Reduced Graphene Oxide Aerogels Cartridges for Solid Phase Extraction of Benzotriazoles.

UV-benzotriazoles have been identified as water micropollutants that cause serious problems for human health and the environment. Their low concentration in water bodies complicates their detection by direct water analysis, slowing the corrective actions to avoid bioaccumulation. In this regard, the use of graphene-based materials with a high affinity for non-polar molecules has been demonstrated to be a potential tool for the optimal separation and concentration of this type of molecules in solid phase extraction (SPE) processes. This work evaluates the potential of novel reduced graphene oxide aerogels (rGO) as extractants of mixtures of three UV-benzotriazoles in water at low concentrations. These rGO aerogels incorporate graphenic domains into a tough structure of polymeric chains by adding graphene oxide during the synthesis of resorcinol-formaldehyde gels. Aerogels with a different content and ordering of graphenic domains were obtained and characterized using Raman, XRD, SEM and nitrogen adsorption isotherms (-196 °C). The rGO aerogels that performed better as solid phase extractants were those containing 60% rGO. Aerogels with lower rGO contents (40%) required a high-temperature (2000 °C) treatment to render competitive results. The SPE methodology using selected rGO aerogels was optimized by varying the elution solvent, elution time and volume. The best performances, i.e., recoveries of 80-100% and enrichment factors of 12.5-50, were accomplished when using 0.8 mL of tetrahydrofuran (THF) as an elution solvent. As a result, a fast (10 min) and simple extraction method of UV-benzotriazoles in water was attained, achieving a detection limit of 1 ng mL-1. Selected aerogels were finally tested for the SPE of spiked samples of river waters, showing a similar performance to that observed with synthetic mixtures.

Water reclamation from anodizing wastewaters by removing reactive silica with adsorption and precipitation methods.

Water stress is a current environmental menace mainly driven by over exploitation of aquifers, which is triggering poor water quality with high concentration of minerals in extracted groundwater. Particularly, silica is widespread in natural water supplies due to weathering processes of silicates occurring in contact with water, light, air, and other factors. However, due to groundwater over extraction the concentration of silica has increased during the last years in aquifer reservoirs from Aguascalientes State (México). In this context, it is very important to note that the removal of silica compounds from water is challenging and different methods can be used to avoid embedding problems in different industries. In the present work, the removal of reactive silica from synthetic solutions as well as from real wastewaters from an industrial anodizing process was studied using adsorption and chemical precipitation methods. Twelve commercial materials of different nature were used for adsorption tests, while seven precipitant agents were applied in the precipitation experiments. Adsorption tests were performed in batch systems with constant stirring at 30 °C and at different pH values (7 and 9). Precipitation experiments were carried out in batch systems and the best conditions for silica removal were found using an L9 orthogonal array of the Taguchi method employing molar ratio, pH of wastewater, stirring time and temperature as experimental factors. Adsorption results showed that Ferrolox (Iron (III) hydroxide-base adsorbent) was the most efficient sorbent for reactive silica removal from synthetic solutions and the anodizing wastewater. Also, the reactive silica adsorption was higher at pH 9 as compared to that measured at pH 7 and the adsorbed quantity at pH 9 was 16.22 and 11.25 mg/g for the synthetic solution and anodizing wastewater, respectively. According to molecular simulation, the main interaction between Ferrolox and silica species was related to the formation of hydroxo-complexes and to the interaction of Fe with oxygen of silica species. Additionally, magnesium chloride was the best precipitating reagent for reactive silica achieving up to 87% removal. According to ANOVA analysis of Taguchi method, pH was the most influential factor during the precipitation of reactive silica with a variance value of 81.42, while values lower than 3 were obtained for the rest of parameters. Overall, the present work is reporting for the first time the removal of reactive silica from anodizing wastewaters with promising results that can be implemented at full scale for water reclamation, which may significantly contribute to manage water reservoir in the region sustainably.

Enhanced anaerobic treatment of synthetic protein-rich wastewater promoted by organic xerogels.

Carbon-based materials have been shown to enhance anaerobic digestion processes by promoting direct interspecies electron transfer in methanogenic consortia. However, little is known on their effects during the treatment of complex substrates, such as those derived from protein-rich wastewaters. Here, organic xerogels (OX) are tested, for the first time, as accelerators of the methanogenic activity of an anaerobic consortium treating a synthetic protein-rich wastewater. Three OX with distinct pore size distribution (10 and 1000 nm for OX-10 and OX-1000, respectively) and structural conformation (graphene oxide integration into OX-10-GO polymeric matrix) were synthesized. OX-1000 promoted the highest methane production rate (5.21 mL/g*h, 13.5% increase with respect to the control incubated without OX) among the synthesized OX. Additionally, batch bioreactors amended with OX achieved higher chemical oxygen demand (COD) removal (up to 88%) as compared to the control, which only showed 50% of COD removal. Interestingly, amendment of bioreactors with OX also triggered the production of medium-chain fatty acids, including caprylate and caproate. Moreover, OX decreased the accumulation of ammonium, derived from proteins hydrolysis, partly explained by their adsorption capacities, and probably involving their electron-accepting capacity promoting anaerobic ammonium oxidation. This is the first time that OX were successfully applied as methanogenic accelerators for the anaerobic treatment of synthetic protein-rich wastewater, increasing the methane production rate and COD removal as well as triggering the production of medium chain fatty acids and attenuating the accumulation of ammonium. Therefore, OX are proposed as suitable materials to boost the efficiency of anaerobic systems to treat complex industrial wastewaters.

Facile Synthesis of Unsupported Pd Aerogel for High Performance Formic Acid Microfluidic Fuel Cell.

In this work, unsupported Pd aerogel catalysts were synthesized for the very first time by using microwaves as a heating source followed by a lyophilization drying process and used towards formic acid electro-oxidation in a microfluidic fuel cell. Aerogels were also made by heating in a conventional oven to evaluate the microwave effect during the synthesis process of the unsupported Pd aerogels. The performance of the catalysts obtained by means of microwave heating favored the formic acid electro-oxidation with H2SO4 as the electrolyte. The aerogels' performance as anodic catalysts was carried out in a microfluidic fuel cell, giving power densities of up to 14 mW cm-2 when using mass loads of only 0.1 mg on a 0.019 cm2 electrode surface. The power densities of the aerogels obtained by microwave heating gave a performance superior to the resultant aerogel prepared using conventional heating and even better than a commercial Pd/C catalyst.

Ultralight-Weight Graphene Aerogels with Extremely High Electrical Conductivity.

The integration of 2D graphene sheets into a porous and macroscopic structure is extremely attractive for application in several electrochemical fields. In this regard, for the first time, the synthesis of 3D graphene aerogels is reported by using a rapid, easy, cost-effective, and scalable at industrial level methodology. These aerogels integrate the intrinsic properties of graphene with a high pore volume. To achieve this ultraporous graphene network, resorcinol/formaldehyde polymer with controllable porosity is employed as a binder and a cross-linker material, and a graphene oxide solution provides the graphene building blocks. Two series of materials with and without catalyst for resorcinol/formaldehyde reaction and with different synthesis conditions and graphene contents are studied. The resulting graphene aerogels present low density, large macroporosity, and electrical conductivity values as high as 852 S m-1 , with 97.58% of porosity, which is the highest value of electrical conductivity reported so far in the literature for ultralight-weight graphene aerogels.

Whey-Derived Porous Carbon Scaffolds for Bone Tissue Engineering.

Porous carbon structures derived from whey powders are described and evaluated as potential scaffolds in bone tissue engineering. These materials have a porosity between 48% and 58%, with a hierarchical pore size distribution ranging from 1 to 400 micrometres. Compressive strength and elastic modulus are outstanding for such a porous material, being up to three times better than those of traditional HA or TCP scaffolds with similar porosities. They also present non-cytotoxic and bioactive behavior, due to their carbon-based composition that also includes some residual mineral salts content.

Competitive adsorption of pollutants from anodizing wastewaters to promote water reuse.

Anodizing wastewater contains principally phosphate (PO43-) anions according to previous studies, but with the purpose to promote water reuse in this type of industry, a complete characterization of wastewater was made to remove other anions and cations also present in significant concentration. Particularly, the adsorption of sodium (Na+), potassium (K+), fluoride (F-), sulfate (SO42-) and phosphate (PO43-) was studied using different sorbents such as: coconut shell activated carbon, bone char, bituminous coal activated carbon, natural zeolite, silica, anionic and cationic exchange resins, a coated manganese-calcium zeolite, coconut shell activated carbon containing iron and iron hydroxide. All sorbents were characterized using FT-IR spectroscopy, potentiometric titration, nitrogen adsorption isotherms at 77 K, X-ray diffraction and SEM/EDX analysis to study the adsorption mechanism. The adsorption studies were performed in batch systems under constant agitation using both standard solutions of each ion and real anodizing wastewater. Results showed that, in general, the adsorption of all anions and cations is higher when mono-component standard solutions were used, since in the anodizing wastewater all species are competing for the active sites of the adsorbent. Na+ present in anodizing wastewater was efficiently adsorbed on coated manganese-calcium zeolite (20.55 mg/g) and natural zeolite (18.55 mg/g); while K+ was poorly adsorbed on all sorbents (less than 0.20 mg/g). Anions such as F-, SO42- and PO43-, were better adsorbed on the anionic resin (0.17, 45.38 and 2.92 mg/g, respectively), the iron hydroxide (0.14, 7.96 and 2.87 mg/g, respectively) and the bone char (0.34, 8.71 and 0.27 mg/g, respectively). All these results suggest that adsorption is a promising tertiary treatment method to achieve water reuse in the anodizing industry.

Adsorption of impurities from nickel-plating baths using commercial sorbents to reduce wastewater discharges.

The presence of moderate concentrations of impurities in the nickel-plating baths generates failures on the coated pieces. This situation entails the necessity of replacing the electroplating bath, which implies the generation of large volumes of wastewater with metallic species and high quantity of sludge. For this reason, the adsorption of the principal impurities of nickel-plating baths of an industry was analyzed in this work. Particularly, the removal of Zn2+ was studied in more detail since the presence of this metal in the baths generates black spots on the coated pieces. Different commercial materials were used as adsorbents and Zn2+ adsorption studies were carried out using both standard solutions and industrial water from the nickel-plating baths. All the adsorption tests were performed in batch systems under constant agitation and the quantification of the impurities was made by ICP-MS analysis. The bone char (BC) was an efficient adsorbent for the removal of the principal impurities of nickel-plating baths. The use of molecular simulation tools helped to understand the preferences of the hydroxyapatite (the principal component of bone char) for different metallic ions present in the industrial waters. According to both the experimental adsorption and molecular simulation results, hydroxyl and phosphate groups of bone char are responsible of the adsorption of impurities of nickel-plating baths.

Graphitized Carbon Xerogels for Lithium-Ion Batteries.

Carbon xerogels with different macropore sizes and degrees of graphitization were evaluated as electrodes in lithium-ion batteries. It was found that pore structure of the xerogels has a marked effect on the degree of graphitization of the final carbons. Moreover, the incorporation of graphene oxide to the polymeric structure of the carbon xerogels also leads to a change in their carbonaceous structure and to a remarkable increase in the graphitic phase of the samples studied. The sample with the highest degree of graphitization (i.e., hybrid graphene-carbon xerogel) displayed the highest capacity and stability over 100 cycles, with values even higher than those of the commercial graphite SLP50 used as reference.

Use of by-products from integrated steel plants as catalysts for the removal of trichloroethylene from groundwater.

The removal of tricholoroethylene (TCE) has been investigated in this work through the Fenton-like process using different catalytic materials obtained from metallic by-products of the steel industry. These materials are the slag produced during the transformation of molten pig iron produced in a blast furnace into liquid steel (SLD), the dry particles (or dust) obtained from the bag filters installed in the coking installations to minimize diffuse emissions (POCA) and the dry particles obtained from the liquid sludge from the scrubber (LHA). This study aims to explore the potential of these materials for being used as permeable catalytic barriers to treat groundwater polluted with trichloroethylene (TCE). The wastes used as catalysts were chemically and physically characterized to determine their composition and porosity. The results of this study point out that among the different catalysts used LHA showed the highest catalytic activity to degrade TCE using hydrogen peroxide. Moreover, LHA was the most efficient catalyst using hydrogen peroxide due to its higher stoichiometric efficiency. It is thus concluded that LHA has a high potential to be combined with hydrogen peroxide in permeable catalytic barriers to remove organic compounds from groundwater.

Load-dependent surface diffusion model for analyzing the kinetics of protein adsorption onto mesoporous materials.

The adsorption of cytochrome c in water onto organic and carbon xerogels with narrow pore size distributions has been studied by carrying out transient and equilibrium batch adsorption experiments. It was found that equilibrium adsorption exhibits a quasi-Langmuirian behavior (a g coefficient in the Redlich-Peterson isotherms of over 0.95) involving the formation of a monolayer of cyt c with a depth of ∼4nm on the surface of all xerogels for a packing density of the protein inside the pores of 0.29gcm-3. A load-dependent surface diffusion model (LDSDM) has been developed and numerically solved to fit the experimental kinetic adsorption curves. The results of the LDSDM show better fittings than the standard homogeneous surface diffusion model. The value of the external mass transfer coefficient obtained by numerical optimization confirms that the process is controlled by the intraparticle surface diffusion of cyt c. The surface diffusion coefficients decrease with increasing protein load down to zero for the maximum possible load. The decrease is steeper in the case of the xerogels with the smallest average pore diameter (∼15nm), the limit at which the zero-load diffusion coefficient of cyt c also begins to be negatively affected by interactions with the opposite wall of the pore.

Bone char with antibacterial properties for fluoride removal: Preparation, characterization and water treatment.

In the present work, it was established a new method for the preparation of bone chars with a double purpose, i.e., the removal of fluoride from water and the antibacterial character. These adsorbents were obtained by doping a commercial bone char with Ag using different reagents. The optimal conditions for the enrichment with silver were established by following the Taguchi method and using as response variable the removal of fluoride from water. Optimal bone chars were thus prepared and they were characterized using FT-IR spectroscopy, SEM/EDX analysis, adsorption isotherms of N2 at -196 °C and X-ray diffraction. All adsorbents were used in the removal of fluoride from water and the antibacterial character was assessed using the technique of total viable count employing standard solutions of Escherichia coli and drinking water. Results clearly indicated that doping of bone chars with silver provides with suitable antibacterial properties, however the fluoride adsorption capacity was not affected by the presence of Ag° on the carbon surface.

Correlation between mesopore volume of carbon supports and the immobilization of laccase from Trametes versicolor for the decolorization of Acid Orange 7.

Immobilization of laccase from Trametes versicolor was carried out using carbon supports prepared from different lignocellulosic wastes. Enzymes were immobilized by physical adsorption. Taguchi methodology was selected for the design of experiments regarding the preparation of the carbon materials, which included the use of activating agents for the promotion of mesoporosity. A good correlation between the mesopore volumes of the carbon supports and the corresponding laccase loadings attained was observed. Specifically, the chemical activation of pecan nut shell with FeCl3 led to a highly mesoporous material that also behaved as the most efficient support for the immobilization of laccase. This particular laccase/carbon support system was used as biocatalyst for the decolorization of aqueous solutions containing Acid Orange 7. Mass spectrometry coupled to a liquid chromatograph allowed us to identify the products of the dye degradation.

Biogas upgrading: optimal activated carbon properties for siloxane removal.

A total of 12 commercial activated carbons (ACs) have been tested for the removal of octamethylcyclotetrasiloxane (D4) in dynamic adsorption experiments using different carrier gases and D4 concentrations. Characterization of the ACs included several physical and chemical techniques. The D4 adsorption capacities were strongly related with the textural development of the ACs. Results showed that the optimum adsorbent for D4 is a wood-based chemically activated carbon, which rendered an adsorption capacity of 1732 ± 93 mg g(-1) using 1000 ppm (v/v) of D4 with dry N2 as the carrier gas. When the concentration of D4 was lowered to typical values found in biogas, the adsorption capacity was halved. The presence of major biogas compounds (i.e., CH4 and CO2) and humidity further reduced the D4 adsorption capacity. The polymerization of D4 over the surface of all ACs was found to be relevant after prolonged contact times. The extent of this phenomenon, which may negatively affect the thermal regeneration of the AC, correlated reasonably well with the presence of phenolic and carboxylic groups on the carbon surfaces.

H2O2-based oxidation processes for the regeneration of activated carbons saturated with volatile organic compounds of different polarity.

This study reports the sequential regeneration treatment of activated carbons (ACs) saturated with volatile organic compounds (VOCs) of different polarity using H(2)O(2) as oxidizing agent. In this process, VOCs were adsorbed onto the AC and further oxidized by H(2)O(2). A commercial AC was selected and saturated with three different VOCs: two non-polar and hydrophobic VOCs, toluene and limonene, and one polar and hydrophilic VOC, methyl ethyl ketone (MEK). The saturated AC was regenerated with H(2)O(2), and the Fenton reagent for comparison. It was found that regeneration efficiencies obtained with the H(2)O(2) treatment were equal to or even higher than those obtained with the Fenton treatment. The fate of the pre-adsorbed VOCs, once the regeneration process is completed was studied. It was found that this regeneration treatment is limited for non-polar VOCs such as toluene and limonene, as they tend to remain adsorbed onto the ACs after regeneration treatment. Contrarily, MEK tend to be transferred to the bulk phase and react with the generated oxidant species.

Linz-Donawitz steel slag for the removal of hydrogen sulfide at room temperature.

Slags collected from the basic oxygen furnaces of two Linz-Donawitz steel making plants were tested as adsorbents for H(2)S removal at room temperature (298 K). Two different particle size fractions, namely <212 and 212-500 µm, were selected from the original slag samples. Dynamic adsorption tests were carried out using a column-bed configuration and retention capacities were calculated after bed exhaustion. Retention capacities as high as 180 mg of H(2)S g(-1) of slag were attained, in spite of the very low specific surface area of the steel slags. As expected, humidity played a crucial role in the removal of H(2)S. Particle size had also an important effect on the capacity of the adsorption beds. Analysis of the exhausted slags revealed considerable amounts of elemental sulfur on the surface of the particles. Sulfates were also found on the exhausted slags, especially on the 212-500 µm size fractions. The characterization of the slags prior and after the H(2)S adsorption experiments allowed us to postulate plausible mechanisms to understand the outstanding capacity of these steel byproduct for H(2)S adsorption.

A new generation of sludge-based adsorbents for H2S abatement at room temperature.

The present paper discusses H2S removal by a new generation of sewage-sludge-derived materials which are characterized by their outstanding textural properties when compared to previous materials obtained by pyrolysis and/or activation of similar precursors. Alkaline hydroxide activation was used to prepare adsorbents/catalysts covering a wide range of porosities (SBET values from 10 to 1300 m2 g(-1)). Our results outline that textural properties are important for H2S abatement. However, not only highly porous sorbents, but also a high metallic content and a basic pH of these materials are required to achieve good performances. Proper combinations of textural properties and alkalinity render superior performances with retention values (x/M) as high as 456 mg of H2S removed per g of material. These retention capacities outperform previously published data for sewage-sludge derived materials and those achieved with commercial materials (including some activated carbons). Sulfur titration shows that most H2S is removed in the form of elemental sulfur, especially in the sewage/NaOH materials.

Dried sludges and sludge-based chars for H2S removal at low temperature: influence of sewage sludge characteristics.

The use of sewage sludge as a precursor of adsorbent/ catalyst materials for environmental applications has been encouraged during the past few years. Due to the heterogeneous nature of sludges, there exists a lack of information regarding the characteristics of these low-cost precursors and how their physicochemical properties affect the final performance of materials prepared from them. In this work, three sewage-sludges collected at WWTPs with assorted sludge/wastewater treatment schemes were used as precursors of adsorbents/catalysts for H2S removal at room temperature. All the solidswere characterized to establish their textural properties and chemical composition, including the speciation of the adsorbents/ catalysts inorganic fraction. Thermal treatment (gasification) of the raw (dried) sludges increased the H2S removal ability in all cases. For these thermally treated materials, catalytic conversion to elemental sulfur and sulfate moieties was found to be the main route of H2S removal. Results indicate that adsorbents based on an iron/calcium-containing sludge were the most reactive and exhibited the highest capacities for H2S retention. Forthis particulartype of sludge, a reasonably good performance was observed even when the dried (raw) sludge was used as adsorbent/ catalyst. Alternatively, the oxidation of H2S by chars obtained from the other two sludges under study was related to their textural properties.

Adsorption of n-alkanes on plasma-oxidized high-strength carbon fibers.

The objective of this work was to characterize the degree of heterogeneity brought about by oxygen plasma treatment of carbon fibers by studying its effects on the adsorption of n-alkanes. Untreated and unsized high-strength carbon fibers were subjected to oxygen plasma treatments with different degrees of severity. A sample of the same material oxidized following a standard industrial method was also studied for comparison. Adsorption of C5-C10n-alkanes at 303-353 K was measured by inverse gas chromatography (IGC). Elution peaks were symmetrical for the fresh and industrially oxidized samples; however, a large extent of asymmetry was observed for the plasma-treated fibers. Differences in surface heterogeneity were quantified in terms of several adsorption thermodynamic magnitudes. Differential heats of adsorption exhibited values similar to those corresponding to the probe-basal plane interaction. The dispersive component of the surface tension of the solids increased clearly upon plasma oxidation, the increase being systematic according to the severity of plasma treatment. It can be concluded that plasma oxidation generates high-surface-energy sites responsible for trapping of n-alkane molecules, this effect being more marked as the chain length increases. The possibility of this effect being associated to creation of micropores was ruled out on the basis of volumetric CO2 adsorption experiments and IGC measurements at finite dilution. Scanning tunneling microscopy observations allowed us to establish a possible connection between fiber surface nanostructure and IGC results. The sites accessible to n-alkane molecules in the industrially oxidized sample seem to be highly disordered, thus leading to a weaker interaction with the adsorbate.