Oxygen reduction reaction mechanism on nitrogen-doped graphene:A density functional theory study

Nitrogen-doped graphene (N-graphene) was reported to exhibit a good activity experimentally as an electrocatalyst of oxygen reduction reaction (ORR) on the cathode of fuel cells under the condition of electropotential of similar to 0.04 V (vs. NNE) and pH of 14. This material is promising to replace or partially replace the conventionally used Pt. In order to understand the experimental results. ORR catalyzed by N-graphene is studied using density functional theory (DFT) calculations under experimental conditions taking the solvent, surface adsorbates, and coverages into consideration. Two mechanisms, i.e., dissociative and associative mechanisms, over different N-doping configurations are investigated. The results show that N-graphene surface is covered by O with 1/6 monolayer, which is used for reactions in this work. The transition state of each elementary step was identified using four different approaches, which give rise to a similar chemistry. A full energy profile including all the reaction barriers shows that the associative mechanism is more energetically favored than the dissociative one and the removal of O species from the surface is the rate-determining step. (C) 2011 Elsevier Inc. All rights reserved.

Development of new technologies for the selective removal of volatile compounds with applications in forensic science and natural aromas

Tese de doutoramento, Farmácia (Química Farmacêutica e Terapêutica), Universidade de Lisboa, Faculdade de Farmácia, 2015

Polystyrene Anchored Vanillin Schiff Base—Complexation and Ion Removal Studies

A set of six new polystyrene anchored metal complexes have been synthesized by the reaction of the metal salt with the polystyrene anchored Schiff base of vanillin. These complexes were characterized by elemental analyses, Fourier transform infrared spectroscopy, diffuse reflectance studies, thermal studies, and magnetic susceptibility measurements. The elemental analyses suggest a metal : ligand ratio of 1 : 2. The ligand is unidentate and coordinates through the azomethine nitrogen. The Mn(II), Fe(III), Co(II), Ni(II), and Cu(II) complexes are all paramagnetic while Zn(II) is diamagnetic. The Cu(II) complex is assigned a square planar structure, while Zn(II) is assigned a tetrahedral structure and Mn(II), Fe(III), Co(II), and Ni(II) are all assigned octahedral geometry. The thermal analyses were done on the ligand and its complexes to reveal their stability. Further, the application of the Schiff base as a chelating resin in ion removal studies was investigated. The polystyrene anchored Schiff base gave 96% efficiency in the removal of Ni(II) from a 20-ppm solution in 15 min, without any interference from ions such as Mn(II), Co(II), Fe(III), Cu(II), Zn(II), U(VI), Na , K , NH4 , Ca2 , Cl , Br , NO3 , NO2 ,and CH3CO2 . The major advantage is that the removal is achieved without altering the pH.

Complexation and ion removal studies of a polystyrene anchored Schiff base

This paper reports the synthesis of a series of six new polystyrene anchored metal complexes of Co(II), Fe(III), Ni(II), Cu(II), Zn(II), and dioxouanium(VI) using the polystyrene anchored Schiff base of 2-nitrobenzaldehyde and the corresponding metal salts. The metal salts used were anhydrous FeCl3, CoCl2 Æ 6H2O, Ni(CH3COO)2 Æ 4H2O, Cu(CH3- COO)2 Æ H2O, Zn(CH3COO)2 Æ 2H2O, and UO2(CH3COO) Æ 2H2O. Physico chemical characterizations have been made from diffuse reflectance and vibrational spectra, elemental analysis, magnetic measurements, and TG studies. The elemental analysis suggest a 1:2 metal:ligand ratio when the complexation has carried out at 70 C for about 12 h reflux. The ligand is monodentate and coordinates through the azomethine nitrogen. The Fe(III), Co(II), Ni(II), and Cu(II) complexes are all paramagnetic whereas Zn(II) and U(VI) are diamagnetic. Zn(II) is assigned a tetrahedral structure, Cu(II) and Co(II) are assigned a square planar structure and Fe(III), Ni(II), and U(VI) are all assigned an octahedral structure. The polystyrene anchored ligand has been developed as an excellent reagent for the removal of Cu(II). Optimum conditions have been developed for the removal of metal ion from solutions by studying the effect of change of concentration of metal ion, ligand, effect of pH, time of reflux, and interference effect of other ions. It was found that within a span of 20 min it is possible to remove 90% of the metal ion from a 30 ppm metal ion solution in the pH range 4–5.5.

Biological nutrient removal in SBR technology: from floccular to granular sludge

Biological nutrient removal has been studied and applied for decades in order to remove nitrogen and phosphorus from wastewater. However, more anthropogenic uses and the continued demand for water have forced the facilities to operate at their maximum capacity. Therefore, the goal of this thesis is to obtain more compact systems for nutrient removal from domestic wastewater. In this sense, optimization and long-term stabilization of high volume exchange ratios reactors, treating higher volumes of wastewater, have been investigated. With the same target, aerobic granular sludge was proposed as a reliable alternative to reduce space and increase loading rates in treatment plants. However, the low organic loading rate from low-strength influents (less than 1 Kg COD•m-3d-1) results in slower granular formation and a longer time to reach a steady state. Because of that, different methodologies and operational conditions were investigated in order to enhance granulation and nutrient removal from domestic wastewater.

Splanchnic metabolism of nitrogenous compounds and urinary nitrogen excretion in steers fed alfalfa under conditions of increased absorption of ammonia and L-arginine supply across the portal-drained viscera

Effects of increased ammonia and/or arginine absorption across the portal-drained viscera (PDV) on net splanchnic (PDV and liver) metabolism of nitrogenous compounds and urinary N excretion were investigated in six cathetenzed Hereford x Angus steers (501 +/- 1 kg BW) fed a 75% alfalfa:25% (as-fed basis) corn-soybean meal diet (0.523 MJ of ME/[kg BW0.15.d]) every 2 h without (27.0 g of N/kg of dietary DM) and with 20 g of urea/kg of dietary DM (35.7 g of N/kg of dietary DM) in a split-plot design. Net splanchnic flux measurements were obtained immediately before beginning and ending a 72-h mesenteric vein infusion of L-arginine (15 mmol/h). For 3 d before and during arginine infusion, daily urine voided was measured and analyzed for N composition. Feeding urea increased PDV absorption (P < 0.01) and hepatic removal (P < 0.01) of ammonia N, accounting for 80% of increased hepatic urea N output (P < 0.01). Numerical increases in net hepatic removal of AA N could account for the remaining portion of increased hepatic urea N output. Arginine infusion increased hepatic arginine removal (P < 0.01) and hepatic urea N output (P < 0.03) and switched hepatic ornithine flux from net uptake to net output (P < 0.01), but numerical changes in net hepatic removal of ammonia and AA N could not account fully for the increase in hepatic urea N output. Increases in urine N excretion equaled quantities of N fed as urea or infused as arginine. Estimated salivary urea N excretion was not changed by either treatment. Urea cycle regulation occurs via a complex interaction of mechanisms and requires N sources other than ammonia, but the effect of increased ammonia absorption on hepatic catabolism of individual AA in the present study was not significant.

Influence of earthworm Eisenia fetida on removal efficiency of N and P in vertical flow constructed wetland.

This study investigates biomass, density, photosynthetic activity, and accumulation of nitrogen (N) and phosphorus (P) in three wetland plants (Canna indica, Typha augustifolia, and Phragmites austrail) in response to the introduction of the earthworm Eisenia fetida into a constructed wetland. The removal efficiency of N and P in constructed wetlands were also investigated. Results showed that the photosynthetic rate (P n), transpiration rate (T r), and stomatal conductance (S cond) of C. indica and P. austrail were (p < 0.05) significantly higher when earthworms were present. The addition of E. fetida increased the N uptake value by above-ground of C. indica, T. augustifolia, and P. australis by 185, 216, and 108 %, respectively; and its P uptake value increased by 300, 355, and 211 %, respectively. Earthworms could enhance photosynthetic activity, density, and biomass of wetland plants in constructed wetland, resulting in the higher N and P uptake. The addition of E. fetida into constructed wetland increased the removal efficiency of TN and TP by 10 and 7 %, respectively. The addition of earthworms into vertical flow constructed wetland increased the removal efficiency of TN and TP, which was related to higher photosynthetic activity and N and P uptake. The addition of earthworms into vertical flow constructed wetland and plant harvests could be the significantly sustainable N and P removal strategy

Spatio-temporal variations of ozone and nitrogen dioxide concentrations under urban trees and in a nearby open area

The evergreen Quercus ilex L. is one of the most common trees in Italian urban environments and is considered effective in the uptake of particulate and gaseous atmospheric pollutants. However, the few available estimates on O3 and NO2 removal by urban Q. ilex originate from model-based studies (which indicate NO2/O3 removal capacity of Q. ilex) and not from direct measurements of air pollutant concentrations. Thus, in the urban area of Siena (central Italy) we began long-term monitoring of O3/NO2 concentrations using passive samplers at a distance of 1, 5, 10 m from a busy road, under the canopies of Q. ilex and in a nearby open-field. Measurements performed in the period June 2011-October 2013 showed always a greater decrease of NO2 concentrations under the Q. ilex canopy than in the open-field transect. Conversely, a decrease of average O3 concentrations under the tree canopy was found only in autumn after the typical Mediterranean post-summer rainfalls. Our results indicate that interactions between O3/NO2 concentrations and trees in Mediterranean urban ecosystems are affected by temporal variations in climatic conditions. We argue therefore that the direct measurement of atmospheric pollutant concentrations should be chosen to describe local changes of aerial pollution.

An evaluation into the potential of biological processing for the removal of metals from sewage sludges

The use of sewage sludge in agricultural land as a means of sludge disposal and recycling has been shown to be economical and suitable because of the presence of nutrients such as nitrogen and phosphorus. However, municipal sludges often contain high quantities of toxic metals and other compounds that must be removed for its safe use in agricultural soils. The biological leaching of metals from sewage sludges has been shown to be a promising technique for metal detoxifying in such complex matrix. The process efficiency is dependent on several physico-chemical parameters, such as total solids concentration, metal forms, pH-ORP, and temperature. Scale-up of the process has not yet been defined and is still pursuing the correct operational design. Current research involving the bioleaching of metals from sewage sludge and its application to land, which affects soil physical properties, are presented and discussed.

Nitrate Removal on a Cu/Cu2O Photocathode under UV Irradiation and Bias Potential

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The reactive surface of Castor leaf [Ricinus communis L.] powder as a green adsorbent for the removal of heavy metals from natural river water

In this study, a green adsorbent was successfully applied to remove toxic metals from aqueous solutions. Dried minced castor leaves were fractionated into 63-μm particles to perform characterization and extraction experiments. Absorption bands in FTIR (Fourier Transform Infrared Spectroscopy) spectra at 1544, 1232 and 1350 cm-1 were assigned to nitrogen-containing groups. Elemental analysis showed high nitrogen and sulfur content: 5.76 and 1.93%, respectively. The adsorption kinetics for Cd(II) and Pb(II) followed a pseudo-second-order model, and no difference between the experimental and calculated Nf values (0.094 and 0.05 mmol g-1 for Cd(II) and Pb(II), respectively) was observed. The Ns values calculated using the modified Langmuir equation, 0.340 and 0.327 mmol g-1 for Cd(II) and Pb(II), respectively, were superior to the results obtained for several materials in the literature. The method proposed in this study was applied to pre-concentrate (45-fold enrichment factor) and used to measure Cd(II) and Pb(II) in freshwater samples from the Paraná River. The method was validated through a comparative analysis with a standard reference material (1643e). © 2013 Elsevier B.V. © 2013 Elsevier B.V. All rights reserved.

Efficient Photoelectrochemical Reduction of Nitrite to Ammonium and Nitrogen Containing Gaseous Species Using Ti/TiO2 Nanotube Electrodes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Cassava root husks powder as green adsorbent for the removal of Cu(II) from natural river water

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Algal wastewater treatment and biomass producing potential: nutrient removal efficiency and cell physiological responses

Microalgae are sun - light cell factories that convert carbon dioxide to biofuels, foods, feeds, and other bioproducts. The concept of microalgae cultivation as an integrated system in wastewater treatment has optimized the potential of the microalgae - based biofuel production. These microorganisms contains lipids, polysaccharides, proteins, pigments and other cell compounds, and their biomass can provide different kinds of biofuels such as biodiesel, biomethane and ethanol. The algal biomass application strongly depends on the cell composition and the production of biofuels appears to be economically convenient only in conjunction with wastewater treatment. The aim of this research thesis was to investigate a biological wastewater system on a laboratory scale growing a newly isolated freshwater microalgae, Desmodesmus communis, in effluents generated by a local wastewater reclamation facility in Cesena (Emilia Romagna, Italy) in batch and semi - continuous cultures. This work showed the potential utilization of this microorganism in an algae - based wastewater treatment; Desmodesmus communis had a great capacity to grow in the wastewater, competing with other microorganisms naturally present and adapting to various environmental conditions such as different irradiance levels and nutrient concentrations. The nutrient removal efficiency was characterized at different hydraulic retention times as well as the algal growth rate and biomass composition in terms of proteins, polysaccharides, total lipids and total fatty acids (TFAs) which are considered the substrate for biodiesel production. The biochemical analyses were coupled with the biomass elemental analysis which specified the amount of carbon and nitrogen in the algal biomass. Furthermore photosynthetic investigations were carried out to better correlate the environmental conditions with the physiology responses of the cells and consequently get more information to optimize the growth rate and the increase of TFAs and C/N ratio, cellular compounds and biomass parameter which are fundamental in the biomass energy recovery.

Use of isotopes for studying nitrogen processes in a wetland within the Venice Lagoon watershed

The present study is based on the use of isotopes for evaluating the efficiency of nutrients removal of a wetland, in particular nitrogen and nitrates, also between the different habitats present in the wetland. Nutrients like nitrogen and phosphorus, normally distributed as fertilizers, are among the principal causes of diffuse pollution. This is particularly important in the Adriatic Sea, which is frequently subjected to eutrophication phenomena. So it is very crucial requalification of wetland, in which there are naturally depurative processes such as denitrification and plant uptake, which allow the reduction of pollutant loads that flow in water bodies. In this study nutrient reduction is analyzed in the wetland of the Comuna drain, which waters flow in the Venice lagoon. Chemical and isotopical analyses were performed on samples of water, vegetation, soil and sediments taken in the wetlands of the Comuna drain in four different periods of the year and on data of nitrogen and phosphorus concentration obtained by the LASA of the University of Padova. Values of total nitrogen and nitrates were obtained in order to evaluate the reduction within the different systems of the wetland. Instead, the isotopic values of nitrogen and carbon were used to evaluate which process influence more nitrogen reduction and to understand the origin of the nutrient, if it is from fertilizers, waste water or sewage. To conclude, the most important process in the wetland of the Comuna drain is plant uptake, in facts the bigger percentage of nitrogen reduction was in the period of vegetative growth. So it is important the study of isotopes in plant tissues and water residence time, whose increase would allow a greater reduction of nutrients.