Zero-valent iron supported on nitrogen-doped carbon xerogel as catalysts for the oxidation of phenol by fenton-like system.

Nitrogen-free and nitrogen-doped carbon xerogel materials, from urea and melamine precursors, were prepared at different pH and evaluated as adsorbents/catalysts in the removal of phenol. Then, zero-valent iron (ZVI) was supported on these carbon xerogel materials and its activity was again evaluated for phenol removal by adsorption and catalytic wet peroxide oxidation (CWPO). The prepared samples were characterized by N2 adsorption at -196°C, pH at the point of zero charge (pHPZC) and elemental analysis. The textural properties of the N-free and N-doped carbon xerogels are strongly influenced by pH of the preparation solution and precursor used. The presence of ZVI on all carbon xerogel supports improved the phenol removal efficiency. ZVI supported on urea- and melamine-doped carbon xerogels show a good performance, reaching above 87% phenol conversion after 60 min of CWPO. On the contrary, pure adsorption and CWPO using the same materials without the presence of ZVI gives low phenol removal efficiency. A correlation was found between the activity of ZVI catalysts in CWPO and the N-content of the supports.

Effect of cobalt loading on the solid state properties and ethyl acetate oxidation performance of cobalt-cerium mixed oxides.

Cobalt-cerium mixed oxides were prepared by the wet impregnation method and evaluated for volatile organic compounds (VOCs) abatement, using ethyl acetate (EtAc) as model molecule. The impact of Co content on the physicochemical characteristics of catalysts and EtAc conversion was investigated. The materials were characterized by various techniques, including N2 adsorption at -196°C, scanning electron microscopy (SEM), X-ray diffraction (XRD), H2-temperature programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS) to reveal the structure-activity relationship. The obtained results showed the superiority of mixed oxides compared to bare CeO2 and Co3O4, demonstrating a synergistic effect. The optimum oxidation performance was achieved with the sample containing 20wt.% Co (Co/Ce atomic ratio of ca. 0.75), in which complete conversion of EtAc was attained at 260°C. In contrast, temperatures above 300°C were required to achieve 100% conversion over the single oxides. Notably, a strong relationship between both the: (i) relative population, and (ii) facile reduction of lattice oxygen with the ethyl acetate oxidation activity was found, highlighting the key role of loosely bound oxygen species on VOCs oxidation. A synergistic Co-Ce interaction can be accounted for the enhanced reducibility of mixed oxides, linked with the increased mobility of lattice oxygen.

Process design for wastewater treatment: catalytic ozonation of organic pollutants.

Emerging micropollutants have been recently the target of interest for their potential harmful effects in the environment and their resistance to conventional water treatments. Catalytic ozonation is an advanced oxidation process consisting of the formation of highly reactive radicals from the decomposition of ozone promoted by a catalyst. Nanocarbon materials have been shown to be effective catalysts for this process, either in powder form or grown on the surface of a monolithic structure. In this work, carbon nanofibers grown on the surface of a cordierite honeycomb monolith are tested as catalyst for the ozonation of five selected micropollutants: atrazine (ATZ), bezafibrate, erythromycin, metolachlor, and nonylphenol. The process is tested both in laboratorial and real conditions. Later on, ATZ was selected as a target pollutant to further investigate the role of the catalytic material. It is shown that the inclusion of a catalyst improves the mineralization degree compared to single ozonation.

Catalytic ozonation of metolachlor under continuous operation using nanocarbon materials grown on a ceramic monolith.

The catalytic ozonation of the herbicide metolachlor (MTLC) was tested using carbon nanomaterials as catalysts. Multiwalled carbon nanotubes were used in semi-batch experiments and carbon nanofibres grown on a honeycomb cordierite monolith were tested in continuous experiments. The application of the carbon catalyst was shown to improve the mineralization degree of MTLC and to decrease the toxicity of the solution subject to ozonation. Degradation by-products were also followed in order to compare the two processes. The application of the carbon coated monolith to the continuous ozonation process was shown to have potential as it improved the TOC removal from 5% to 35% and decreased the inhibition of luminescent activity of Vibrio Fischeri from 25% to 12%.

Catalytic ozonation of oxalic acid using carbon nanofibres on macrostructured supports.

Carbon nanofibres (CNFs) were grown on different macrostructured supports such as cordierite monoliths, carbon felts and sintered metal fibres. The resulting composites exhibited excellent resistance to attrition/corrosion and its porosity is mainly due to mesoporous structures. The CNF/structured materials were tested in the ozonation of oxalic acid in a conventional semi-batch reactor after being crushed to powder form, and in a newly designed reactor that may operate in semi-batch or continuous operation. The CNFs supported on the different structured materials exhibited high catalytic activity in the mineralization of oxalic acid.

Composites of manganese oxide with carbon materials as catalysts for the ozonation of oxalic acid.

Manganese oxide and manganese oxide-carbon composites were prepared and tested as catalysts for the removal of oxalic acid by ozonation. Their performances were compared with the parent carbon material (activated carbon or carbon xerogel) used to prepare the composites. Oxalic acid degradation by carbon materials is slower than that attained with manganese oxide or manganese oxide-carbon composites. A complete degradation after 90 and 45 min of reaction was obtained for carbon materials and for the catalysts containing manganese, respectively. The ozonation in the presence of the prepared composites are supposed to occur mainly by surface reactions, following a direct oxidation mechanism by molecular ozone and/or surface oxygenated radicals.

Mixture effects during the oxidation of toluene, ethyl acetate and ethanol over a cryptomelane catalyst.

The catalytic oxidation of two-component VOC mixtures (ethanol, ethyl acetate and toluene) was studied over cryptomelane. Remarkable mixture effects were observed on the activity and the selectivity. Toluene inhibits both ethyl acetate and ethanol oxidation, this effect being more evident in the case of ethyl acetate. For instance, the temperature for 100% conversion is about 210 °C when ethyl acetate is oxidised alone, and 250 °C or higher, when it is oxidised in mixtures with toluene. On the contrary, toluene oxidation is only slightly inhibited by the presence of ethyl acetate, while the presence of ethanol has a promoting effect. Concerning the mixtures of ethyl acetate and ethanol, both compounds have a mutual inhibitory effect, which is more evident in the case of ethyl acetate (the temperature for 100% conversion of ethyl acetate is about 45 °C higher when ethyl acetate is oxidised in mixtures with ethanol, while in the case of ethanol the corresponding increase is only 10 °C).

Cerium, manganese and cobalt oxides as catalysts for the ozonation of selected organic compounds.

Several metal oxides, as well as metal oxides supported on activated carbon, were assessed as ozonation catalysts for the removal of selected organic compounds. Two transition metals (Mn, Co) and one rare earth element (Ce) were chosen for the preparation of the two series of catalysts. These materials were used in the ozonation of two aromatic compounds (aniline and sulfanilic acid) and one textile azo dye (CI Acid Blue 113). The results were compared with those obtained with non-catalytic ozonation. All the tested materials were found to be effective ozonation catalysts. Among the metal oxides, those containing mixtures of cerium and manganese or cerium and cobalt enabled the highest mineralisation degrees. After 120 min of reaction the TOC removal achieved with Ce-Mn-O was 63% for sulfanilic acid and 67% for aniline, while Ce-Co-O allowed TOC removals of 58 and 66%, respectively. With single ozonation, the mineralisation of sulfanilic acid and aniline solutions was 34% and 40% after identical reaction period. Regarding the metal oxides supported on activated carbon, cerium and manganese oxides were, in general, the most active for the degradation of the studied compounds.

Decolourisation of dye solutions by oxidation with H(2)O(2) in the presence of modified activated carbons.

The decolourisation of dye solutions by oxidation with H(2)O(2), using activated carbon as catalyst, is studied. For this purpose, three different samples, mainly differing in the respective surface chemistries, were prepared and characterized. Moreover, this work involved three pH levels, corresponding to acid, neutral and alkaline solutions, and six dyes belonging to several classes. The catalytic decolourisation tests were performed in a laboratorial batch reactor. Adsorption on activated carbon and non-catalytic peroxidation kinetic experiments were also carried out in the same reactor, in order to compare the efficiencies of the three processes. The non-catalytic reaction is usually inefficient and, typically, adsorption presents a low level of decolourisation. In these cases, the combination of activated carbon with hydrogen peroxide may significantly enhance the process, since the activated carbon catalyses the decomposition of H(2)O(2) into hydroxyl radicals, which are very reactive. Based on the experiments with the different activated carbon samples, which have similar physical properties, it is proved that the surface chemistry of the catalyst plays a key role, being the basic sample the most active. This is discussed considering the involvement of the free electrons on the graphene basal planes of activated carbon as active centres for the catalytic reaction. Additionally, it is shown that the decolourisation is enhanced at high pH values, and a possible explanation for this observation, based on the proposed mechanism, is given.

Ozonation of aniline promoted by activated carbon.

The removal of aniline from aqueous solutions by simultaneous use of ozone and activated carbon was investigated at different solution pH. For comparative purposes, single ozonation and adsorption on activated carbon were carried out in the same experimental set-up. In order to evaluate the role of the activated carbon surface chemistry during ozonation, a commercial activated carbon, Norit GAC 1240 PLUS, was submitted to oxidation in the liquid phase with HNO(3). The texture and surface chemistry of the activated carbon samples were characterized. During ozonation, complete conversion of aniline was achieved after approximately 20 min, regardless of the presence of activated carbon. In all cases, several by-products were formed during ozonation. Nitrobenzene, o- and p-aminophenol were the primary aromatic oxidation by-products identified. In terms of TOC removal, best results were achieved by the simultaneous use of ozone and activated carbon. Though there is a strong contribution of adsorption, a considerable synergetic effect between ozone and activated carbon is observed. In general, activated carbon promotes the reaction of ozonation enhancing the efficiency of this treatment process. The basic activated carbon presented greater activity in this process leading to higher mineralization rates.

Adsorption of a reactive dye on chemically modified activated carbons--influence of pH.

The surface chemistry of a commercial activated carbon with a slightly basic nature was modified by appropriate treatments in order to obtain two additional samples, respectively with acidic and basic properties, without changing its textural parameters significantly. Different techniques (N2 adsorption at 77 K, temperature programmed desorption, and determination of acidity, basicity, and pH at the point of zero charge) were used to characterize the adsorbents. Kinetic and equilibrium adsorption data of a selected textile reactive dye (Rifafix Red 3BN, C.I. reactive red 241) on the mentioned materials were obtained at the pH values of 2, 7, and 12. The kinetic curves are fitted using the second-order model. The respective rate constants seem to diminish progressively with the initial concentration for the more diluted solutions tested, reaching a constant value at higher concentrations, which depends on the experimental system under consideration (adsorbent and pH). In general, the Langmuir model provides the best fit for the equilibrium data. The different uptakes obtained are discussed in relation to the surface chemical properties of the adsorbents. It is shown that the adsorption of the reactive (anionic) dye on the basic sample (prepared by thermal treatment under H2 flow at 700 degrees C) is favored. This conclusion is explained on the basis of the dispersive and electrostatic interactions involved. Moreover, it is also shown that the optimal adsorption condition for all the activated carbons tested corresponds to solution pH values not higher than the pH(pzc) of the adsorbents, which may be interpreted by taking into account the electrostatic forces present.

Adsorption of anionic and cationic dyes on activated carbons with different surface chemistries.

The influence of the surface chemical groups of an activated carbon on the removal of different classes of dyes is evaluated. Starting from the same material (NORIT GAC 1240 PLUS), the following treatments were carried out in order to produce a series of samples with different surface chemical properties but with no major differences in their textural properties: oxidation in the liquid phase with 6M HNO(3) and 10 M H(2)O(2) (acid materials) and heat treatment at 700 degrees C in H(2) or N(2) flow (basic materials). The specific micropores volume and mesopores surface area of the materials were obtained from N(2) adsorption equilibrium isotherms at 77K. The surface chemistry was characterised by temperature programmed desorption, by the determination of the point of zero charge (pH(pzc)) and by the evaluation of the acidity/basicity of the samples. Elemental and proximate analyses were also carried out. Equilibrium isotherms of selected dyes (an acid, a basic and a reactive dye) on the mentioned samples were obtained and the results discussed in relation to their surface chemistry. In general, the Langmuir model provided the best fit for the adsorption data. It is shown that the surface chemistry of the activated carbon plays a key role in dye adsorption performance. The basic sample obtained by thermal treatment under H(2) flow at 700 degrees C is the best material for the adsorption of all the tested dyes.

[Changes in cognitive function performance in patients after anesthesia]. / Alterações no desempenho de funções cognitivas em doentes submetidos a anestesia.

This study evaluates the mental performance of 112 patients (ASA grade 1 and 2) submitted to Orthopaedic, Urologic, Gynecologic, General and ENT surgery in Santo Antonio General Hospital. These patients received different types of anaesthesia: General Balanced Anaesthesia--GBA (n = 80), Total Intravenous Anaesthesia--TIVA (n = 17) and Regional Anaesthesia--RA (n = 15). Cognitive function was tested using the mini mental state test (MMS), which was done 24 hours before and 24 hours after anaesthesia. There was a high correlation between pre and postoperative MMS scores (R = 0.94). Patients in the GBA group show a significant (p < 0.001) decrease in cognitive performance 24 hours after surgery in comparison to the preoperative test. No differences were observed between the pre and postoperative MMS tests in the TIVA and RA groups.