Insights on the Synthesis of Al-MCM-41 with Optimized Si/Al Ratio for High-Performance Antibiotic Adsorption.

Studies indicate that approximately two-thirds of the rivers of the world are contaminated by pharmaceutical compounds, especially antibiotics and hormones. Data reported by the World Health Organization (WHO, 2015) revealed an increase of 65% in antibiotic consumption between 2000 and 2015, with a worldwide increase of 200% expected up to 2030. Environmental contamination by antibiotics and their metabolites can cause the alteration of bacterial genes, leading to the generation of superbacteria. In this work, adsorption was explored as a strategy to mitigate antibiotic contamination, proposing the use of the Al-MCM-41 mesoporous material as an efficient and high-capacity adsorbent. Evaluation of the influence of the synthesis parameters enabled understanding of the main variables affecting the adsorption capacity of Al-MCM-41 for the removal of a typical antibiotic, amoxicillin (AMX). It was found that the adsorbent composition and specific surface area were the main factors that should be optimized in order to obtain the highest AMX removal capacity. Using statistical tools, the best Si/Al ratio in Al-MCM-41 was found to be 10.5, providing an excellent AMX uptake of 132.2 mg per gram of adsorbent. The Si/Al ratio was the most significant factor affecting the adsorption. The cation-π interactions increased with an increase of the Al content, while the interactions involving silanols (Yoshida H-bonding and dipole-dipole hydrogen bridges) decreased.

Experimental and Theoretical Estimations of Atrazine's Adsorption in Mangosteen-Peel-Derived Nanoporous Carbons.

Nanoporous carbons were prepared via chemical and physical activation from mangosteen-peel-derived chars. The removal of atrazine was studied due to the bifunctionality of the N groups. Pseudo-first-order, pseudo-second-order, and intraparticle pore diffusion kinetic models were analyzed. Adsorption isotherms were also analyzed according to the Langmuir and Freundlich models. The obtained results were compared against two commercially activated carbons with comparable surface chemistry and porosimetry. The highest uptake was found for carbons with higher content of basic surface groups. The role of the oxygen-containing groups in the removal of atrazine was estimated experimentally using the surface density. The results were compared with the adsorption energy of atrazine theoretically estimated on pristine and functionalized graphene with different oxygen groups using periodic DFT methods. The energy of adsorption followed the same trend observed experimentally, namely the more basic the pH, the more favored the adsorption of atrazine. Micropores played an important role in the uptake of atrazine at low concentrations, but the presence of mesoporous was also required to inhibit the pore mass diffusion limitations. The present work contributes to the understanding of the interactions between triazine-based pollutants and the surface functional groups on nanoporous carbons in the liquid-solid interface.

Kinetic study of CO2 adsorption of granular-type activated carbons prepared from palm shells.

The adsorption kinetics of activated carbon (AC)-type adsorbent materials, which were prepared from a by-product of African palm (shells) processing by chemical activation with dehydrating metal salts at two different concentrations, was studied. N2 physisorption was performed in order to determine the textural characteristics of the adsorbent solids, obtaining materials with BET areas between 721 and 1334 m2g-1 and micropore volumes between 0.33 and 0.55 cm3g-1; FTIR determination was also used as a chemical characterization technique in order to observe variations in the functional groups present. CO2 adsorption was determined, obtaining values between 175 and 274 mg∙g-1; these results are correlated with the physicochemical characteristics of the materials. With the experimental data obtained in this adsorption, the kinetic study was carried out taking into account the kinetic models of pseudo-first-order, pseudo-second-order, and intraparticle diffusion, showing a better adjustment to this last model of a physisorption process. Finally, CO2 adsorption calorimetry was performed on the two adsorbents that presented the highest adsorption capacities, evidencing variations in the characteristics of the activated carbons with the change of the impregnant used. A correlation is observed between the speed of the CO2 adsorption process and the adsorption capacity.

Materiales carbonosos preparados a partir de cuesco de palma en la adsorción de CO2. Caracterización elemental, próxima y morfológica / Carbonaceous materials prepared from Palm shells for the adsorption of CO2. Elemental, proximal, and morphological characterization / Materiais carbonosos preparados a partir de Cuesco de Palma en a adsorção de CO2. Caracterização elementar, proximal e morfológica

Resumen En la presente investigación se prepararon sólidos porosos tipo carbón activado (CA) a partir de la activación química del cuesco de palma africana procedente de los cultivos de la región de la Guajira, Colombia, con soluciones de Fe(NO3)3 y Cu(NO3)2 con cambio en la concentración a dos diferentes temperaturas: 973 y 1073 K. Los sólidos adsorbentes preparados se caracterizaron para determinar sus propiedades fisicoquímicas y capacidades de adsorción de CO2. Los CA obtenidos presentan micro mesoporosidad con áreas superficiales entre 5 y 1300 m2g-1. Los valores con respecto al contenido de carbono fijo se encuentran entre 47,1 y 78,4%; los resultados evidencian que el proceso de activación tiene efectos sobre los parámetros texturales, composición elemental y proximal de los sólidos obtenidos. También se realizó la caracterización morfológica de la superficie de los materiales con SEM evidenciando la formación de mayor rugosidad en las muestras activadas a 1073 K, específicamente, los carbones activados con el nitrato cúprico; además, mediante EDX se cuantificó la presencia de algunos elementos. Los valores obtenidos de la adsorción de CO2 a bajas presiones se encuentran entre 80 y 250 mg•g-1, evidenciándose una mayor afinidad hacia los sólidos adsorbentes (MCu3 y MFe5).

Abstract In the present investigation, porous solids type activated carbon (CA) were prepared from the chemical activation of the African palm shells from the crops of the Guajira region, Colombia, with solutions of Fe(NO3)3 and Cu(NO3)2 with change in concentration at two different temperatures: 973 and 1073 K. The prepared adsorbent solids were characterized to determine their physicochemical properties and CO2 adsorption capacities. The CAs obtained present micro-mesoporosity with surface areas between 5 and 1300 m2g-1. The values with respect to the fixed carbon content are between 47.1% and 78.4%; the results show that the activation process has effects on the textural parameters, elemental and proximal composition of the solids obtained. The morphological characterization of the surface of the materials was also carried out with SEM, evidencing the formation of greater roughness in the samples activated at 1073 K, specifically, the activated carbons with cupric nitrate; furthermore, the presence of some elements was quantified by EDX. The values obtained from the adsorption of CO2 at low pressures are between 80 and 250 mg•g-1, showing a greater affinity towards adsorbent solids (MCu3 and MFe5).

Resumo Na presente investigação, sólidos porosos do tipo carvão ativado (CA) foram preparados a partir da ativação química do Cuesco de Palma Africana de lavouras da região de Guajira-Colômbia com soluções de Fe(NO3)3 e Cu(NO3)2 com alteração em concentração em duas temperaturas diferentes 973 e 1073 K. Os materiais preparados foram caracterizados para avaliar suas propriedades físico-químicas e capacidades de adsorção de CO2. Os (CAs) obtidos apresentam micro-mesoporosidade com áreas superficiais entre 5 e 1300 m g-1. Os valores com relação ao teor de carbono fixo estão entre 47,1 - 78,4%, os resultados mostram que o processo de ativação tem efeitos nos parâmetros texturais, composição elementar e proximal dos sólidos obtidos. A caracterização morfológica da superfície dos materiais também foi realizada com MEV, evidenciando a formação de maior rugosidade nas amostras ativadas a 1073 K, especificamente os carbonos ativados com nitrato cúprico, e a presença de alguns elementos foi quantificada por EDX. Os valores obtidos na adsorção de CO2 em baixas pressões estão entre 80-250 mg•g-1, mostrando uma maior afinidade para sólidos adsorventes (MCu3 e MFe5).

Physicochemical Parameters of the Methylparaben Adsorption from Aqueous Solution Onto Activated Carbon and Their Relationship with the Surface Chemistry.

The methylparaben adsorption from aqueous solution onto activated carbon is a relevant topic because of the toxicity of this compound for human and environmental health. The physicochemical parameters allow us to evaluate the performance of the adsorption and the relationship between the surface chemistry and the adsorbed amount of methylparaben. The effect of the solution chemistry on the adsorption was also evaluated. In this work, the methylparaben adsorption on three activated carbons with different physicochemical properties, specifically different contents of oxygenated groups and total basicity, is presented. Kinetic, equilibrium, and calorimetry tests were conducted. The maximum adsorbed amount of methylparaben was achieved on an activated carbon with basic characteristics, Q max = 1.64 mmol g-1; in the same activated carbon, the initial rate was 0.20 mmol g-1 h-1, and the value determined for the interaction enthalpy was -12.6 × 10-20 J molecules-1, and the Gibbs energy change was close to -14.96 kJ mol-1.

The Cramer's rule for the parametrization of phenol and its hydroxylated byproducts: UV spectroscopy vs. high performance liquid chromatography.

A linear algebra theorem like Cramer's rule was used for the analysis of a system of equations obtained from UV spectroscopy, and results were compared against those obtained from HPLC analysis. This parametrization allowed to quantify the concentration of the main intermediate products detected along the photodegradation of phenol under UV-Vis irradiation of TiO2. UV spectroscopy data for phenol, hydroquinone, and benzoquinone were analyzed using the Cramer's rule. The overlapping interference of the intermediate products in the UV spectra was corrected. It can be concluded that the Cramer's rule can be used for the parametrization of the UV absorbance data of phenol and its main intermediate products. This methodology permitted to obtain the concentration of phenol and their intermediate products by UV-visible with a high precision in comparison of HPLC. The parametrization showed a correlation coefficient of ca. 0.9775 between the phenol concentration obtained by UV spectroscopy and values obtained from HPLC analysis. In this sense, results can be considered with good precision, and accordingly, it can be concluded that the methodology is reliable, and UV-visible spectroscopy can be selected instead of HPLC in much of the experiments concerning with aqueous-phase reactions.

Sustainable production of nanoporous carbons: Kinetics and equilibrium studies in the removal of atrazine.

Nanoporous carbons have been prepared from mangosteen peels-derived chars by physical activation under CO2 flow as a function of temperature. As an example of circular bioeconomy, these sustainable adsorbents were used to remove atrazine, a common pesticide from the agroindustry. Several adsorption models such as Langmuir (two parameter), Sips and Redlich-Peterson (three parameters) were applied to verify the influence of carbon's properties on the uptake of atrazine. Additional kinetic models (pseudo-first order, pseudo-second order and Avrami's) allowed to establish that a mixture of physisorption and chemisorption describes the interaction between the nanoporous carbons and atrazine. As a general fact, an important diffusion of atrazine from the bulk of solution to the surface of carbons was observed. All samples were able to remove atrazine, but the highest uptake was found in the carbon with the highest contribution of micropores to the total pore of volume and with the lowest content of basic surface groups. Several correlations between the kinetic and equilibrium parameters for the atrazine adsorption were found as a function of the textural properties and surface chemistry. Based on the kinetics and equilibrium parameters, the present work proposes a mechanism for the atrazine adsorption on nanoporous carbons contributing to the understanding of the interactions between pollutant molecules and the surface functional groups on nanoporous carbons in the liquid-solid interface.

CO2adsorption on activated carbon honeycomb-monoliths: a comparison of Langmuir and Tóth Models.

Activated carbon honeycomb-monoliths with different textural properties were prepared by chemical activation of African palm shells with H(3)PO(4), ZnCl(2) and CaCl(2) aqueous solutions of various concentrations. The adsorbents obtained were characterized by N(2) adsorption at 77 K, and their carbon dioxide adsorption capacities were measured at 273 K and 1 Bar in volumetric adsorption equipment. The experimental adsorption isotherms were fitted to Langmuir and Tóth models, and a better fit was observed to Tóth equation with a correlation coefficient of 0.999. The maximum experimental values for adsorption capacity at the highest pressure (2.627-5.756 mmol·g(-1)) are between the calculated data in the two models.

Monolitos de cabbón activado a partir de cáscara de coco e impregnación con níquel ccobre / Monolths of actiivated carbon from coconut shell and impregnation with nickel and copper / Monolitos de arbbon ativado a partir de casca de coco e impregnacion com niquel e cobre

Una serie de diferentes monolitos de carbón activado fueron preparados a partir de cáscara de coco por medio de activación química con ácido fosfórico a diferentes concentraciones sin utilizar aglomerantes ni plastificantes. Al monolito que mayor área desarrolló se le impregnó vía húmeda con soluciones de Ni y Cu a diferentes relaciones molares. Las estructuras fueron caracterizadas por la adsorción de N2 a 77 K, y se exploró su morfología por medio de microscopía electrónica de barrido. Los materiales carbonosos obtenidos, níquel-cobre-monolito, fueron analizados por Reducción Térmica Programada (RTP). Los resultados experimentales indicaron que la activación con ácido fosfórico genera una microporosidad, con volúmenes de microporos entre 0,39 y 0,81 cm3g-1 y áreas superficiales entre 703 y 1450 m2g-1, y buenas propiedades mecánicas. Se muestra que tanto el cobre como el níquel se fijan al monolito y se interpretan los resultados de RTP respecto a cuándo se modifica su relación molar.

A series of different monoliths of activated carbon were prepared from coconutshell by means of chemical activation with phosphoric acid at different concentrations without using binders or plastificantes. The monolith that developed the biggest surface area was impregnated by humidic route with solutions of Ni and Cu at diferents molar relations. The structures were characterized by N2 adsorption at 77 K, and the morphology was explored by means of scanning electron microscopy. The carbonaceous materials obtained, Nikel-Copper-Monolithe, were analyzed by Thermal Programmed Reduction (TPR). The experimental results indicated that the activation with the acid generated a microporosity, with micropores volume between 0.40 and 0.81 cm3g-1 and surface areas between 703 and 1450 m2g-1, and a good mechanical properties. It shows that, both the copper and the nickel, are fixed to the monolith and TPR’s results are interpreted when these molar relation are modified.

Uma série de diferentes monolitos de carvão ativado foram preparados a partir de casca de coco por meio de activação química com ácido fosfórico a diferentes concentrações sem utilizar aglomerantes nem plastificantes. Ao monolito que maior área desenvolve se lhe impregno via úmida com soluções de Ni e Cu a deferentes relações molares. As estruturas foram caracterizadas pela adsorção de N2 a 77 K, e se exploro sua morfologia por meio de microscopía eletrônica de varredura. Os materiais carbonosos obtidos Níquel-Cobre-Monolito foram analisados por Redução Térmica Programada (RTP). Os resultados experimentais indicaram que a activação com ácido fosfórico gera uma microporosidad, com volumenes de microporos entre 0,39 e 0,81 cm3g-1 e áreas superficiais entre 703 e 1450 m2g-1, e umas boas propriedades mecânicas. Mostra-se que tanto o cobre como o níquel se fixam ao monolito e se interpretam os resultados de RTP com respeito a quando se modifica sua relação molar.

Stabilization/solidification of ashes in clays used in the manufacturing of ceramic bricks.

This paper presents the results of the lixiviation of metals from different mixtures of fly and bottom ashes that have been stabilized and solidified in clays used in the manufacture of bricks. The ashes used for this study were obtained from a Hoffmann-type brick furnace adapted for the incineration of municipal solid waste during the manufacturing of ceramic bricks. The ashes were stabilized in clay in different proportions of clay:ash mix (99:1, 95:5, 90:10, 80:20 and 60:40). Such mixes were used to manufacture bricks that were calcined at a temperature ranging from 50 to 1100 degrees C. The clay, ashes and manufactured bricks were characterized using X-ray diffraction, fluorescent X-ray, thermogravimetry, differential thermal analysis, atomic absorption spectroscopy and scanning electronic microscopy. In addition, toxicity characteristic leaching procedure lixiviation tests were performed according to the EPA 1311 method for the determination of heavy metals. The results showed an affinity between clay and ash, and also that the bricks manufactured with these mixtures present low lixiviation levels. The tests also showed the highest decrease in the concentration of arsenic, nickel, chromium, zinc and silver for 99:1 mixtures. The 95:5 mixture was found to be the most favourable for the stabilization (greater concentration decrease) of lead and cadmium. Selenium was the metal with the lowest concentration change whereas arsenic, nickel, chromium, zinc and cadmium showed the greatest concentration change in all mixtures, with the exception of cadmium in the mixture 99:1.