation showed to be the best synthesis option, leading to granular ACs with a suitable microporosity and surface chemistry. These results could favour the integration of this type of inexpensive materials on devices for the preservation of climacteric fruits, in a clear example of circular economy by reusing the agricultural residues.

Magnetite Nanoparticles as Solar Photo-Fenton Catalysts for the Degradation of the 5-Fluorouracil Cytostatic Drug.

Heterogeneous catalysts based on magnetite nanoparticles, Fe3O4, were prepared by the chemical coprecipitation method using iron (III) chloride as a salt precursor. The physicochemical properties of the nanoparticles were determined by different techniques and the efficiency was evaluated for the degradation of the cytostatic drug, 5-fluorouracil (5-FU), in aqueous solution by photo-Fenton process under simulated solar radiation. The most influential parameters, namely pH of the solution, catalyst load, H2O2 dosage, and use of radiation, were studied and optimized in the degradation process. The optimal conditions to achieve a 100% degradation of 5-FU (10 mg L-1) and a high mineralization degree (76%) were established at the acidic pH of 3.0, 100 mg L-1 of catalyst loading, and 58 mM of H2O2 under simulated solar radiation. The contribution of iron leaching to the catalyst deactivation, the role of the dissolved iron ions on homogenous reactions, and the stability of the catalyst were assessed during consecutive reaction cycles.

One-Pot Thermal Synthesis of g-C3N4/ZnO Composites for the Degradation of 5-Fluoruracil Cytostatic Drug under UV-LED Irradiation.

Graphitic carbon nitride (g-C3N4) was used to enhance the photocatalytic activity of ZnO nanoparticles for the degradation of 5-fluorouracil (5-FU) cytostatic drug under UV-LED irradiation. CN/ZnO composites were synthetized by an easy one-pot thermal method, varying the g-C3N4 loading, i.e., from 10 to 67 wt% and a post-thermal exfoliation in air. The physicochemical and optical properties of the materials were analyzed by several techniques. CN/ZnO composites showed a coral-like structure of spherical ZnO wurtzite particles on the g-C3N4 structure. In general, the synergism and heterojunction interface between both phases allowed the enhancement of the mesoporosity, light absorption ability, and the aromaticity of the corresponding composites. Moreover, the photocatalytic activity of the CN/ZnO composites was increased with the addition of g-C3N4 in comparison with pristine ZnO. The highest activity was found for the composite containing 25 wt% of g-C3N4 (i.e., CN25/ZnO), reaching the total degradation of 5-FU and a mineralization of 48% at 180 min, as well as a good photostability during four reuse cycles. Experiments with different pH solutions and scavengers allowed for the assessment of the reactive oxygen species (ROS) involved in the 5-FU degradation pathway, with radicals and non-radical species as the main responsible active species. Furthermore, a tentative photocatalytic mechanism was proposed for CN/ZnO composites.

Specific adsorbents for the treatment of OMW phenolic compounds by activation of bio-residues from the olive oil industry.

A series of adsorbents was developed by physical (CO2) and chemical (KOH) activation of two bio-residues: olive stones (OS) and wood from olive tree pruning (OTP). The physicochemical properties of such materials were determined and correlated with their adsorptive performance in the removal of phenolic compounds of olive mill wastewater (OMW). Adsorption isotherms and kinetics of single phenolic acids, as well as the kinetics for competitive multi-compound adsorption, were fitted by applying different models, though Langmuir and pseudo-second order models fitted better the experimental results, respectively. The intraparticle diffusion model pointed out that mesoporosity reduces the influence of phenolic compounds' restrictions in the external film diffusion of the adsorbent particle-solution interphase, but adsorption capacity linearly increases with the micropore volume accessible to N2 at -196 °C (and also with BET surface area), while diffusion into ultramicropores (<0.7 nm, determined by CO2-adsorption) is slow and presents minor influence on the total adsorption capacity. After saturation, thermal regeneration of spent adsorbents allows the removal of adsorbed products, enabling the reuse of samples whilst maintaining a significant performance.

Photocatalytic Perfomance of ZnO-Graphene Oxide Composites towards the Degradation of Vanillic Acid under Solar Radiation and Visible-LED.

Graphene oxide (GO) is used to enhance the photocatalytic activity of ZnO nanoparticles for the degradation of vanillic acid (VA) under simulated solar light and visible-LED (λ > 430 nm). ZnO-GO composites are prepared by a mixing and sonication process with different GO loadings (i.e., from 1.8 to 6.5 wt.%). The materials are extensively characterized by thermogravimetric analysis (TGA), physisorption of N2, X-ray diffraction (XRD), infrared spectroscopy (FTIR), scanning electron microscopy (SEM), point of zero charge (pHPZC), and UV-Vis diffuse reflectance spectroscopy (DRUV). The presence of GO increases the photocatalytic activity of all the prepared composites in comparison with the pristine ZnO. The highest photocatalytic activity is found for the composite containing 5.5 wt.% of GO (i.e., ZnO-GO5.5), reaching a VA degradation of 99% and 35% under solar light and visible-LED, respectively. Higher TOC removal/VA degradation ratios are obtained from the experiments carried out under visible-LED, indicating a more effective process for the mineralization of VA than those observed under simulated solar light. The influence of hole, radical, and non-radical scavengers is studied in order to assess the occurrence of the reactive oxygen species (ROS) involved in the photocatalytic mechanism. The study of the photo-stability during three reuse experiments indicates that the presence of GO in the composites reduces the photocorrosion in comparison with pristine ZnO.

Supported Biofilms on Carbon-Oxide Composites for Nitrate Reduction in Agricultural Waste Water.

Escherichia coli colonies were grown on different supports for the removal of nitrates from water. A carbon material and different commercial metal oxides, such as SiO2, TiO2 and Al2O3, and their corresponding carbon-metal oxide composites were studied. The physicochemical properties were analyzed by different techniques and the results were correlated with their performance in the denitrification process. Developed biofilms effectively adhere to the supports and always reach the complete reduction of nitrates to gaseous products. Nevertheless, faster processes occur when the biofilm is supported on mesoporous and non-acid materials (carbon and silica).

Functionalized Graphene Derivatives and TiO2 for High Visible Light Photodegradation of Azo Dyes.

Functionalized graphene derivatives including graphene oxide (GO), reduced graphene oxide (rGO), and heteroatom (nitrogen/sulphur (N/S) or boron (B))-doped graphene were used to synthesize composites with TiO2 (T). The photocatalytic performance of composites was assessed for the degradation of Orange G dye (OG) under simulated solar light. All the prepared graphene derivatives-TiO2 composites showed better photocatalytic performance than bare TiO2. A higher photocatalytic activity was found for the composites containing GO and N/S co-doped rGO (kapp = 109.2 × 10-3 and 48.4 × 10-3 min-1, for GO-T and rGONS-T, respectively). The influence of both initial solution pH and the reactive species involved in the OG degradation pathway were studied. The photocatalytic activity of the samples decreased with the increase of the initial pH (from 3.0 to 10.0) due to the occurrence of electrostatic repulsive forces between the photocatalysts surface and the molecules of OG, both negatively charged. The use of selective scavengers showed that although the photogenerated holes dominate the degradation mechanism, radicals and singlet oxygen also participate in the OG degradation pathway. In addition, reutilization experiments indicated that the samples were stable under the reaction conditions used.

Fitting Biochars and Activated Carbons from Residues of the Olive Oil Industry as Supports of Fe- Catalysts for the Heterogeneous Fenton-Like Treatment of Simulated Olive Mill Wastewater.

A series of biochars and activated carbons (ACs) was prepared combining carbonization and physical or chemical activation of cheap and abundant residues of the olive oil industry. These materials were used as Fe-support to develop low-cost catalysts for the heterogeneous Fenton-like oxidation of simulated olive mill wastewater (OMW), the highly pollutant effluent generated by this agroindustry. Commercial ACs were also used as reference. All catalysts prepared were extensively characterized and results related with their performances in the catalytic wet peroxide oxidation (CWPO). Results showed a linear relationship of the textural properties of the catalysts with the adsorptive and catalytic performance, as well as the preferential adsorption and degradation of some phenolic compounds (caffeic and gallic acids) by specific interactions with the catalysts' surface. Despite the best performance of catalysts developed using commercial supports, those prepared from agro-industrial residues present some advantages, including a smaller catalyst deactivation by iron leaching. CWPO results show that catalysts from physically activated olive stones are the most promising materials, reaching total organic carbon and toxicity reductions of 35% and 60%, respectively, as well an efficient use of H2O2, comparable with those obtained using commercial supports. This approach showed that the optimized treatment of this type of residues will allow their integration in the circular economic process of the olive oil production.

Functionalized Cellulose for the Controlled Synthesis of Novel Carbon-Ti Nanocomposites: Physicochemical and Photocatalytic Properties.

Carbon-Ti nanocomposites were prepared by a controlled two-step method using microcrystalline cellulose as a raw material. The synthesis procedure involves the solubilization of cellulose by an acid treatment (H3PO4 or HNO3) and the impregnation with the Ti precursor followed of a carbonization step at 500 or 800 °C. The type of acid treatment leads to a different functionalization of cellulose with phosphorus- or oxygen-containing surface groups, which are able to control the load, dispersion and crystalline phase of Ti during the composite preparation. Thus, phosphorus functionalities lead to amorphous carbon-Ti composites at 500 °C, while TiP2O7 crystals are formed when prepared at 800 °C. On the contrary, oxygenated groups induce the formation of TiO2 rutile at an unusually low temperature (500 °C), while an increase of carbonization temperature promotes a progressive crystal growth. The removal of Orange G (OG) azo dye in aqueous solution, as target pollutant, was used to determine the adsorptive and photocatalytic efficiencies, with all composites being more active than the benchmark TiO2 material (Degussa P25). Carbon-Ti nanocomposites with a developed micro-mesoporosity, reduced band gap and TiO2 rutile phase were the most active in the photodegradation of OG under ultraviolet irradiation.

Cobalt oxide-carbon nanocatalysts with highly enhanced catalytic performance for the green synthesis of nitrogen heterocycles through the Friedländer condensation.

A novel series of eco-sustainable catalysts developed by supporting CoO nanoparticles on different carbon supports, highly efficient in the synthesis of quinolines and naphthyridines, through the Friedländer condensation, are reported for the first time. Textural properties, dispersion and location of the Co-phase are influenced by the nature of the carbon support, Co-precursor salt and metal loading, having a significant impact on the catalytic performance. Thus, the presence of the mesopores and macropores in carbon aerogels together with the homogeneous distribution of the active phase favours the formation of product 3a as a function of the metal loading. However, an increase in the metal content when using CNTs indicates the formation of CoO aggregates and an optimal concentration of 3 wt% CoO was observed, providing the highest conversion values. The carbon-based catalysts herein reported can be considered to be a sustainable alternative having advantages such as easy preparation, superior stability and notably enhanced catalytic performance, operating at lower temperature and under solvent-free conditions.

The use of functionalized carbon xerogels in cells growth.

In the present study carbon xerogels are used for the first time to study the fibroblast cell growth. For that, carbon xerogel microspheres are synthesized and thereafter functionalized with carbon nanofibers followed by the 1,3-dipolar cycloaddition of azomethine ylides (the so called "Prato reaction") or the addition of aryl diazonium salts (the so called "Tour reaction") to improve its wettability. The presence of nanofibers produces a huge improvement of the functionalization degree (59 versus 372 µmol/g for pristine carbon spheres and carbon spheres with 30% of carbon nanofibers, respectively) in spite of the blockage of the carbon spheres porosity caused after the nanofibers growth. This improvement was explained on the base of the increase of the number of probable active sites for the addition reactions (CC bonds) and the accessibility to these active sites (accessible surface area) by the presence of nanofibers. These high functionalization degrees reflect a promising potential of these materials in biomedical applications. Toxicity results obtained using a fibroblast cell line showed that samples are biocompatible for this kind of cells and that the presence of carbon fibers on the surface of the spheres increases the cells proliferation in a high extend reaching in some case values around 150% regarding the control. This study evidences that carbon aerogels could be interesting materials in biological applications, an unexplored field for this type of materials, being biocompatible, favouring the proliferation of cells and achieving high functionalization degrees.

On the Interactions and Synergism between Phases of Carbon⁻Phosphorus⁻Titanium Composites Synthetized from Cellulose for the Removal of the Orange-G Dye.

Carbon⁻phosphorus⁻titanium composites (CPT) were synthesized by Ti-impregnation and carbonization of cellulose. Microcrystalline cellulose used as carbon precursor was initially dissolved by phosphoric acid (H3PO4) to favor the Ti-dispersion and the simultaneous functionalization of the cellulose chains with phosphorus-containing groups, namely phosphates and polyphosphates. These groups interacted with the Ti-precursor during impregnation and determined the interface transformations during carbonization as a function of the Ti-content and carbonization temperature. Amorphous composites with high surface area and mesoporosity were obtained at low Ti-content (Ti:cellulose ratio = 1) and carbonization temperature (500 °C), while in composites with Ti:cellulose ratio = 12 and 800 °C, Ti-particles reacted with the cellulose groups leading to different Ti-crystalline polyphosphates and a marked loss of the porosity. The efficiency of composites in the removal of the Orange G dye in solution by adsorption and photocatalysis was discussed based on their physicochemical properties. These materials were more active than the benchmark TiO2 material (Degussa P25), showing a clear synergism between phases.

Electrodes Based on Carbon Aerogels Partially Graphitized by Doping with Transition Metals for Oxygen Reduction Reaction.

A series of carbon aerogels doped with iron, cobalt and nickel have been prepared. Metal nanoparticles very well dispersed into the carbon matrix catalyze the formation of graphitic clusters around them. Samples with different Ni content are obtained to test the influence of the metal loading. All aerogels have been characterized to analyze their textural properties, surface chemistry and crystal structures. These metal-doped aerogels have a very well-developed porosity, making their mesoporosity remarkable. Ni-doped aerogels are the ones with the largest surface area and the smallest graphitization. They also present larger mesopore volumes than Co- and Fe-doped aerogels. These materials are tested as electro-catalysts for the oxygen reduction reaction. Results show a clear and strong influence of the carbonaceous structure on the whole electro-catalytic behavior of the aerogels. Regarding the type of metal doping, aerogel doped with Co is the most active one, followed by Ni- and Fe-doped aerogels, respectively. As the Ni content is larger, the kinetic current densities increase. Comparatively, among the different doping metals, the results obtained with Ni are especially remarkable.

Chemical interactions of surface-active agents with growing resorcinol-formaldehyde gels.

The influence of cationic, anionic, and nonionic surfactants (S) on the characteristics of carbon xerogels was analyzed. The polymerization of resorcinol (R) and formaldehyde (F) was developed in an aqueous solution of S without any additional catalyst. The gels obtained were dried in air to obtain organic xerogels and then carbonized to carbon xerogels. The prepared samples were characterized by FTIR, TG, SEM, and N(2) and CO(2) adsorption. The formation of RF-S copolymers was observed for cationic and nonionic surfactants, but this was not observed for anionic S, probably because of repulsive electrostatic interactions between the two organic phases. Nevertheless, anionic S leads to a greater morphological transformation with the formation of nonporous needle particles associated with the higher pH induced by this S. Carbon xerogels are microporous materials with interesting molecular sieve behavior. The RF-S composites undergo greater shrinkage than do the pure RF xerogel; consequently, a narrower microporosity is obtained.

Synthesis and properties of phloroglucinol-phenol-formaldehyde carbon aerogels and xerogels.

Carbon aerogels and xerogels were successfully prepared from phloroglucinol-phenol mixtures and characterized by different techniques to determine their potential. We examined the influence of the phloroglucinol/phenol ratio, reactant concentration, cure conditions, and drying method on the morphology and porosity of the samples. The gelation time was found to be independent of the phloroglucinol/phenol ratio in spite of the different reactivities of both monomers. In general, carbon aerogels have a high volume of mesopores and of micropores without diffusion restrictions. Carbon xerogels are denser materials without mesopores but with a well-developed microporosity that shows a strong molecular sieve effect. Therefore, while micro-/mesoporous carbon aerogels can be used as catalyst supports or VOC adsorbents, the microporous carbon xerogel could offer high selectivity in the separation of small molecules from gaseous mixtures.

Reversible toluene adsorption on monolithic carbon aerogels.

Thirteen monolithic carbon aerogels with different pore textures were used as toluene adsorbents. Adsorption was carried out under both static and dynamic conditions. Under static conditions at 25 degrees C and at saturation, an adsorption capacity as high as 1.36 cm(3) g(-1) or 1180 mg g(-1) was obtained. Toluene adsorption was a reversible process in all carbon aerogels, and the adsorbed toluene was completely recovered by heating them at 400 degrees C. Regenerated adsorbents showed larger surface area and micropore width than the original samples, indicating that no pore blockage was produced. Adsorption under dynamic conditions at 100 degrees C was also completely reversible after at least three consecutive adsorption-desorption cycles. The ability of these carbon aerogels to reversibly adsorb toluene could be useful for their application in thermal swing adsorption or pressure swing adsorption equipment.

Experimental design to optimize preparation of activated carbons for use in water treatment.

A series of seven activated carbons was obtained for use in drinking water treatments by steam-activation of olive-waste cakes. This raw material is an abundant and cheap waste byproduct of oil production, making these activated carbons economically feasible. The activated carbons, prepared by the one step method, were characterized, and the evolution of their characteristics (yield, adsorption capacities, and porosity) was analyzed as a function of the experimental parameters (activation temperature and activation time), using the Doehlert matrix. The Doehlert matrix allows the response surface to be studied with a good quality parameter estimation of the quadratic model. Each response has been described by a second order model that was adequate to predict responses in all experimental regions. The coefficients of the postulated model were calculated from the experimental responses by means of least squares regression, using the NEMROD software. We determined the region in which the optimum values of both activation temperature and activation time were achieved for the preparation of activated carbons suitable for use in water treatments. The "optimal activated carbon" was experimentally obtained, and its characteristic parameters showed a good agreement with those calculated from the model. The results obtained for activated carbons prepared by the one-step method were compared with those for activated carbons prepared by the two-step method. The characteristics of activated carbons obtained by the one-step and two-step methods showed that "one-step" activated carbons have a highly developed porous texture formed mainly of large macropores and micropores, whereas "two-step" activated carbons have a predominance of mesopores and narrow micropores. These activated carbons from olive-waste cakes showed a high capacity to adsorb herbicides (2,4-dichlorophenoxyacetic acid, 2,4-D; and 2-methyl, 4-chlorophenoxyacetic acid, MCPA) from water, with adsorption capacity values higher than those corresponding to a commercial activated carbon used from drinking water treatments.