Degradation of dipyrone via advanced oxidation processes using a cerium nanostructured electrocatalyst material

This work studied the degradation of dipyrone, via electrochemical processes and via electro-Fenton reaction using a 4% CeO2/C gas diffusion electrode (GDE) prepared via modified polymeric precursor method. This material was used to electrochemically generate H2O2 through oxygen reduction. The mean crystallite sizes estimated by the Scherrer equation for 4% CeO2/C were 4 nm for CeO2-x (0 4 4) and 5 nm for CeO2 (1 1 1) while using transmission electron microscopy (TEM) the mean nanoparticle size was 5.4 nm. X-ray photoelectron spectroscopy (XPS) measurements revealed nearly equal concentrations of Ce(III) and Ce(IV) species on carbon, which contained high oxygenated acid species like CO and OCO. Electrochemical degradation using Vulcan XC 72R carbon showed that the dipyrone was not removed during the two hour electrolysis in all applied potentials by electro-degradation. Besides, when the Fenton process was employed the degradation was much similar when using cerium catalysts but the mineralization reaches just to 50% at -1.1 V. However, using the CeO2/C GDE, in 20 min all of the dipyrone was degraded with 26% mineralization at -1.3 V and when the Fenton process was employed, all of the dipyrone was removed after 5 min with 57% mineralization at -1.1 V. Relative to Vulcan XC72R, ceria acts as an oxygen buffer leading to an increase in the local oxygen concentration, facilitating H2O2 formation and consequently improving the dipyrone degradation © 2013 Elsevier B.V. All rights reserved.

Effect of soaking time on the photoluminescence properties of cerium oxide nanoparticles

The structural and photoluminescence properties at room temperature of CeO2 nanoparticles synthesized by a microwave-assisted hydrothermal method (MAH) under different soaking times on KOH mineralizer added to a cerium ammonium nitrate aqueous solution were undertaken. X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Fourier transform Raman (FT-Raman) and photoluminescence (PL) measurements were employed. XRD revealed that the nanoparticles are free of secondary phases and crystallize in the cubic structure. The UV/vis absorption spectroscopy suggested the presence of intermediate energy levels in the band gap of structurally ordered powders. The most intense PL emission was obtained for nanoparticles which represent a lower particle size. © 2013 Elsevier Ltd and Techna Group S.r.l.

Influence of the preparation method and the support on H2O 2electrogeneration using cerium oxide nanoparticles

This work describes the influence of the preparation method and the carbon support using a low contentof cerium oxide nanoparticles (CeO2/C 4%) on H2O2electrogeneration via the oxygen reduction reac-tion (ORR). For this purpose, the polymeric precursor (PPM) and sol-gel (SGM) methods with Vulcan XC72R (V) and Printex L6 (P) supports were employed. The materials were characterized by X-ray diffrac-tion (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). TheXRD analysis identified two phases comprising CeO2and CeO 2-x. The smallest mean crystallite size wasexhibited for the 4% CeO2/C PPM P material, which was estimated using the Debye-Scherrer equation tobe 6 nm and 4 nm for the CeO2and the CeO 2-xphases, respectively, and was determined by TEM to be5.9 nm. XPS analysis was utilized to compare the oxygen content of the 4% CeO2/C PPM P to Printex L6.The electrochemical analysis was accomplished using a rotating ring-disk electrode. The results showedthat the 4% CeO2/C specimen, prepared by PPM and supported on Printex L6, was the best electrocatalystfor H2O2production in 1 mol L -1NaOH. This material showed the highest ring current, producing 88%H2O2and transferring 2.2 electrons per O 2molecule via the ORR at the lowest onset potential. Addition-ally, the ring-current of the 4% CeO2/C PPM P material was higher than that of Vulcan XC 72R and PrintexL6, the reference materials for H2O 2production, indicating the highest electrocatalytic activity for the 4%CeO2/C PPM P material. © 2013 Elsevier Ltd. All rights reserved.

Photoluminescence properties of praseodymium doped cerium oxide nanoparticles

The structural and photoluminescent properties at room temperature of CeO2 nanoparticles synthesized by a Microwave-Assisted Hydrothermal Method (MAH) under different praseodymium contents was undertaken. X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM), UV-vis Spectroscopy (UV-vis), Fourier Transform Raman (FT-Raman) and Photoluminescence (PL) measurements were employed. XRD revealed that the nanoparticles are free of secondary phases and crystallize in the cubic structure while FT-Raman revealed a typical scattering mode of fluorite type. The UV/vis absorption spectroscopy suggested the presence of intermediate energy levels in the band gap of structurally ordered powders. The most intense PL emission was obtained for nanoparticles which represent a lower particle size. © 2013 Elsevier Ltd and Techna Group S.r.l.

Caracterização de sistemas vítreos baseados no formador B2O3 e P2O5 dopados com CeO2

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Structural study of copper oxide supported on a ceria-modified titania catalyst system

A structural study of CuO supported on a CeO2-TiO2 system was undertaken using X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) techniques. The results of XRD revealed the presence of only two phases, TiO2 anatase and CeO2 cerianite. A trend towards smaller TiO2 crystallites was observed when cerium content increased. When the amount of cerium increased, Ti K-edge XANES analysis showed an increasing distortion of Ti sites. The results of Ce LIII-edge EXAFS showed that Ce atoms are coordinated by eight oxygen atoms at 2.32 Å. For the sample containing a small amount of cerium, the EXAFS analysis indicated that the local structure around Ce atoms was highly distorted. The catalysts presented quite different Cu K-edge XANES spectra compared to the spectra of the CuO and Cu2O reference compounds. The Cu-O mean bond length was close to that of the CuO and the Cu atoms in the catalysts are surrounded by approximately four oxygen atoms in their first shell. Copper supported on the ceria-modified titania support catalysts displayed a better performance in the methanol dehydrogenation when compared to copper supported only on titania or on ceria. © 2002 Plenum Publishing Corporation.

Preparation, structural characterization and catalytic properties of Co/CeO2 catalysts for the steam reforming of ethanol and hydrogen production

In this paper, Co/CeO2 catalysts, with different cobalt contents were prepared by the polymeric precursor method and were evaluated for the steam reforming of ethanol. The catalysts were characterized by N-2 physisorption (BET method), X-ray diffraction (XRD), UV-visible diffuse reflectance, temperature programmed reduction analysis (TPR) and field emission scanning electron microscopy (FEG-SEM). It was observed that the catalytic behavior could be influenced by the experimental conditions and the nature of the catalyst employed. Physical-chemical characterizations revealed that the cobalt content of the catalyst influences the metal-support interaction which results in distinct catalyst performances. The catalyst with the highest cobalt content showed the best performance among the catalysts tested, exhibiting complete ethanol conversion, hydrogen selectivity close to 66% and good stability at a reaction temperature of 600 degrees C. (c) 2012 Elsevier B.V. All rights reserved.

CuO-CeO2 catalysts synthesized in one-step: Characterization and PROX performance

PEM fuel cells seem to be the most affordable and commercially viable hydrogen-based cells, the biggest challenge being to obtain CO-free H-2 (<100 ppm) as the fuel. In this study, the use of CuO-CeO2 catalysts in preferential oxidation of CO to obtain CO-free H-2 (PROX reaction) was investigated. Ce1-xCuxO2 catalysts, with x (mol%) = 0, 0.01, 0.03, 0.05 and 0.10, were synthesized in one-step by the polymeric precursor method, to obtain a very fine dispersion and strong metal-support interaction, to favor active copper species and a preference for the PROX reaction. The results obtained from catalyzed reactions and characterization of the catalysts by XRD, Rietveld refinement, BET surface area, UV-Vis and TPR, suggest that this one-step synthesis method gives rise to catalysts with copper species selective for the PROX reaction, which reaches a maximum rate on Ce0.97Cu0.03O2 catalyst. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Low content cerium oxide nanoparticles on carbon for hydrogen peroxide electrosynthesis

A comparative study using different proportions of CeO2/C (4%, 9% and 13% CeO2) was performed to produce H2O2, a reagent used in the oxidation of organic pollutants and in electro-Fenton reactions for the production of the hydroxyl radical (OH center dot), a strong oxidant agent used in the electrochemical treatment of aqueous wastewater. The CeO2/C materials were prepared by a modified polymeric precursor method (PPM). X-ray diffraction analysis of the CeO2/C prepared by the PPM identified two phases. CeO2 and CeO2. The average size of the crystallites in these materials was close to 7 nm. The kinetics of the oxygen reduction reaction (ORR) were evaluated by the rotating ring-disk electrode technique. The results showed that the 4% CeO2/C prepared by the PPM was the best composite for the production of H2O2 in a 1 mol L-1 NaOH electrolyte solution. For this material, the number of electrons transferred and the H2O2 percentage efficiency were 3.1 and 44%, respectively. The ring-current of the 4% CeO2/C was higher than that of Vulcan carbon, the reference material for H2O2 production, which produced 41% H2O2 and transferred 3.1 electrons per molecule of oxygen. The overpotential for this reaction on the ceria-based catalyst was substantially lower (approximately 200 mV), demonstrating the higher catalytic performance of this material. Gas diffusion electrodes (GDE) containing the catalyst were used to evaluate the real amount of H2O2 produced during exhaustive electrolysis. The 4% CeO2/C GDE produced 871 mg L-1 of H2O2, whereas the Vulcan carbon GDE produced a maximum amount of only 407 mg L-1. Thus, the 4% CeO2/C electrocatalyst prepared by the PPM is a promising material for H2O2 electrogeneration in alkaline media. (C) 2011 Elsevier B.V. All rights reserved.

Chemistry on manganese nodules from the Pacific Ocean

Three manganese nodules from the Pacific Ocean have been analysed for 35 elements by using mainly spectrophotometric and spectrographic methods. Cu, Co, Ni, Zn, and Pb were found in amounts approaching 1 %, which far exceeds their average concentrations in igneous rocks. On the other hand, elements having readily hydrolysable ions, such as Ga, Sc, Zr, Y, La and Ti, are present only in amounts comparable with their concentrations in igneous rocks. Sb, Bit Be, and Cr were not detected. The hydrochloric acid-insoluble fraction of nodules is practically free of the heavy metals that are characteristic of the acid-soluble fraction; it consists principally of clay minerals, together with lesser amounts of quartz, apatite, biotite and sodium and potassium felspars.

Ni-CeO2/C Catalysts with Enhanced OSC for the WGS Reaction

In this work, the WGS performance of a conventional Ni/CeO2 bulk catalyst is compared to that of a carbon-supported Ni-CeO2 catalyst. The carbon-supported sample resulted to be much more active than the bulk one. The higher activity of the Ni-CeO2/C catalyst is associated to its oxygen storage capacity, a parameter that strongly influences the WGS behavior. The stability of the carbon-supported catalyst under realistic operation conditions is also a subject of this paper. In summary, our study represents an approach towards a new generation of Ni-ceria based catalyst for the pure hydrogen production via WGS. The dispersion of ceria nanoparticles on an activated carbon support drives to improved catalytic skills with a considerable reduction of the amount of ceria in the catalyst formulation.

CeO2-promoted Ni/activated carbon catalysts for the water–gas shift (WGS) reaction

The low temperature water–gas shift (WGS) reaction has been studied over carbon-supported nickel catalysts promoted by ceria. To this end, cerium oxide has been dispersed (at different loadings: 10, 20, 30 and 40 wt.%) on the activated carbon surface with the aim of obtaining small ceria particles and a highly available surface area. Furthermore, carbon- and ceria-supported nickel catalysts have also been studied as references. A combination of N2 adsorption analysis, powder X-ray diffraction, temperature-programmed reduction with H2, X-ray photoelectron spectroscopy and TEM analysis were used to characterize the Ni–CeO2 interactions and the CeO2 dispersion over the activated carbon support. Catalysts were tested in the low temperature WGS reaction with two different feed gas mixtures: the idealized one (with only CO and H2O) and a slightly harder one (with CO, CO2, H2, and H2O). The obtained results show that there is a clear effect of the ceria loading on the catalytic activity. In both cases, catalysts with 20 and 10 wt.% CeO2 were the most active materials at low temperature. On the other hand, Ni/C shows a lower activity, this assessing the determinant role of ceria in this reaction. Methane, a product of side reactions, was observed in very low amounts, when CO2 and H2 were included in the WGS feed. Nevertheless, our data indicate that the methanation process is mainly due to CO2, and no CO consumption via methanation takes place at the relevant WGS temperatures. Finally, a stability test was carried out, obtaining CO conversions greater than 40% after 150 h of reaction.

The influence of promoters (Zr, La, Tb, Pr) on the catalytic performance of CuO-CeO2 systems for the preferential oxidation of CO in the presence of CO2 and H2O

CuO supported on CeO2 and Ce0.9X0.1O2, where X is Zr, La, Tb or Pr, were synthesized using nitrate precursors, giving rise ceria based materials with a small particle size which interact with CuO species generating a high amount of interfacial sites. The incorporation of cations to the ceria framework modifies the CeO2 lattice parameter, improving the redox behavior of the catalytic system. The catalysts were characterized by X-ray fluorescence spectrometry (XRFS), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), Raman spectroscopy, thermoprogrammed reduction with H2 (H2-TPR) and X-ray photoelectron spectroscopy (XPS). The catalysts were tested in the preferential oxidation of CO under a H2-rich stream (CO-PROX), reaching conversion values higher than 95% between 115 and 140 °C and being the catalyst with 6 wt.% of Cu supported on Ce0.9Zr0.1O2 (sample 6CUZRCE) the most active catalyst. The influence of the presence of CO2 and H2O was also studied simulating a PROX unit, taking place a decrease of the catalytic activity due to the inhibitor effect both CO2 and H2O.

Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands

A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.