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In this work, a novel sustainable approach was proposed for the integral valorisation of Arctium lappa (burdock) seeds and roots. Firstly, a preliminary recovery of bioactive compounds, including unsaturated fatty acids, was performed. Then, simple sugars (i.e., fructose and sucrose) and phenolic compounds were extracted by using compressed fluids (supercritical CO2 and propane). Consequently, a complete characterisation of raw biomass and extraction residues was carried out to determine the starting chemical composition in terms of residual lipids, proteins, hemicellulose, cellulose, lignin, and ash content. Subsequently, three alternative ways to utilise extraction residues were proposed and successfully tested: (i) enzymatic hydrolysis operated by Cellulases (Thricoderma resei) of raw and residual biomass to glucose, (ii) direct ethanolysis to produce ethyl levulinate; and (iii) pyrolysis to obtain biochar to be used as supports for the synthesis of sulfonated magnetic iron-carbon catalysts (Fe-SMCC) to be applied in the dehydration of fructose for the synthesis of 5-hydroxymethylfurfural (5-HMF). The development of these advanced approaches enabled the full utilisation of this resource through the production of fine chemicals and value-added compounds in line with the principles of the circular economy.
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Arctium , Arctium/química , Lignina/química , Extratos Vegetais/química , Celulose , FrutoseRESUMO
The mother earth is a source of natural resources that, in conjunction with anthropogenic activities, generates a wide spectrum of different biowastes. These biomaterials can be used as low-cost raw feedstock to produce bioenergy, value-added products, and other commodities. However, the improper management and disposal of these biowastes can generate relevant environmental impacts. Consequently, it is imperative to explore alternative technologies for the valorization and exploitation of these wastes to obtain benefits for the society. This review covers different aspects related to valorization of biowastes and their applications in water pollution, soil fertility and green energy generation. The classification and characteristics of different biowastes (biosolids, animal wastes and effluents, plant biomass, wood and green wastes) including their main generation sources are discussed. Different technologies (e.g., pyrolysis, hydrothermal carbonization, anaerobic digestion, gasification, biodrying) for the transformation and valorization of these residues are also analyzed. The application of biowastes in soil fertility, environmental pollution and energy production are described and illustrative examples are provided. Finally, the challenges related to implement low-cost and sustainable biowaste management strategies are highlighted. It was concluded that reliable simulation studies are required to optimize all the logistic stages of management chain of these residues considering the constraints generated from the economic, environmental and social aspects of the biowaste generation sources and their locations. The recollection and sorting of biowastes are key parameters to minimize the costs associated to their management and valorization. Also, the concepts of Industry 4.0 can contribute to achieve a successful commercial production of the value-added products obtained from the biowaste valorization. Overall, this review provides a general outlook of biowaste management and its valorization in the current context of circular economy.
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Solo , Tecnologia , Animais , Solo/químicaRESUMO
A seasonal study of the lipid composition of a primary sludge (dry and dewatered base) obtained from an urban wastewater treatment plant located in Aguascalientes (Mexico) is reported. This study assessed the variability in sludge composition to establish its potential as a raw material for biodiesel production. Lipid recovery was achieved by extraction using two solvents. Hexane was employed for lipid extraction from dry sludge, whereas hexane and ethyl butyrate were used for comparison with dewatered sludge. The formation (%) of fatty acid methyl esters (biodiesel) was determined using extracted lipids. The extraction results from the dry sludge showed 14 and 6% of recovered lipids and their conversion to biodiesel, respectively. For the dewatered sludge, the lipid recovery and biodiesel formation were 17.4 and 60% using hexane, and 23 and 77% for ethyl butyrate, respectively, on a dry basis. Statistical data indicated that lipid recovery depended on the physicochemical characteristics of sewage sludge, which were related to seasonal changes, population activities, and changes in plant configuration, among other factors. These variables must be considered in the design of large-scale extraction equipment for the application and commercial exploitation of biomass waste in biofuel production.
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Esgotos , Águas Residuárias , Esgotos/química , Hexanos , Biocombustíveis/análise , Estações do Ano , Lipídeos/química , Ácidos Graxos/químicaRESUMO
Recently, the potential dangers of viral infection transmission through water and air have become the focus of worldwide attention, via the spread of COVID-19 pandemic. The occurrence of large-scale outbreaks of dangerous infections caused by unknown pathogens and the isolation of new pandemic strains require the development of improved methods of viruses' inactivation. Viruses are not stable self-sustaining living organisms and are rapidly inactivated on isolated surfaces. However, water resources and air can participate in the pathogens' diffusion, stabilization, and transmission. Viruses inactivation and elimination by adsorption are relevant since they can represent an effective and low-cost method to treat fluids, and hence limit the spread of pathogen agents. This review analyzed the interaction between viruses and carbon-based, oxide-based, porous materials and biological materials (e.g., sulfated polysaccharides and cyclodextrins). It will be shown that these adsorbents can play a relevant role in the viruses removal where water and air purification mostly occurring via electrostatic interactions. However, a clear systematic vision of the correlation between the surface potential and the adsorption capacity of the different filters is still lacking and should be provided to achieve a better comprehension of the global phenomenon. The rationalization of the adsorption capacity may be achieved through a proper physico-chemical characterization of new adsorbents, including molecular modeling and simulations, also considering the adsorption of virus-like particles on their surface. As a most timely perspective, the results on this review present potential solutions to investigate coronaviruses and specifically SARS-CoV-2, responsible of the COVID-19 pandemic, whose spread can be limited by the efficient disinfection and purification of closed-spaces air and urban waters.
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Due to increasing anthropogenic activities, especially industry and transport, the fossil fuel demand and consumption have increased proportionally, causing serious environmental issues. This attracted researchers and scientists to develop new alternative energy sources. Therefore, this review covers the biofuel production potential and challenges related to various feedstocks and advances in process technologies. It has been concluded that the biofuels such as biodiesel, ethanol, bio-oil, syngas, Fischer-Tropsch H2, and methane produced from crop plant residues, micro- and macroalgae and other biomass wastes using thermo-bio-chemical processes are an eco-friendly route for an energy source. Biofuels production and their uses in industries and transportation considerably minimize fossil fuel dependence. Literature analysis showed that biofuels generated from energy crops and microalgae could be the most efficient and attractive process. Recent progress in the field of biofuels using genetic engineering has larger perspectives in commercial-scale production. However, its large-scale production is still challenging; hence, to resolve this problem, it is essential to convert biomass in biofuels by developing novel technology to increase biofuel production to fulfil the current and future energy demand.
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Biocombustíveis , Microalgas , Biomassa , Fontes Geradoras de Energia , Combustíveis FósseisRESUMO
The fast growth in the anthropogenic activities, that involve a wide use of pharmaceuticals, has led to the appearance of new toxic and hazardous chemical compounds, called "emerging pollutants", which could cause unpredictable consequences to the ecosystems. The current review is focused on emerging pollutants occurring in food or air and include caffeine and nicotine, as well as on pharmaceuticals, in particular amoxicillin, and the concerns caused by its wide usage for medical purposes. This review, for the first time, analyzes and discusses the potential risks and implications of caffeine, nicotine and amoxicillin as emerging environmental pollutants, a field that remains underrepresented to date. Both caffeine and nicotine belong to life style compounds, while pharmaceutical amoxicillin is one of the very popular ß-lactam antibiotics used to take care of human and animal infections. The review covers the toxic effect caused by caffeine, nicotine and amoxicillin on humans and animals and describes some of the main adsorbents utilized for their removal (e.g., grape stalk, tea waste, wheat grains, bentonite, activated carbon, acid and base modified grape slurry wastes, graphene oxides, modified graphene oxides, zeolites, etc.). The isotherm and kinetic models for the analysis of caffeine, nicotine and amoxicillin adsorption by different adsorbents are presented. The impact of pH, temperature, adsorbent dosage and thermodynamic studies were deeply analyzed. The review also discusses the mechanism of adsorption for the above-mentioned emerging pollutants, which includes π-π interaction, cation-π bonding, electron-donor and electron-acceptor forces, van der Waals forces, electrostatic interactions, etc. The present review has a potential value for chemists, ecologists, toxicologists, environmental engineers, and other professionals that are involved in environmental protection.
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Águas Residuárias , Poluentes Químicos da Água , Adsorção , Amoxicilina , Cafeína , Ecossistema , Cinética , NicotinaRESUMO
The search for reliable and efficient global optimization algorithms for solving phase stability and phase equilibrium problems in applied thermodynamics is an ongoing area of research. In this study, we evaluated and compared the reliability and efficiency of eight selected nature-inspired metaheuristic algorithms for solving difficult phase stability and phase equilibrium problems. These algorithms are the cuckoo search (CS), intelligent firefly (IFA), bat (BA), artificial bee colony (ABC), MAKHA, a hybrid between monkey algorithm and krill herd algorithm, covariance matrix adaptation evolution strategy (CMAES), magnetic charged system search (MCSS), and bare bones particle swarm optimization (BBPSO). The results clearly showed that CS is the most reliable of all methods as it successfully solved all thermodynamic problems tested in this study. CS proved to be a promising nature-inspired optimization method to perform applied thermodynamic calculations for process design.
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Algoritmos , Modelos TeóricosRESUMO
The removal of caffeine (CFN) and acetaminophen (ACT) from water using low-cost activated carbons prepared from artichoke leaves (AAC) and pomegranate peels (PAC) was reported in this paper. These activated carbons were characterized using various analytical techniques. The results showed that AAC and PAC had surface areas of 1203 and 1095 m2 g-1, respectively. The prepared adsorbents were tested for the adsorption of these pharmaceuticals in single and binary solutions. These experiments were performed under different operating conditions to evaluate the adsorption properties of these adsorbents to remove CFN and ACT. AAC and PAC showed maximum adsorption capacities of 290.86 and 258.98 mg g-1 for CFN removal, 281.18 and 154.99 mg g-1 for the ACT removal over a wide pH range. The experimental equilibrium adsorption data fitted to the Langmuir model and the kinetic data were correlated with the pseudo-second order model. AAC showed the best adsorption capacities for the removal of these pharmaceuticals in single systems and, consequently, it was tested for the simultaneous removal of these pollutants in binary solutions. The simultaneous adsorption of these compounds on AAC was improved using the central composite design and response surface methodology. The results indicated an antagonistic effect of CFN on the ACT adsorption. AAC regeneration was also analyzed and discussed. A statistical physics model was applied to describe the adsorption orientation of the tested pollutants on both activated carbon samples. It was concluded that AAC is a promising adsorbent for the removal of emerging pollutants due to its low cost and reusability properties.
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Poluentes Ambientais , Poluentes Químicos da Água , Carvão Vegetal/química , Cafeína , Acetaminofen , Água , Biomassa , Poluentes Químicos da Água/análise , Adsorção , Cinética , Preparações Farmacêuticas , Concentração de Íons de HidrogênioRESUMO
Glycerol carbonate (GC) is one of the most attractive green chemicals involved in several applications such as polymer synthesis, e. g., the production of polyurethanes and polycarbonates. This relevant chemical can be produced, in a green way, using CO2 (from carbon capture) and glycerol (a byproduct from biodiesel manufacturing). Therefore, in this work, a comprehensive analysis of the GC production process is conducted based on the following synthesis route: urea-dimethyl carbonate-GC using carbon dioxide and glycerol as the main raw materials where the synthesis pathway was efficiently integrated using Aspen Plus. A techno-economic analysis was performed in order to estimate the required capital investment and operating cost for the whole GC process, providing insights on individual capital cost requirements for the urea, dimethyl carbonate, and GC production sections. A total capital cost of $192.1â MM, and a total operating cost of $225.7â MM/y were estimated for the process. The total annualized cost was estimated as $1,558â USD/t of GC produced, competitive with current market price.
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The double layer adsorption of sulfamethoxazole, ketoprofen and carbamazepine on a phosphorus carbon-based adsorbent was analyzed using statistical physics models. The objective of this research was to provide a physicochemical analysis of the adsorption mechanism of these organic compounds via the calculation of both steric and energetic parameters. Results showed that the adsorption mechanism of these pharmaceuticals was multimolecular where the presence of molecular aggregates (mainly dimers) could be expected in the aqueous solution. This adsorbent showed adsorption capacities at saturation from 15 to 36 mg/g for tested pharmaceutical molecules. The ketoprofen adsorption was exothermic, while the adsorption of sulfamethoxazole and carbamazepine was endothermic. The adsorption mechanism of these molecules involved physical interaction forces with interaction energies from 5.95 to 19.66 kJ/mol. These results contribute with insights on the adsorption mechanisms of pharmaceutical pollutants. The identification of molecular aggregates, the calculation of maximum adsorption capacities and the characterization of thermodynamic behavior provide crucial information for the understanding of these adsorption systems and to optimize their removal operating conditions. These findings have direct implications for wastewater treatment and environmental remediation associated with pharmaceutical pollution where advanced adsorption technologies are required.
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Antibiotics are considered as the new generation water pollutants as these disturb endocrine systems if water contaminated with antibiotics is consumed. Among many antibiotics norfloxacin is present in various natural water bodies globally. This antibiotic is considered an emerging pollutant due to its low degradation in aquatic animals. Besides, it has many side effects on human vital organs. Therefore, the present article discusses the recent advances in the removal of norfloxacin by adsorption. This article describes the presence of norfloxacin in natural water, consumption, toxicity, various adsorbents for norfloxacin removal, optimization factors for norfloxacin removal, kinetics, thermodynamics, modeling, adsorption mechanism and regeneration of the adsorbents. Adsorption takes place in a monolayer following the Langmuir model. The Pseudo-second order model represents the kinetic data. The adsorption capacity ranged from 0.924 to 1282 mg g-1. In this sense, the parameters such as the NFX concentration added to the adsorbent textural properties exerted a great influence. Besides, the fixed bed-based removal at a large scale is also included. In addition to this, the simulation studies were also discussed to describe the adsorption mechanism. Finally, the research challenges and future perspectives have also been highlighted. This article will be highly useful for academicians, researchers, industry persons, and government authorities for designing future advanced experiments.
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Recuperação e Remediação Ambiental , Poluentes Químicos da Água , Animais , Humanos , Norfloxacino/análise , Água , Adsorção , Antibacterianos , Cinética , Concentração de Íons de HidrogênioRESUMO
This study presents a theoretical analysis of the adsorption process of pharmaceutical pollutants, specifically acetaminophen (ATP) and diclofenac (DFC), onto activated carbon (AC) derived from avocado biomass waste. The adsorption isotherms of ATP and DFC were analyzed using a multilayer model, which revealed the formation of two to four adsorption layers depending on the temperature of the aqueous solution. The saturation adsorption capacities for ATP and DFC were 52.71 and 116.53 mg/g, respectively. A steric analysis suggested that the adsorption mechanisms of ATP and DFC involved a multi-molecular process. The calculated adsorption energies (ΔE1 and ΔE2) varied between 12.86 and 22.58 kJ/mol, with the highest values observed for DFC removal. Therefore, the adsorption of these organic molecules was associated with physisorption interactions: van der Waals forces and hydrogen bonds. These findings enhance the understanding of the depollution processes of pharmaceutical compounds using carbon-based adsorbents and highlight the potential of utilizing waste biomass for environmental remediation.
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Carvão Vegetal , Poluentes Químicos da Água , Adsorção , Carvão Vegetal/química , Poluentes Químicos da Água/química , Diclofenaco/química , Preparações Farmacêuticas/química , Carbono/química , Acetaminofen/químicaRESUMO
Herein, a mixture of eggshell (ES) and magnetite nanoparticles (MNPs) was alkali-activated using NaOH/Na2SiO3 solution and then, impregnated with sodium alginate (SA) to prepare a magnetic bio-based adsorbent (namely SAAES/SA/MNPs) for the decontamination of water containing basic dyes, in particular, methylene blue (MB) and crystal violet (CV). The physicochemical properties of magnetic spheres of SAAES/SA/MNPs were characterized using XRD, FTIR, FESEM, EDX, elemental mapping, TEM, and zeta potential techniques. Dye adsorption equilibrium was studied experimentally at pH 8.0 and 25-55 °C, and a statistical physics multilayer model was applied to understand the removal mechanism of these dyes including the adsorption orientations on the adsorbent surface. The number of adsorbed dye molecules per functional group (n) of this bio-based adsorbent ranged from 0.70 to 0.91, indicating the presence of vertical and horizontal adsorption orientations for these organic molecules at all tested solution temperatures. The calculated saturation adsorption capacities (Qsat) were 332.57-256.62 mg/g for CV and 304.47-240.62 mg/g for MB, and an exothermic adsorption was observed for both adsorbates. The estimated adsorption energies (∆E) were < 25 kJ/mol, confirming that the SAAES/SA/MNPs-dye interactions were governed by physical forces as electrostatic interactions. This bio-based adsorbent was effectively regenerated using ethanol and it can be reused showing a removal of 71 and 74 % of MB and CV, respectively, after fourth adsorption-desorption cycles. Overall, the results of this article suggest the attractive performance of SAAES/SA/MNPs for removing basic dyes from aqueous solutions, thus highlighting the promising potential of this magnetic bio-based adsorbent for sustainable wastewater treatment at an industrial level.
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Nanopartículas , Poluentes Químicos da Água , Animais , Adsorção , Corantes/química , Álcalis , Casca de Ovo/química , Cátions , Azul de Metileno/química , Fenômenos Magnéticos , Poluentes Químicos da Água/química , Concentração de Íons de Hidrogênio , CinéticaRESUMO
The adsorption of ammonium from water was studied on an activated carbon obtained using raw oil palm shell and activated with acetic acid. The performance of this adsorbent was tested at different operating conditions including the solution pH, adsorbent dosage, and initial ammonium concentration. Kinetic and equilibrium studies were carried out, and their results were analyzed with different models. For the adsorption kinetics, the pseudo-first order equation was the best model to correlate this system. Calculated adsorption rate constants ranged from 0.071 to 0.074 g/mg min. The ammonium removal was 70-80% at pH 6-8, and it was significantly affected by electrostatic interaction forces. Ammonium removal (%) increased with the adsorbent dosage, and neutral pH condition favored the adsorption of this pollutant. The best ammonium adsorption conditions were identified with a response surface methodology model where the maximum removal was 91.49% with 2.27 g/L of adsorbent at pH 8.11 for an initial ammonium concentration of 36.90 mg/L. The application of a physical monolayer model developed by statistical physics theory indicated that the removal mechanism of ammonium was multi-ionic and involved physical interactions with adsorption energy of 29 kJ/mol. This activated carbon treated with acetic acid is promising to depollute aqueous solutions containing ammonium.
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Ácido Acético , Compostos de Amônio , Poluentes Químicos da Água , Adsorção , Ácido Acético/química , Compostos de Amônio/química , Poluentes Químicos da Água/química , Cinética , Concentração de Íons de Hidrogênio , Arecaceae/química , Carvão Vegetal/química , Purificação da Água/métodosRESUMO
Magnetite nanoparticles (MNPs) synthesized from heated basalt were used to support a biocomposite prepared from muscovite (Mus) and carbohydrate polymer starch (St). The developed Mus/St/MNPs composite was characterized by XRD, FTIR, FESEM, TGA, DSC, and Zeta potential techniques. This multifunctional composite showed outstanding adsorption properties for hexavalent chromium (Cr(VI)) and methyl orange (MO) removal at 25-55 °C and pH 3.0. The adsorption isotherms were fitted to Langmuir model for Cr(VI) and Freundlich equation for MO. To understand microscopically these systems and to analyze their adsorption geometry and interactions mechanism, three statistical physics models were utilized. Theoretical calculations indicated that Cr(VI) ions were adsorbed on composite surface presenting a combination of horizontal and vertical positions, while the aggregated MO molecules displayed a non-parallel adsorption orientation and multi-interactions mechanism. The saturation adsorption capacity increased from 243.37 to 371.59 mg/g for Cr(VI) and 409.29 to 457.62 mg/g for MO at 25 and 55 °C (i.e., endothermic interactions). Cr(VI) and MO adsorption on Mus/St/MNPs was controlled by van der Waals forces, hydrogen bonding, and electrostatic interactions where the calculated adsorption energies were 12.5-30.62 kJ/mol. The utilized adsorbent was easily reactivated and reused several times where regenerated Mus/St/MNPs composite showed nearly 79 % of Cr(VI) and 85 % of MO adsorption capacities even after the fourth adsorption-desorption cycle. This study contributes to understand the physicochemical factors of Cr(VI) and MO adsorption on multifunctional adsorbents like MNPs/carbohydrate polymers/aluminosilicates interface.
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Poluentes Químicos da Água , Purificação da Água , Animais , Camundongos , Óxido Ferroso-Férrico/química , Amido , Cromo/química , Adsorção , Poluentes Químicos da Água/química , Cinética , Concentração de Íons de Hidrogênio , Purificação da Água/métodosRESUMO
The multicomponent adsorption of synthetic dyes has great relevance in the treatment of effluents due to the complexity of the adsorbate-adsorbent interactions. Therefore, this study provides useful information about the adsorption capacity of methylene blue (MB) and crystal violet (CV) in a bioadsorbent (mandarin peels) in a single-component and competitive system using detailed multivariate calibration analysis. The PLS1 multivariate calibration model was used to quantify the adsorbates. In mono and two-component systems, the adsorption capacity of CV (1.26-1.36 mg g-1) was superior when compared to MB (0.925-0.913 mg g-1), characterizing synergistic adsorption for CV and antagonistic adsorption for MB. The Sips model was effective for describing single-component systems, suggesting that adsorption did not occur in the monolayer. For competitive adsorption, modified, unmodified, and extended models were used to understand the interactions between the dyes and the bioadsorbent. The modified Redlich-Peterson (MRP) model was effective in describing the behavior of the binary system, indicating that the interaction forces with the adsorbate were significant. Thus, the bioadsorbent showed promising results for competitive adsorption, thus being of relevance to the industrial sector. Density functional calculations were also performed to characterize the atomic interactions for the removal of both dyes on mandarin peels.
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Azul de Metileno , Poluentes Químicos da Água , Azul de Metileno/química , Violeta Genciana , Adsorção , Calibragem , Teoria da Densidade Funcional , Cinética , Corantes/química , Poluentes Químicos da Água/análiseRESUMO
Low-cost and reliable wastewater treatment is a relevant issue worldwide to reduce the concentration of environmental pollutants. Industrial effluents containing dyes, heavy metals, and other inorganic and organic compounds can pollute water resources; therefore, novel technologies are required to mitigate and control their release into the environment. Adsorption is one of the simplest methods for treating contaminated water in which a wide spectrum of adsorbents can be used to remove emerging compounds. Hydrogels are interesting materials with high adsorption capacities that can be synthesized via green routes. These adsorbents are promising for large-scale industrial wastewater treatment applications; however, gaps still exist in achieving sustainable commercial implementation. This review focuses on the discussion and analysis of preparation, characterization, and adsorption properties of hydrogels for water purification. The advantages of these polymeric materials for water treatment were analyzed, including their performance in the removal of different organic and inorganic contaminants. Recent advances in the functionalization of hydrogels and the synthesis of novel composites have also been described. The adsorption capacities of hydrogel-based adsorbents are higher than 500 mg/g for different organic and inorganic pollutants, and can reach values of up to >2000 mg/g for organic compounds, significantly outperforming other materials reported for water cleaning. The main interactions involved in the adsorption of water pollutants using hydrogel-based adsorbents were described and explained to allow the interpretation of their removal mechanisms. The current challenges in the implementation of hydrogels for water purification in real-life operations are also highlighted. This review provides an updated picture of hydrogels as interesting materials to address water depollution worldwide.
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Poluentes Ambientais , Metais Pesados , Poluentes Químicos da Água , Purificação da Água , Hidrogéis , Águas Residuárias , Poluentes Químicos da Água/análise , Metais Pesados/análise , Polímeros , Poluentes Ambientais/análise , Purificação da Água/métodos , AdsorçãoRESUMO
This paper evaluates the adsorption mechanism of perfluorooctanoic carboxylic acid (PFCA) and heptadecafluorooctane sulfonic acid (HFOSA) on magnetic chitosan for the first time via a statistical physics modeling. Magnetic chitosan (MC-CoFe2O4) was produced from shrimp wastes and used in standard batch adsorption systems to remove PFCA and HFOSA. The experimental isotherms indicated that the maximum adsorption capacities ranged from 14 to 27.12 mg/g and from 19.16 to 45.12 mg/g for PFCA and HFOSA, respectively, where an exothermic behavior was observed for both compounds. The adsorption data were studied via an advanced model hypothesizing that a multilayer process occurred for these adsorption systems. This theoretical approach indicated that the total number of formed layers of PFCA and HFOSA adsorbates is about 3 (Nt = 2.83) at high temperatures (328 K) where a molecular aggregation process was noted during the adsorption. The maximum saturation-multilayer adsorption of PFCA and HFOSA on magnetic chitosan was 30.77 and 50.26 mg/g, respectively, and the corresponding adsorption mechanisms were successfully investigated. Two energies were responsible for the formed adsorbate layer directly on the surface and the vertical layers were computed and interpreted, reflecting that physical interactions were involved to bind these molecules on the adsorbent surface at different temperatures where the calculated adsorption energies ranged from 14 to 31 kJ/mol. Overall, this work provides theoretical insights to understand the adsorption mechanism of PFCA and HFOSA using the statistical physics modeling and its results can be used to improve the adsorbent performance for engineering applications.
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Quitosana , Poluentes Químicos da Água , Adsorção , Fenômenos Magnéticos , Ácidos Sulfônicos , Cinética , Concentração de Íons de HidrogênioRESUMO
Undoped and manganese doped ZnS nanocrystals encapsulated with thioglycolic acid (ZnS-TGA) were synthesized and characterized with different techniques, and finally tested in the photodegradation of a methyl orange in aqueous solution under UV and sunlight irradiations. FTIR and X-ray diffraction results confirmed the functionalization of these nanocrystal surface by thioglycolic acid and the formation of crystalline structures of ZnS and Mn-doped ZnS with cubic and hexagonal phases. Calculated average size of ZnS nanocrystals was in the range of 2-3 nm. It was observed a blue shift of the absorbance threshold and the estimated bandgap energies were higher than that of Bulk ZnS thus confirming the quantum confinement effect of charge carriers. Photoluminescence spectra of ZnS nanocrystals exhibited emission in the range of 410-490 nm and the appearance of an additional emission band around 580 nm (2.13 eV) connected to the 4T1 â 6A1 transition of the Mn2+ions. Photodegradation of methylene orange with undoped and Mn-doped ZnS-TGA nanocrystals was investigated. Dye adsorption prior to photocatalysis using nanocrystals was studied via kinetic and equilibrium experiments. The maximum dye adsorption capacity on doped ZnS-TGA was ~ 26.98 mg/g. The adsorption kinetic was found to follow the pseudo-second-order kinetic model. A statistical physics model was used to analyze the equilibrium data where the calculated adsorption energy was 17-18 kJ/mol. It was concluded that the dye adsorption was associated to the hydrogen interaction where the removal process was feasible and multi-molecular at 25 °C. The photocatalytic activity of undoped ZnS nanoparticles under UV irradiation showed better efficiency than doped nanocrystals thus indicating that manganese doping generated a dropping of the photocatalytic degradation of the dye. Dye degradation efficiency of 81.37% using ZnS-TGA nanocrystals was achieved after 6 min, which indicated that ZnMnS-TGA nanocrystals may be considered an alternative low cost and environmental friendly material for facing water pollution caused by organic compounds via photodegradation processes.
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Manganês , Nanopartículas , Corantes , Manganês/química , Nanopartículas/química , Sulfetos/química , Compostos de Zinco/químicaRESUMO
This work describes the modeling and analysis of methylene blue molecule on different adsorbents, namely, nickel alginate/graphene oxide (NA/GO) aerogel, nickel alginate/activated carbon (NA/AC) aerogel, and Trichosanthes kirilowii maxim shell activated carbon (TKAC). A multilayer statistical physics model was used to calculate the energetic and steric parameters of the adsorption of methylene blue on these adsorbents. Based on the modeling investigation, it was concluded that the formation of multiple dye adsorbed layers on these adsorbents could be feasible where physical adsorption interactions could be involved. Adsorption capacities at saturation of these adsorbents ranged from 542.97 to 470.03 mg/g, 790.66 to 684.47 mg/g, and 401.11 to 1236.24 mg/g for NA-GO aerogel, NA-AC aerogel, and TKAC, respectively. This research contributes with new findings for the understanding of dye adsorption on novel materials, which can be used in water pollution control.