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1.
J Environ Manage ; 352: 120029, 2024 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-38184877

RESUMO

Using biowaste-based adsorbents to remove phosphorus (P) from wastewater offers significant benefits concerning eutrophication mitigation and addressing waste management challenges. In this work, Ca-biocomposites were prepared by pyrolysis (700 °C) of a mixture of banana peel (BP) and eggshell (ES). The mass ratio of BP to ES was varied in 2:1, 1:1, and 1:2 ratios. Among the tested mixtures, the BPES-1:2 sample exhibited excellent P removal performance, reaching a maximum P adsorption capacity (Qmax) of 214 ± 5 mg P/g. The adsorption process fitted well with the Avrami order kinetic model (R2 > 0.996) and the Liu isotherms model (R2 > 0.997). The excellent fit of the experimental data to the Avrami model suggests that chemisorption is the dominant interaction mechanism, leading to precipitation through the formation of calcium phosphates. Additionally, the Liu model anticipates that the energetic characteristics of the adsorbent's active sites cannot be identical. This is in agreement with the presence of Ca(OH)2 and CaCO3 in the adsorbent material, where the Ca(OH)2 active sites are preferred by the adsorbate molecules (PO43-) for occupation. Furthermore, thermodynamic analysis revealed that P adsorption is a spontaneous process of exothermic nature (ΔH° < 0). The calculated activation energy for the process (72.81 kJ/mol) suggests the P adsorption mechanism involves strong chemical bonding between the adsorbent and P species. In addition, precipitation of apatite (Ca5(PO4)3OH), a vital component in fertilizer production, was observed during the adsorption process. In tertiary treated wastewater applications, the BPES-1:2 biocomposite demonstrated a P removal efficiency of 90%. The solubility of P in a 2% formic acid solution was 100%, while the water-soluble P content was measured at 5.6%. These findings highlight the product's sustainable and environmentally beneficial nature by demonstrating its potential as a slow-release fertilizer, contributing to the application of the 3R slogan: Reduce, Reuse, Recycle. This value-added product is promising in supplying nutrients to plants over an extended period while minimizing the risk of nutrients leaching into the environment.


Assuntos
Musa , Poluentes Químicos da Água , Animais , Fosfatos , Águas Residuárias , Casca de Ovo/química , Fertilizantes/análise , Adsorção , Cinética , Poluentes Químicos da Água/química
2.
J Environ Manage ; 323: 116148, 2022 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-36088761

RESUMO

Biochar (BP) obtained from palm fiber wastes was combined with H2O2, peroxymonosulfate (PMS), or persulfate (PDS) to treat valsartan, acetaminophen, and cephalexin in water. BP activated PMS and PDS but no H2O2. Computational calculations indicated that interactions of PMS and PDS with BP are more favored than those with HP. The highest synergistic effect was obtained for the removal of valsartan by BP + PMS. This carbocatalytic process was optimized, evaluating the effects of pH, BP dose, and peroxymonosulfate concentration, and minimizing the oxidant quantity to decrease costs and environmental impacts of the process. SO4•-, HO•, 1O2, and O2•- were the agents involved in the degradation of the pharmaceuticals. The reusability of BP was tested, showing that the carbocatalytic process removed ∼80% of target pollutants after 120 min of treatment even at the fourth reuse cycle. Also, the process decreased the phytotoxicity of the treated sample. Simulated hospital wastewater was treated and its components induced competing effects, but the system achieved the target pharmaceuticals removal in this matrix. Additionally, the analysis of environmental impact using a life cycle assessment unraveled that the carbocatalytic process had a carbon footprint of 2.87 Kg CO2-Eq, with the biochar preparation (which involves the use of ZnCl2 and electric energy consumption) as the main hotspot in the process.


Assuntos
Oxidantes , Poluentes Químicos da Água , Acetaminofen , Dióxido de Carbono/análise , Cefalexina/análise , Carvão Vegetal , Peróxidos , Preparações Farmacêuticas , Valsartana/análise , Águas Residuárias/análise , Água/análise , Poluentes Químicos da Água/análise
3.
Chemphyschem ; 23(23): e202200456, 2022 12 05.
Artigo em Inglês | MEDLINE | ID: mdl-35962558

RESUMO

The effects of the formal charge in the stability and bonding of water cavities when solvating a cation are studied here using [X(H2 O)20 ]q+ clusters starting with the well known 512 isomer of (water)20 , placing a single mono, di, or trivalent Xq+ cation at the interior, and then optimizing and characterizing the resulting clusters. Highly correlated interaction and deformation energies are calculated using the CCSD(T)-DLPNO formalism. Bonding interactions are characterized using the tools provided by the quantum theory of atoms in molecules, natural bond orbitals, and non-covalent surfaces. Our results indicate that water to water hydrogen bonds are sensibly strengthened resulting in strong cooperative effects, which amount to ≈ 2 ${ \approx 2}$  kcal/mol per hydrogen bond in the bare cavity and to larger values for the systems including the cations. Approximate encapsulation, that is, surrounding the cation by a network of hydrogen bonds akin to the well known methane clathrate seems to be preferred by cations with smaller charge densities while microsolvation, that is, cluster structures having explicit X⋯O contacts seem to be preferred by cations with larger charge densities which severely deform the cavity.


Assuntos
Teoria Quântica , Água , Modelos Moleculares , Ligação de Hidrogênio , Cátions/química , Água/química
4.
Molecules ; 27(16)2022 Aug 11.
Artigo em Inglês | MEDLINE | ID: mdl-36014346

RESUMO

Pollution by dyes and heavy metals is one of the main concerns at the environmental level due to their toxicity and inefficient elimination by traditional water treatment. Orange peel (OP) without any treatment was applied to effectively eliminate methylene blue (MB) and cadmium ions (Cd2+) in mono- and multicomponent systems. Although the single adsorption processes for MB and Cd2+ have been investigated, the effects and mechanisms of interactions among multicomponent systems are still unclear. Batch experiments showed that in monocomponent systems, the maximum adsorption capacities were 0.7824 mmol g-1 for MB and 0.2884 mmol g-1 for Cd2+, while in multicomponent systems (Cd2+ and MB), both contaminants competed for the adsorption sites on OP. Particularly, a synergic effect was observed since the adsorption capacity of Cd2+ increased compared to the monocomponent system. Results of desorption and adsorbent reuse confirmed that the adsorbent presents good regeneration performance. The low cost of this material and its capacity for the individual or simultaneous removal of Cd2+ and MB in aqueous solutions makes it a potential adsorbent for polluted water treatment processes.


Assuntos
Citrus sinensis , Poluentes Químicos da Água , Purificação da Água , Adsorção , Cádmio , Concentração de Íons de Hidrogênio , Cinética , Azul de Metileno , Águas Residuárias , Purificação da Água/métodos
5.
Phys Chem Chem Phys ; 24(27): 16556-16565, 2022 Jul 13.
Artigo em Inglês | MEDLINE | ID: mdl-35770743

RESUMO

Transition metal carbides are increasingly used as catalysts for the transformation of CO2 into useful chemicals. Recently, the effect of nanostructuring of such carbides has started to gain relevance in tailoring their catalytic capabilities. Catalytic materials based on molybdenum carbide nanoparticles (MoCy) have shown a remarkable ability to bind CO2 at room temperature and to hydrogenate it into oxygenates or light alkanes. However, the involved chemistry is largely unknown. In the present work, a systematic computational study is presented aiming to elucidate the chemistry behind the bonding of CO2 with a representative set of MoCy nanoparticles of increasing size, including stoichiometric and non-stoichiometric cases. The obtained results provide clear trends to tune the catalytic activity of these systems and to move towards more efficient CO2 transformation processes.

6.
Bioresour Technol ; 343: 126106, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34637908

RESUMO

Potato peel (PP) waste are generated in huge quantities, causing environmental pollution and health problems. Therefore, obtaining value-added products from PP is a current research challenge. In this work, novel Ca-biocomposites for phosphorus (P) removal were prepared by pyrolysis (500-800 °C) using eggshell (ES) and PP (ES/PP = 1:2 ratio by weight). ESPP-700 (pyrolyzed at 700 °C), reached a Qmax of 174.8 mg P/g, while the application of Ca-biocomposites in domestic wastewater showed 85.96% of P removal. According to the pseudo-second-order kinetic model, P adsorption was dominated by chemisorption, follows by apatite precipitation. The P solubility (62.5 wt.%) in formic acid (2.0 wt.%) and the water-soluble P (3.2 wt.%) for ESPP-700 after P adsorption, indicated that the final product would work as fertilizer for acidic soils. This is an important step in the management of agricultural wastes to implement the 3R slogan "Reduce, Reuse, Recycle" towards a circular economy.


Assuntos
Solanum tuberosum , Poluentes Químicos da Água , Adsorção , Animais , Casca de Ovo/química , Cinética , Fósforo , Águas Residuárias , Poluentes Químicos da Água/análise
7.
Chemphyschem ; 23(2): e202100716, 2022 01 19.
Artigo em Inglês | MEDLINE | ID: mdl-34761856

RESUMO

A detailed analysis under a comprehensive set of theoretical and computational tools of the thermodynamical factors and of the intermolecular interactions behind the stabilization of a well known set of (water)20 cavities and of the methane clathrate is offered in this work. Beyond the available reports of experimental characterization at extreme conditions of most of the systems studied here, all clusters should be amenable to experimental detection at 1 atm and moderate temperatures since 280 K marks the boundary at which, ignoring reaction paths, formation of all clusters is no longer spontaneous from the 20H2 O→(H2 O)20 and CH4 +20H2 O→CH4 @512 processes. As a function of temperature, a complex interplay leading to the free energy of formation occurs between the destabilizing entropic contributions, mostly due to cluster vibrations, and the stabilizing enthalpic contributions, due to intermolecular interactions and the PV term, is best illustrated by the highly symmetric 512 cage consistently showing signs of stronger intermolecular bonding despite having smaller binding energy than the other clusters. A fluxional wall of attractive non-covalent interactions, arising because of the cumulative effect of a large number of tiny individual charge transfers to the interstitial region, plays a pivotal role stabilizing the CH4 @512 clathrate.


Assuntos
Metano , Água , Fenômenos Biofísicos , Entropia , Metano/química , Termodinâmica , Água/química
8.
Chemosphere ; 287(Pt 3): 132333, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34563780

RESUMO

Phosphorus (P) adsorption from aqueous solutions is usually evaluated by monitoring the P concentration and employed kinetic models. In this work, three adsorbents obtained from eggshell (ES) and eggshell mixed with palm mesocarp fiber (ESF-1:1 and ESF-1:10) at different Ca(OH)2/CaCO3 compositions were evaluated, and the Ca-P species formed monitored as a function of time deconvoluting Fourier Transform Infrared (FTIR) spectra. At 0.25 h the ESF-1:10 (Ca(OH)2: 26.2 wt%) exhibited better adsorption performance of 35 mgg-1 while ESF-1:1 and ES (Ca(OH)2: 2.8 and 3.0 wt%) showed 26 and 4 mgg-1, respectively. Characteristic PO43- bands in apatite were corroborated by XRD and FTIR. It was found that the role of Ca(OH)2 in the adsorption ends before 0.25 h, and thereafter CaCO3 becomes the phase responsible for the removal of orthophosphate H2PO4-/HPO42-/PO43- ions. The results indicate a direct ligand exchange of CO32- for PO43- that takes place while increasing the apatite crystallinity. On the other hand, the P adsorption process is also dependent on P concentration. At low P concentrations, characteristic bands of PO43- in apatite were observed in FTIR, while at high concentrations, characteristic bands for adsorbed HPO42- were obtained. The obtained results give a relevant role to CaCO3 in P adsorption. Kinetic analysis for Ca-based biocomposites showed that the Avrami order kinetic model fits better for the adsorbents. For P adsorption isotherm process the Langmuir's isotherms showed a good fit, with a maximum adsorption capacity of 90.8, 134.0, and 67.9 mgg-1 for ES, ESF-1:1, and ESF-1:10, respectively.


Assuntos
Fósforo , Purificação da Água , Adsorção , Animais , Casca de Ovo , Cinética
9.
Phys Chem Chem Phys ; 23(36): 20255-20267, 2021 Sep 22.
Artigo em Inglês | MEDLINE | ID: mdl-34477186

RESUMO

Hydrogenation reactions are involved in several processes in heterogeneous catalysis. Platinum is the best-known catalyst; however, there are limitations to its practical use. Therefore, it is necessary to explore alternative materials and transition metal carbides (TMCs) have emerged as potential candidates. We explore the possibility of using cheap TMCs as supports for a Pt monolayer, aiming to reduce the amount of the noble metal in the catalyst without a significant loss of its activity towards H2 dissociation. Hence, analyzing H2 dissociation from a fundamental point of view is a necessary step towards a further practical catalyst. By means of periodic DFT calculations, we analyze H2 adsorption and dissociation on Pt/ß-Mo2C and Pt/α-WC surfaces, as a function of hydrogen surface coverage (ΘH), resembling a more realistic model of a catalyst. H2 dissociation rates were analyzed as a function of the reaction temperature. The results show that Pt/C-WC and Pt/Mo-Mo2C have a Pt-like behavior for H2 dissociation at ΘH > 1/2 ML. At a particular temperature of 298 K, Pt/C-WC and Pt/Mo-Mo2C have low energy barriers for H2* → 2H* (0.13 and 0.11 eV, respectively), close to the value of Pt (0.06 eV). For the highest coverage, i.e. ΘH = 1, Pt/C-WC has a lower activation energy and a higher reaction rate than Pt. Finally, the H2 dissociation rate is higher in Pt/Mo-Mo2C than in Pt when increasing the temperature above 298 K. Our results put Pt/C-WC and Pt/Mo-Mo2C under the spotlight as potential catalysts for H2 dissociation, with a similar performance to Pt, paving the way for further experimental and/or theoretical studies, addressing the capability of Pt/TMC as practical catalysts in hydrogenation reactions.

10.
Molecules ; 26(15)2021 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-34361706

RESUMO

Chemical and thermochemical transformations were performed on orange peel to obtain materials that were characterized and further tested to explore their potential as adsorbents for the removal of methylene blue (MB) from aqueous solutions. The results show the high potential of some of these materials for MB adsorption not only due to the surface area of the resulting substrate but also to the chemistry of the corresponding surface functional groups. Fitting of the kinetic as well as the equilibrium experimental data to different models suggests that a variety of interactions are involved in MB adsorption. The overall capacities for these substrates (larger than 192.31 mg g-1) were found to compare well with those reported for activated carbon and other adsorbents of agro-industrial origin. According to these results and complementary with theoretical study using Density Functional Theory (DFT) approximations, it was found that the most important adsorption mechanisms of MB correspond to: (i) electrostatic interactions, (ii) H-bonding, and (iii) π (MB)-π (biochar) interactions. In view of these findings, it can be concluded that adsorbent materials obtained from orange peel, constitute a good alternative for the removal of MB dye from aqueous solutions.


Assuntos
Citrus sinensis/química , Frutas/química , Azul de Metileno/isolamento & purificação , Águas Residuárias/química , Poluentes Químicos da Água/isolamento & purificação , Adsorção , Carvão Vegetal/química , Teoria da Densidade Funcional , Humanos , Ligação de Hidrogênio , Concentração de Íons de Hidrogênio , Cinética , Pós , Eletricidade Estática , Resíduos/análise
11.
Bioresour Technol ; 326: 124753, 2021 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-33545628

RESUMO

Acetaminophen (ACE), cephalexin (CPX), and valsartan (VAL) are recognized water pollutants, which can be removed by adsorption. Herein, the removal of these pharmaceuticals using a biochar (BP), prepared from oil palm fiber, was tested. It was studied the structural effects of the pharmaceuticals and biochar on the adsorption process supported by experimental and computational results, plus characterizations of the material. The biochar has 76.05 m2 g-1 of surficial area, and carboxylic groups (1.343 mmol g-1) predominantly. The maximum adsorption uptakes were 7.3, 7.9, and 23.85 mg g-1 for ACE, CPX, and VAL, respectively; following pseudo-second-order kinetics. The best pollutants removal was obtained at acidic pH (3.0). Computational analyses indicated that oxygenated groups of BP (able to generate H-bond interactions) influenced the adsorption of pharmaceuticals. It can be remarked that BP is a low-cost adsorbent synthesized easily from wastes, with high feasibility to remove pharmaceutical structures from water.


Assuntos
Preparações Farmacêuticas , Poluentes Químicos da Água , Adsorção , Carvão Vegetal , Concentração de Íons de Hidrogênio , Cinética , Água , Poluentes Químicos da Água/análise
12.
Environ Sci Pollut Res Int ; 28(18): 23204-23219, 2021 May.
Artigo em Inglês | MEDLINE | ID: mdl-33439444

RESUMO

In the current work, a deep study to understand the adsorption phenomena occurring in single and multicomponent systems was conducted by using spectroscopic characterization, and computational tools. The experimental results showed that the adsorption capacity of chili seed is higher for Pb2+ (48 mg/g) than Cu2+ (4.1 mg/g) ions in single systems. However, the adsorption study in multicomponent systems provides important conclusions of the concentration effect of the metal ions, showing a significant antagonistic and competitive effect of both ions under equivalent concentrations of them (qPb2+ is 56% reduced) or high concentration of Pb2+ (qCu2+ is 50% reduced). Computational results correlated well with the experimental ones and evidenced all interactions proposed from spectroscopy results, accounting for the occurrence of complexation and electrostatic mechanisms between metal ions and the surface oxygenated functional groups (hydroxyl, carboxyl, and carboxylate) onto chili seed. Chemistry quantum descriptors supported the reactivity behavior of the chemical species implicated. All results evidenced that Pb2+ and Cu2+ adsorption on chili seed surface is governed by the occurrence of combined ionic exchange, π-interaction, complexation, and electrostatic attraction.


Assuntos
Cobre , Poluentes Químicos da Água , Adsorção , Concentração de Íons de Hidrogênio , Íons , Cinética , Chumbo , Poluentes Químicos da Água/análise
13.
ACS Appl Mater Interfaces ; 12(24): 27150-27165, 2020 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-32441912

RESUMO

Modification of electronic and chemical properties of a material by the introduction of another element into its lattice is one of the most common methods for designing new catalysts for different applications. In this work the effect of modifying molybdenum carbide with transition metals (Fe, Co, Ni, Cu), TM-Mo2C composites, upon the catalytic activity toward hydrogen evolution reaction (HER) in mild acidic and alkaline media has been studied. Catalysts were prepared by carbothermal reduction of molybdenum and TM oxides precursors and were characterized by different physicochemical techniques. Results evidenced a strong pH effect on the catalytic performance of TM-Mo2C, while, at pH = 5, inclusion of TM into the Mo2C lattice has a deleterious effect on the HER activity and, at pH = 9, a promoting effect was observed, highlighting the importance of considering specific operation conditions during the catalyst design process. Analysis of in situ near-edge X-ray adsorption data reveals a decrease on the oxidation state and average bond ionicity of dopant metal upon a pH increase, shedding light of the different effects of TMs on the resulting HER activity in acidic and alkaline media. Finally, stability tests demonstrated no deterioration on catalysts' performance after 8 h of continuous cycling within the HER working range, confirming the suitability of Mo2C materials as promising HER catalysts.

14.
Data Brief ; 29: 105292, 2020 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-32140510

RESUMO

Chromium (Cr) is a widely used metal in metallurgical and chemical industries, whose waste contaminates the surface and groundwater. Cr (VI) is toxic and produces carcinogenic effects owing to its high mobility in water and soil. In this work, computational and experimental studies from the adsorption of Cr(VI) from aqueous solutions on teak wood residues activated with ZnCl2 (AT) are presented. Full interpretation of data can be found in DOI:10.1016/j.jece.2020.103702 [1]. Experimental data were adjusted to Langmuir, Freundlich and Temkin isothermal models and the nonlinear and linear forms of the Pseudo-first and Pseudo-second order kinetic models. Computational data allow to understand the adsorption process of Cr(VI) on carbonaceous materials.

15.
Rev. biol. trop ; Rev. biol. trop;68(4)2020.
Artigo em Espanhol | LILACS, SaludCR | ID: biblio-1507720

RESUMO

Introducción: La investigación y el diagnóstico de fuentes hídricas es de interés académico y gubernamental, la exploración de instrumentos numéricos aplicados al ordenamiento de cuencas brinda la posibilidad de identificar dónde y qué variables son útiles en programas de monitoreo y rehabilitación en ecosistemas acuáticos, lo cual incluye la calidad del agua, convencionalmente analizada por índices fisicoquímicos e hidrobiológicos. En el 2014 a través de la guía de ordenamiento hídrico en Colombia, se desarrolló una evaluación del índice de calidad ecológica (ICE); la cual genera un sistema numérico de correlaciones que diagnostica, clasifica y detecta afectaciones ambientales. Objetivo: Esta investigación pretende demostrar que el ICE permite evaluar la calidad de ecosistemas acuáticos afectados por diferentes situaciones ambientales. Métodos: Se analizaron tres escenarios ubicados en diferentes regiones de Colombia y como grupo hidrobiológico indicador se utilizaron las algas perifíticas y fitoplanctónicas. Los ecosistemas fueron monitoreados entre el 2007 y 2016 y corresponden a una planicie de inundación, un río andino de alta montaña y un grupo de quebradas en un bosque húmedo tropical. Resultados: Las correlaciones canónicas fueron significativas (P < 0.005) y se estimó el óptimo y la tolerancia de cada taxa; variables relacionadas con la concentración de iones, la amortiguación de la acidez, la temperatura y la hidráulica, incidieron en la distribución de las abundancias de los organismos y la clasificación ecológica mediante el índice. Conclusiones: La aplicación del índice permite identificar variables, organismos y ordenamientos numéricos que posibilitan clasificar el estado ecológico en un sistema, resultados útiles en el diagnóstico y seguimiento de los ecosistemas acuáticos estudiados y que pueden ser implementados con otros escenarios.


Introduction: Research and diagnosis of water sources is of academic and governmental interest, for this reason, the exploration of numerical tools applied to watershed management, offers the possibility to identify where and what variables are useful in monitoring and rehabilitation programs of aquatic ecosystems. Environmental planning and management, which includes water quality, is conventionally analyzed by physical, chemical and hydrobiological indexes. In 2014, through the water management guide, included the assessment of the ecological quality index (EQI); it was generated a comprehensive approach through a numerical system of correlations that diagnoses, classifies and detects environmental impacts. Objective: This research aims to demonstrate that the EQI allows to assess the quality of aquatic ecosystems affected by different environmental situations. Methods: In order to analyze the application of this tool, we studied three scenarios located in different biogeographical regions of Colombia and, as a hydrobiological group indicator, we used peripheral and phytoplankton algae. The ecosystems were monitored between 2007 and 2015 and correspond to a flood plain, a high mountain Andean river and a group of water stream in a tropical humid forest. Results: Canonical correlations were significant (P < 0.005)and a model of weighted averages, allowed to estimate the optimum and the tolerance of each taxa for the sites ecological classification; variables related to ion concentration, acidity damping, temperature and hydraulics, influenced the models that explained the abundances distribution of the studied biological groups. Conclusions: The application of the EQI makes it possible to identify variables, organisms and numerical systems to classify ecological status. These results are useful in the diagnosis and monitoring of aquatic ecosystems and that can be implemented in other scenarios.


Assuntos
Ecossistema , Conservação dos Recursos Hídricos/estatística & dados numéricos , Colômbia
16.
J Phys Chem A ; 123(40): 8650-8656, 2019 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-31532674

RESUMO

Two stochastic methods in conjunction with ab initio computations were used to explore the potential energy surfaces for the microsolvation of SO42- with up to six explicit water molecules. At least three water molecules are needed to stabilize the Coulomb repulsion that prevents the existence of isolated SO42-. The formal charge in SO42- is strong enough to induce water dissociation and subsequent microsolvation of the resulting HSO4-, OH- ionic pair. Hydrogen bonds characterized as having complex contributions from covalency and from ionicity are at play stabilizing [SO4(H2O)n]2- clusters. Ionicity and covalency act concomitantly rather than opposedly to strengthen both intermolecular interactions and the resulting O-H bond in HSO4- after proton abstraction.

17.
Phys Chem Chem Phys ; 21(31): 17332-17342, 2019 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-31355380

RESUMO

Density functional calculations were used to evaluate the ability of cubic and hexagonal phases of tungsten carbide to bind ethylene, as a model compound of unsaturated hydrocarbons, since its adsorption is the first step in important catalytic processes. The calculations give the following trend in stability: α-WC(0001)-C > α-WC(0001)-W > Pt(111) > γ-WC(001), with the binding energy varying in the range of -0.72 to -2.91 eV. The sub-surface layers play a crucial role in the binding, favoring a charge reorganization at extended ranges (above 6 Å) from bulk towards the surface, however, the electronic structure of the surface was modified only in the topmost layer. The surface sites for geometric C2H4 activation were identified, leading to a surface distortion due to an upwards shifting of surface atoms in the range 0.13-0.61 Å observed in Pt(111), α-WC(0001)-C, and γ-WC(001), with distortion energies of 0.13, 0.15 and 0.61 eV, respectively. The activation of C2H4 on tungsten carbides was compared with other transition metal carbide surfaces, which leads to a general classification of the elongation of carbon-carbon bond into a set of only three groups. If the interest is to activate ethylene C[double bond, length as m-dash]C bond, the surface sites and the binding modes should be those of the groups II and III. The infrared spectra show mainly four useful signals as a fingerprint to support and complement future experiments. The results of this work indicate that the α-WC-W surface could be directly responsible for the catalytic performance, while the binding of olefins on α-WC-C could cause surface poisoning. The metastable γ-WC(001) surface could be a promising system as compared to the known α-WC(0001) surface, but challenges arise regarding its synthesis, stability and catalytic performance. These results pave the way to address further experimental and theoretical studies focused on the hydrogenation of ethylene and more complex unsaturated hydrocarbons.

18.
Rev Chilena Infectol ; 36(1): 9-15, 2019 Feb.
Artigo em Espanhol | MEDLINE | ID: mdl-31095199

RESUMO

BACKGROUND: Ertapenem has proven to be effective for extended-spectrum beta-lactamases-producing Enterobacteriaceae but lacks activity against non-fermenters; de-escalation to this antibiotic may reduce the selection of resistance to Pseudomonas aeruginosa and improve clinical outcomes. AIM: To evaluate the clinical impact of de-escalation from broad-spectrum anti-pseudomonal agents to ertapenem, a non-pseudomonal antibiotics for Enterobacteriaceae infections in critically-ill patients. METHODS: We conducted a prospective cohort study in adult patients admitted to intensive care units (ICUs) who had Enterobacteriaceae infections and were de-escalated from empiric anti-pseudomonal coverage to non-pseudomonal antibiotics. Cox proportional hazards models were performed comparing all-cause mortality and length of hospital stay between patients who remained on anti-pseudomonal coverage versus those who were de-escalated to ertapenem. RESULTS: 105 patients in the anti-pseudomonal group were compared to 148 patients in the ertapenem de-escalation group. De-escalation was associated with lower all-cause mortality compared to patients who remained on anti-pseudomonal coverage (adjusted Hazard Ratio 0.24; 95% CI: 0.12-0.46). The length of ICU stay was similar between the groups. DISCUSSION: ICU patients with Enterobacteriaceae infections de-escalated to ertapenem therapy had better outcomes compared to patients who remained on broad-spectrum, anti-pseudomonal therapy, suggesting that de-escalation is a safe approach amongst ICU patients.


Assuntos
Antibacterianos/administração & dosagem , Infecções por Enterobacteriaceae/tratamento farmacológico , Ertapenem/administração & dosagem , Unidades de Terapia Intensiva , Adulto , Idoso , Colômbia , Estado Terminal , Infecções por Enterobacteriaceae/mortalidade , Feminino , Humanos , Estimativa de Kaplan-Meier , Tempo de Internação , Masculino , Pessoa de Meia-Idade , Modelos de Riscos Proporcionais , Estudos Prospectivos , Pseudomonas/efeitos dos fármacos , Fatores de Risco , Estatísticas não Paramétricas , Fatores de Tempo , Resultado do Tratamento
19.
Environ Sci Pollut Res Int ; 26(16): 15725-15753, 2019 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-30989600

RESUMO

This article presents a review of the main physical, chemical, electrochemical, and biological technologies used for treating heavy metals in the wastewater of industrial processes and in synthetic aqueous solutions which could be applied to leachate from landfills. This paper outlines the generalities, operating principles, and modifications made to the technologies described. It discusses and assesses which of these have better removal rates and higher levels of efficiency in minimizing the heavy metal concentrations contained in leachates, such as mercury, chromium, lead, nickel, and copper among others. The first part of the document presents the so-called conventional technologies, such as chemical, physical, and electrochemical treatment. These have been used to treat different wastewater, especially industrial waste, operating adequately from the technical topic, but with high costs and the secondary products' production. The second part exposes biological treatments tend to be most widely used due to their versatility, effectiveness, and low cost, when compared with traditional technologies. It is important to note that there is no single treatment and that each of the technologies reviewed has different heavy metal decontamination rates. All technologies search to reduce concentrations of heavy metals to values that are safe for the natural resources where they are discharged or disposed, thereby complying with the regulatory limits regulated in each of the regions.


Assuntos
Cromo/análise , Cobre/análise , Metais Pesados/análise , Níquel/análise , Poluentes Químicos da Água/análise , Cromo/química , Cobre/química , Resíduos Industriais , Níquel/química , Águas Residuárias
20.
Rev. chil. infectol ; Rev. chil. infectol;36(1): 9-15, feb. 2019. tab, graf
Artigo em Espanhol | LILACS | ID: biblio-1003651

RESUMO

Resumen Introducción: Ertapenem ha demostrado eficacia frente a Enterobacteriaceae productoras de β-lactamasas de espectro extendido, pero carece de actividad contra bacterias no fermentadoras; el desescalamiento a este antimicrobiano cuando no existe la presencia de P. aeruginosa podría reducir la presión selectiva contra esta bacteria y mejorar los resultados clínicos. Objetivo: Evaluar el impacto clínico del desescalamiento de antimicrobianos con cobertura anti-pseudomonas a ertapenem, un agente sin este espectro, en pacientes críticos con infecciones por Enterobacteriaceae. Métodos: Se realizó un estudio de cohorte prospectivo en adultos admitidos a Unidades de Cuidado Intensivo (UCI) con infecciones por Enterobacteriaceae, que habían sido desescalados de una cobertura anti-pseudomonas, a un antimicrobiano sin la misma (ertapenem). Se realizó un modelo de riesgo proporcional de Cox comparando mortalidad por cualquier causa y duración de estancia hospitalaria entre aquellos pacientes que permanecieron con cobertura anti-pseudomonas versus aquellos que fueron desescalados a ertapenem. Resultados: 105 pacientes en el grupo anti-pseudomonas fueron comparados con 148 pacientes del grupo de desescalamiento a ertapenem. El desescalamiento estuvo asociado con una menor mortalidad por cualquier causa comparado con los pacientes que permanecieron con cobertura anti-pseudomonas (hazard ratio ajustado 0,24; IC 95%: 0,12-0,46). La estancia hospitalaria en UCI fue similar en ambos grupos. Discusión: Los pacientes de UCI con infecciones por Enterobacteriaceae desescalados a terapia con ertapenem, tuvieron mejores resultados clínicos comparados con aquellos que permanecieron en terapia anti-pseudomonas, sugiriendo que el desescalamiento es una práctica segura en esta población.


Background: Ertapenem has proven to be effective for extended-spectrum beta-lactamases-producing Enterobacteriaceae but lacks activity against non-fermenters; de-escalation to this antibiotic may reduce the selection of resistance to Pseudomonas aeruginosa and improve clinical outcomes. Aim: To evaluate the clinical impact of de-escalation from broad-spectrum anti-pseudomonal agents to ertapenem, a non-pseudomonal antibiotics for Enterobacteriaceae infections in critically-ill patients. Methods: We conducted a prospective cohort study in adult patients admitted to intensive care units (ICUs) who had Enterobacteriaceae infections and were de-escalated from empiric anti-pseudomonal coverage to non-pseudomonal antibiotics. Cox proportional hazards models were performed comparing all-cause mortality and length of hospital stay between patients who remained on anti-pseudomonal coverage versus those who were de-escalated to ertapenem. Results: 105 patients in the anti-pseudomonal group were compared to 148 patients in the ertapenem de-escalation group. De-escalation was associated with lower all-cause mortality compared to patients who remained on anti-pseudomonal coverage (adjusted Hazard Ratio 0.24; 95% CI: 0.12-0.46). The length of ICU stay was similar between the groups. Discussion: ICU patients with Enterobacteriaceae infections de-escalated to ertapenem therapy had better outcomes compared to patients who remained on broad-spectrum, anti-pseudomonal therapy, suggesting that de-escalation is a safe approach amongst ICU patients.


Assuntos
Humanos , Masculino , Feminino , Adulto , Pessoa de Meia-Idade , Idoso , Infecções por Enterobacteriaceae/tratamento farmacológico , Ertapenem/administração & dosagem , Unidades de Terapia Intensiva , Antibacterianos/administração & dosagem , Pseudomonas/efeitos dos fármacos , Fatores de Tempo , Modelos de Riscos Proporcionais , Estudos Prospectivos , Fatores de Risco , Resultado do Tratamento , Estado Terminal , Colômbia , Estatísticas não Paramétricas , Infecções por Enterobacteriaceae/mortalidade , Estimativa de Kaplan-Meier , Tempo de Internação
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