Physicochemical characteristics of calcined MnFe2O4 solid nanospheres and their catalytic activity to oxidize para-nitrophenol with peroxymonosulfate and n-C7 asphaltenes with air.

Manganese ferrite solid nanospheres (MSNs) were prepared by a solvothermal method and calcined at various temperatures up to 500 °C. Their surface area, morphology, particle size, weight change during calcination, surface coordination number of metal ions, oxidation state, crystal structure, crystallite size, and magnetic properties were studied. The MSNs were used as catalysts to activate potassium peroxymonosulfate (PMS) for the oxidative degradation of para-nitrophenol (PNP) from water and for the oxidation of n-C7 asphaltenes in flowing air at atmospheric (0.084 MPa) and high pressure (6 MPa). Mn was in oxidation states (II) and (III) at calcination temperature of 200 °C, and the crystalline structure corresponded to jacobsite. Mn was in oxidation states (III) and (IV) at 350 °C and in oxidation states (II), (III), and (IV) at 500 °C, and the crystalline structure was maghemite at both temperatures. MSN catalysts generated hydroxyl (HO·) and sulfate (SO4·-) radicals in the PMS activation and generated HO· radicals in the n-C7 asphaltene oxidation. In both reactions, the best catalyst was MSN calcined at 350 °C (MSN350), because it has the highest concentration of Mn(III) in octahedral B sites, which are directly exposed to the catalyst surface, and the largest total and lattice oxygen contents, favoring oxygen mobility for Mn redox cycles. The MSN350 sample reduces the decomposition temperature of n-C7 asphaltenes from 430 to 210 °C at 0.084 MPa and from 370 to 200 °C at 6.0 MPa. In addition, it reduces the effective activation energy by approximately 77.6% in the second combustion (SC) region, where high-temperature oxidation reactions take place.

Removal of Phenolic Compounds from Water Using Copper Ferrite Nanosphere Composites as Fenton Catalysts.

Copper ferrites containing Cu+ ions can be highly active heterogeneous Fenton catalysts due to synergic effects between Fe and Cu ions. Therefore, a method of copper ferrite nanosphere (CFNS) synthesis was selected that also permits the formation of cuprite, obtaining a CFNS composite that was subsequently calcined up to 400 °C. Composites were tested as Fenton catalysts in the mineralization of phenol (PHE), p-nitrophenol (PNP) and p-aminophenol (PAP). Catalysts were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and magnetic measurements. Degradation of all phenols was practically complete at 95% total organic carbon (TOC) removal. Catalytic activity increased in the order PHE < PNP < PAP and decreased when the calcination temperature was raised; this order depended on the electronic effects of the substituents of phenols. The as-prepared CFNS showed the highest catalytic activity due to the presence of cubic copper ferrite and cuprite. The Cu+ surface concentration decreased after calcination at 200 °C, diminishing the catalytic activity. Cuprite alone showed a lower activity than the CFNS composite and the homogeneous Fenton reaction had almost no influence on its overall activity. CFNS activity decreased with its reutilization due to the disappearance of the cuprite phase. Degradation pathways are proposed for the phenols.

Removal of bisphenols A and S by adsorption on activated carbon clothes enhanced by the presence of bacteria.

This study investigated the adsorption of two endocrine-disrupting chemicals, bisphenol A (BPA) and S (BPS), from water using activated carbon clothes (ACCs), as-received and oxidized, in the absence and presence of bacteria, analyzing both kinetic and equilibrium adsorption data. Kinetic study of the different systems showed that the adsorption rate was affected both by the oxidation of the adsorbent and by the presence of bacteria. Bisphenol adsorption kinetics followed a second-order kinetic model, with rate constants between 0.0228 and 0.0013 g min-1 mol-1. ACC was a much better adsorbent of E. coli compared to granular activated carbons, achieving 100% adsorption at 24 h. ACC oxidation reduced the adsorption capacity and the adsorbent-adsorbate relative affinity due to the decrease in carbon surface hydrophobicity. Conversely, the presence of bacteria in aqueous solution increased the ACC surface hydrophobicity and therefore enhanced the adsorption capacity of BPA and BPS on ACC, which was 33% and 24%, respectively. In all cases, more BPS than BPA was removed due to the greater dipolar moment of the former. Results found show that activated carbon clothes in the presence of bacteria can be an adequate process to remove bisphenol A and S from different aqueous systems.

Effect of calcination temperature of a copper ferrite synthesized by a sol-gel method on its structural characteristics and performance as Fenton catalyst to remove gallic acid from water.

A copper ferrite synthesized by a sol-gel combustion method was calcined at different temperatures up to 800°C, determining changes in its structural characteristics and magnetic measurements and studying its catalytic performance in gallic acid removal by Fenton reaction. The main objective was to study the effect of the calcination temperature of copper ferrite on its crystalline phase formation and transformation, activity and metal ion leaching. The cubic-to-tetragonal transformation of the spinel occurred via its reaction with the CuO phase, displacing Fe3+ ions in B (octahedral) sites out of the spinel structure by the following reaction: 2Fe3+B+3CuO→Fe2O3+3Cu2+B. The catalysts showed superparamagnetic or substantial superparamagnetic behaviour. At higher calcination temperatures, catalyst activity was lower, and Cu ion leaching was markedly decreased. There was no Fe ion leaching with any catalyst. The as-prepared catalyst showed better catalytic performance than a commercial copper ferrite. Leached Cu ions acted as homogeneous catalysts, and their contribution to the overall removal mechanism was examined. Cu2O present in the as-prepared catalysts made only a small contribution to their activity. Finally, the reutilization of various catalysts was studied by performing different catalytic cycles.

Symmetric Supercapacitor Electrodes from KOH Activation of Pristine, Carbonized, and Hydrothermally Treated Melia azedarach Stones.

Waste biomass-derived activated carbons (ACs) are promising materials for supercapacitor electrodes due to their abundance and low cost. In this study, we investigated the potential use of Melia azedarach (MA) stones to prepare ACs for supercapacitors. The ash content was considerably lower in MA stones (0.7% ash) than that found in other lignocellulosic wastes. ACs were prepared by KOH activation of pristine, carbonized, and hydrothermally-treated MA stones. The morphology, composition, surface area, porosity, and surface chemistry of the ACs were determined. Electrochemical measurements were carried out in three- and two-electrode cells, 3EC and 2EC, respectively, using 1 M H2SO4 as the electrolyte. The highest capacitance from galvanostatic charge-discharge (GCD) in 2EC ranged between 232 and 240 F·g-1 at 1 A·g-1. The maximum energy density reached was 27.4 Wh·kg-1 at a power density of 110 W·kg-1. Electrochemical impedance spectroscopy (EIS) revealed an increase in equivalent series resistance (ESR) and charge transfer resistance (RCT) with greater ash content. Electrochemical performance of MA stone-derived ACs was compared with that of other ACs described in the recent literature that were prepared from different biomass wastes and results showed that they are among the best ACs for supercapacitor applications.

Colloidal and micro-carbon spheres derived from low-temperature polymerization reactions.

Carbon spheres (CSs) have recently attracted major interest due to their new applications, mainly in energy storage and conversion but also in hard-templating, sorption/catalysis processes, and drug delivery systems. This is attributable to their physico-chemical properties, including their tunable morphology (solid, hollow and core-shell), size, surface area/porosity, good electrical conductivity, low external surface-to-volume ratio, high packing density, enhanced mass transport, robust mechanical stability, low cytotoxicity, and excellent biocompatibility. They can be obtained from a wide variety of carbon precursors and methods. This review covers their production by carbonization of polymer spheres from low-temperature polymerization reactions, considered here as below 250°C. This is a very important method because it allows the synthesis of CSs with different morphologies and doped with other elements or chemical compounds. The preparation of polymer spheres by this technique is well documented in the literature, and the objective of this review is to summarize and give an overview of the most significant publications, proposing a novel classification based on the formation mechanism of the polymer spheres. This classification includes the following polymerization processes: emulsion polymerization and its derivatives, seeded emulsion and inverse emulsion polymerization; precipitation polymerization and its derivative, dispersion polymerization; hard-templating; spray-drying; and hydrothermal or solvothermal treatment of carbohydrates and biomass in general. This review also reports on the morphology and surface characteristics of the CSs obtained by different synthetic approaches. The final section of the review describes the current applications of these CSs, notably in energy storage (supercapacitors and rechargeable batteries) and energy conversion (fuel cells and dye-sensitized solar cells). Besides the numerous applications listed above, they are utilized as sacrificial hard templates to prepare single- and multi-shell hollow spheres of metal oxides and other inorganic compounds and filters, as well as in adsorption and catalysis processes, drug delivery systems, and other minority applications (e.g., lubricants, black pigment in e-papers, and microwave absorber).

Fenton oxidation of gallic and p-coumaric acids in water assisted by an activated carbon cloth.

The objective of this study was to investigate the effect of the presence of an activated carbon cloth (ACC) during the degradation and removal of gallic acid (GA) and p-coumaric acid (pCA) by Fenton oxidation using H2O2 and FeSO4 as catalyst. Removal of GA or pCA by Fenton oxidation was much higher than that of total organic carbon (TOC), indicating that a large proportion of GA or pCA degradation products was not mineralized. The presence of ACC increased the concentration of hydroxyl radicals generated in the FeSO4 + H2O2 system. The presence of ACC during Fenton oxidation largely increased TOC and GA removal, attributable to the adsorption of GA and its degradation products and the increased generation of OH(•) radicals that mineralize them. In the Fenton oxidation of pCA, the presence of ACC produced the same effects as for GA, but now the increased removal of pCA was due to adsorption on the activated carbon and not to the increased generation of hydroxyl radicals, due to the greater affinity of pCA for the carbon surface and its more difficult mineralization in comparison to GA.

Influence of the boron precursor and drying method on surface properties and electrochemical behavior of boron-doped carbon gels.

Two series of B-doped carbon gels were prepared by the polymerization of resorcinol and formaldehyde in water using either boric acid or phenyl boronic acid as dopants. Both organic hydrogels were dried by four methods: supercritical, freeze, microwave oven, and vacuum oven drying. The effects of the boron precursor and drying method on the surface characteristics were studied by N2 and CO2 adsorption at -196 and 0 °C, respectively, immersion calorimetry into benzene and water, temperature-programmed desorption coupled with mass spectrometry, X-ray photoelectron spectroscopy, and thermogravimetric analysis. Electrochemical characterization was carried out in a three-electrode cell, using Ag/AgCl as a reference electrode and a Pt wire as a counter electrode. The surface area obtained from immersion calorimetry into benzene was more realistic than that yielded by the Brunauer-Emmett-Teller (BET) equation. The hydrophobicity of the samples decreased linearly with a higher oxygen content. In addition, the oxygen content of the B-doped carbon gels increased linearly with a higher B content, and the interfacial or areal capacitance decreased linearly with a larger surface area. The capacitance was increased by B addition because of the pseudocapacitance effects of the higher oxygen content of the samples. The cryogel and vacuum-dried xerogel obtained from the boric acid series, Bc and Bv, respectively, showed the largest gravimetric and volumetric capacitances, around 140 F/g and 95 F/cm(3), respectively.

Carbon xerogel microspheres and monoliths from resorcinol-formaldehyde mixtures with varying dilution ratios: preparation, surface characteristics, and electrochemical double-layer capacitances.

Carbon xerogels in the form of microspheres and monoliths were obtained from the sol-gel polymerization of resorcinol and formaldehyde in the presence of potassium carbonate as catalyst, using water as solvent and two different molar dilution ratios. The objectives of this study were as follows: to investigate the effect of the dilution ratio, polymerization reaction time, and temperature on the rheological properties of the sols used to prepare the carbon xerogel microspheres and monoliths; and to determine the influence of their preparation methods and shapes on their surface characteristics and electrochemical double-layer (EDL) capacitance. An increase in the molar dilution ratio produced a decrease in the apparent activation energy of the sol-gel transition. Carbon xerogel microspheres were steam-activated at different burnoff percentages. The morphology, surface area, porosity, and surface chemistry of samples were determined. The main difference between the carbon xerogel microspheres and monoliths was that the latter are largely mesoporous. Better electrochemical behavior was shown by carbon xerogels in monolith than in microsphere form, but higher gravimetric and volumetric capacitances were found in activated carbon xerogel microspheres than in carbon xerogel monoliths.

Growth and spontaneous differentiation of umbilical-cord stromal stem cells on activated carbon cloth.

We have investigated the capacity of activated carbon cloth to support the growth and differentiation of human mesenchymal umbilical-cord stromal stem cells. Our results demonstrate that this scaffold provides suitable conditions for the development of cell-derived matrix proteins and facilitates the growth of undifferentiated stem cells with the ability to induce osteogenic and chondrogenic differentiation. Immunoflourescence staining revealed extensive expression of collagen in all the samples, and collagen type II and osteopontin within the samples cultivated in specific differentiation-inducing media. Cell growth and the formation of natural collagen, calcium-magnesium carbonate and hydroxyapatite crystals, together with the self-assemblage of collagen to produce suprafibrillar arrangements of fibrils all occur simultaneously and can be studied together ex vivo under physiological conditions. Furthermore, the spontaneous differentiation of stem cells cultured on activated carbon cloth with no osteogenic supplements opens up new possibilities for bone-tumour engineering and treatment of traumatic and degenerative bone diseases.

Activated carbons from KOH-activation of argan (Argania spinosa) seed shells as supercapacitor electrodes.

Activated carbons were prepared by KOH-activation of argan seed shells (ASS). The activated carbon with the largest surface area and most developed porosity was superficially treated to introduce oxygen and nitrogen functionalities. Activated carbons with a surface area of around 2100 m(2)/g were obtained. Electrochemical measurements were carried out with a three-electrode cell using 1M H(2)SO(4) as electrolyte and Ag/AgCl as reference electrode. The O-rich activated carbon showed the lowest capacitance (259 F/g at 125 mA/g) and the lowest capacity retention (52% at 1A/g), due to surface carboxyl groups hindering electrolyte diffusion into the pores. Conversely, the N-rich activated carbon showed the highest capacitance (355 F/g at 125 mA/g) with the highest retention (93% at 1A/g), due to its well-developed micro-mesoporosity and the pseudocapacitance effects of N functionalities. This capacitance performance was among the highest reported for other activated carbons from a large variety of biomass precursors.

Surface chemistry, porous texture, and morphology of N-doped carbon xerogels.

N-doped carbon xerogels were obtained from organic xerogels prepared using different N-containing organic compounds, including 3-hydroxy aniline, melamine, and 3-hydroxy pyridine. Carbonization was carried out between 500 and 900 degreeC. The surface chemistry of samples was determined by elemental analysis and X-ray photoelectron spectroscopy, their porous texture was determined by N2 and CO2 adsorption at (-)196 and 0degreeC, respectively, and their morphology was determined by scanning electron microscopy. N-doped carbon xerogels with a wide variety of N contents and functionalities were obtained according to the ingredients and carbonization temperature used. Carbon xerogels contained, in different proportions, three/four N functionalities: pyridinic, pyrrolic and/or pyridonic, and quaternary N functionalities. They were microporous carbons with narrow micropores that had constrictions at their entrances, producing higher CO2(-) than N2-determined micropore surface areas. Morphology studies showed samples to be constituted by isolated microspheres or microsphere clusters. Microsphere diameters depended on the recipe and carbonization temperature used.

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.

Temperature dependence of herbicide adsorption from aqueous solutions on activated carbon fiber and cloth.

Diuron and amitrole adsorption from aqueous solution on an activated carbon fiber and an activated carbon cloth were studied as a function of temperature. Diuron adsorption was greater than that of amitrole and increased with rising temperature, whereas amitrole adsorption decreased when the temperature increased. Endothermicity of diuron adsorption was due to an increase in the planarity and diffusion of diuron molecules with higher temperatures. However, the exothermicity found for amitrole was due to the increase in amitrole solubility and in vibrational energy of adsorbed molecules with higher temperature. External mass transfer resistance was also found to play an important role in diuron adsorption on activated carbon cloth.

Surface area and microporosity of carbon aerogels from gas adsorption and small- and wide-angle X-ray scattering measurements.

A carbon aerogel was obtained by carbonization of an organic aerogel prepared by sol-gel polymerization of resorcinol and formaldehyde in water. The carbon aerogel was then CO(2) activated at 800 degrees C to increase its surface area and widen its microporosity. Evolution of these parameters was followed by gas adsorption and small- and wide-angle X-ray scattering (SAXS and WAXS, respectively) with contrast variation by using dry and wet (immersion in benzene and m-xylene) samples. For the original carbon aerogel, the surface area, S(SAXS), obtained by SAXS, is larger than that obtained by gas adsorption (S(ads)). The values become nearly the same as the degree of activation of the carbon aerogel increases. This feature is due to the widening of the narrow microporosity in the carbon aerogel as the degree of activation is increased. In addition, WAXS results show that the short-range spatial correlations into the assemblies of hydrocarbon molecules confined inside the micropores are different from those existing in the liquid phase.

A study of the static and dynamic adsorption of Zn(II) ions on carbon materials from aqueous solutions.

The effect of surface oxidation, solution pH, and ionic strength on the adsorption of Zn(II) ions from aqueous solution under static conditions was studied using commercial activated carbons in the form of grains and cloth. In addition, the effects of surface oxidation and the presence of dissolved natural organic matter (tannic acid) were studied under dynamic conditions using activated carbon cloth column beds. Under static conditions, surface oxidation largely increased Zn2+ uptake and two H+ ions were displaced from the oxidized carbon surface per Zn(II) ion adsorbed. It is proposed that adsorption of Zn(II) on the as-received basic carbons was due to C(pi)-cation interactions. An increase in solution pH in the range 3-6 increased Zn(II) uptake, whereas an increase in ionic strength decreased Zn(II) uptake because of the screening effect of the added salt. In the experiments carried out with carbon column beds, the oxidized activated carbon cloth was also more effective than the as-received carbon to remove Zn(II) ions. In this case, the presence of tannic acid decreased the efficiency of the oxidized activated carbon cloth bed to remove Zn(II) ions. An increase in the tannic acid initial concentration had a greater effect on the removal of tannic acid than on the removal of Zn(II) by the column bed. This may be a consequence of the greater size of tannic acid molecules and their low affinity for oxidized carbon surfaces.

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.