CeO2 nanoparticles synthesized by a microwave-assisted hydrothermal method: evolution from nanospheres to nanorods

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

Synthesis of PTSH-modified CeO2 nanoparticles: Effect of the modifier on structure, optical properties, and dispersibility

CeO2 nanoparticles were synthesized by the precipitation method and modified with para-toluene sulfonic acid (PTSH), either in situ or post-synthesis. The presence of PTSH in the samples was confirmed by FTIR. PXRD and FTIR analyses showed that the post-synthesis PTSH modification altered the CeO2 structure, whereas the in situ modification maintained intact the crystalline structure and UV-vis absorbance properties. For both in situ and post-synthesis modifications, TEM images revealed the presence of nanoparticles that were 5nm in size. The dispersibility of the in situ PTSH-modified material in a hydrophilic ureasil-poly(ethylene oxide) matrix was investigated using SAXS measurements, which indicated that CeO2 nanoparticles modified with PTSH in situ were less aggregated within the matrix, compared to unmodified CeO2 nanoparticles. © 2013 Elsevier B.V.

Influence of solvent on the morphology and photocatalytic properties of ZnS decorated CeO2 nanoparticles

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

CeO2 nanoparticles synthesized by a microwave-assisted hydrothermal method: evolution from nanospheres to nanorods

Ceria (CeO2) plays a vital role in emerging technologies for environmental and energy-related applications. The catalytic efficiency of ceria nanoparticles depends on its morphology. In this study, CeO2 nanoparticles were synthesized by a microwave-assisted hydrothermal method under different synthesis temperatures. The samples were characterized by X-ray diffraction, transmission electron microscopy, Raman scattering spectroscopy, electron paramagnetic resonance spectroscopy and by the Brunauer-Emmett-Teller method. The X-ray diffraction and Raman scattering results indicated that all the synthesized samples had a pure cubic CeO2 structure. Rietveld analysis and Raman scattering also revealed the presence of structural defects due to an associated reduction in the valence of the Ce4+ ions to Ce3+ ions caused by an increasing molar fraction of oxygen vacancies. The morphology of the samples was controlled by varying the synthesis temperature. The TEM images show that samples synthesized at 80 degrees C consisted of spherical particles of about 5 nm, while those synthesized at 120 degrees C presented a mix of spherical and rod-like nanoparticles and the sample synthesized at 160 degrees C consisted of nanorods with 10 nm average diameter and 70 nm length. The microwave-assisted method proved to be highly efficient for the synthesis of CeO2 nanoparticles with different morphologies.

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.

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.

Estudo das propriedades óticas e fotoluminescentes das nanopartículas do CeO2 modificadas com La pelo método hidrotermal assistido por microondas

Pós-graduação em Engenharia Mecânica - FEG

Preparation and characterization of ceria nanospheres by microwave-hydrothermal method

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

Influence of mineralizer agents on the growth of crystalline CeO 2 nanospheres by the microwave-hydrothermal method

Cystalline ceria (CeO2) nanoparticles have been synthesized by a simple and fast microwave-assisted hydrothermal (MAH) under NaOH, KOH, and NH4OH mineralizers added to a cerium ammonium nitrate aqueous solution. The products were characterized by X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Fourier transformed-IR and Raman spectroscopies. Rietveld refinement reveals a cubic structure with a space group Fm3m while infrared data showed few traces of nitrates. Field emission scanning microcopy (FEG-SEM) revealed a homogeneous size distribution of nanometric CeO2 nanoparticles. The MAH process in KOH and NaOH showed most effective to dehydrate the adsorbed water and decrease the hydrogen bonding effect leaving a weakly agglomerated powder of hydrated ceria. TEM micrographs of CeO2 synthesized under MAH conditions reveal particles well-dispersed and homogeneously distributed. The MAH enabled cerium oxide to be synthesized at 100 °C for 8 min. © 2012 Elsevier B.V. All rights reserved.

Atmospheric corrosion of quaternary bronzes (Cu-Sn-Zn-Pb): laboratory tests (accelerated ageing in wet & dry conditions)and field studies (the Bottego monument in Parma, Italy).

The interactions between outdoor bronzes and the environment, which lead to bronze corrosion, require a better understanding in order to design effective conservation strategies in the Cultural Heritage field. In the present work, investigations on real patinas of the outdoor monument to Vittorio Bottego (Parma, Italy) and laboratory studies on accelerated corrosion testing of inhibited (by silane-based films, with and without ceria nanoparticles) and non-inhibited quaternary bronzes are reported and discussed. In particular, a wet&dry ageing method was used both for testing the efficiency of the inhibitor and for patinating bronze coupons before applying the inhibitor. A wide range of spectroscopic techniques has been used, for characterizing the core metal (SEM+EDS, XRF, AAS), the corroded surfaces (SEM+EDS, portable XRF, micro-Raman, ATR-IR, Py-GC-MS) and the ageing solutions (AAS). The main conclusions were: 1. The investigations on the Bottego monument confirmed the differentiation of the corrosion products as a function of the exposure geometry, already observed in previous works, further highlighting the need to take into account the different surface features when selecting conservation procedures such as the application of inhibitors (i.e. the relative Sn enrichment in unsheltered areas requires inhibitors which effectively interact not only with Cu but also with Sn). 2. The ageing (pre-patination) cycle on coupons was able to reproduce the relative Sn enrichment that actually happens in real patinated surfaces, making the bronze specimens representative of the real support for bronze inhibitors. 3. The non-toxic silane-based inhibitors display a good protective efficiency towards pre-patinated surfaces, differently from other widely used inhibitors such as benzotriazole (BTA) and its derivatives. 4. The 3-mercapto-propyl-trimethoxy-silane (PropS-SH) additivated with CeO2 nanoparticles generally offered a better corrosion protection than PropS-SH.

Synthesis of Nb(2)O(5)center dot nH(2)O nanoparticles by water-in-oil microemulsion

Hydrous niobium oxide (Nb(2)O(5)center dot nH(2)O) nanoparticles had been Successfully prepared by water-in-oil microemulsion. They were characterized by X-ray diffraction (XRD), thermal analysis (TG/DTG), Fourier transform infrared spectroscopy (FTIR), BET surface area measurement, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The results showed that the nanoparticle was exactly Nb(2)O(5)center dot nH(2)O with spherical shape. Their BET surface area was 60 m(2) g(-1). XRD results showed that Nb(2)O(5)center dot nH(2)O nanoparticles with crystallite size in nanometer scale were formed. The crystallinity and crystallity size increased with increasing annealing temperature. TT-phase of Nb(2)O(5) was obtained when the sample is annealed at 550 degrees C. (C) 2009 Elsevier B.V. All rights reserved.

Redox behavior of the model catalyst Pd/CeO2-x/Pt(111)

Photoelectron spectroscopy and scanning tunneling microscopy have been used to investigate how the oxidation state of Ce in CeO2-x(111) ultrathin films is influenced by the presence of Pd nanoparticles. Pd induces an increase in the concentration of Ce3+ cations, which is interpreted as charge transfer from Pd to CeO2-x(111) on the basis of DFT+U calculations. Charge transfer from Pd to Ce4+ is found to be energetically favorable even for individual Pd adatoms. These results have implications for our understanding of the redox behavior of ceria-based model catalyst systems.

Microstructural and morphological analysis of pure and Ce-doped tin dioxide nanoparticles

Structural morphological studies in pure and Ce-doped tin dioxide nanoparticles with high stability against particle growth were performed in samples, obtained using the polymeric precursor method and prepared at different annealing temperatures. A Ce-rich surface layer was used to control the particle size and stabilize SnO2 against particle growth. The formation of this segregated layer can contribute to a decreased surface energy, acting in the driving force, or reducing the surface mobility. Only the cassiterite SnO2 phase was observed below 1000 degreesC and a secondary phase (CeO2) was observed for the Ce-doped SnO2 at temperatures higher than 1000 degreesC, when de-mixing process occurs. The evolution of crystallite size, microstrain and morphology of the nanoparticles with annealing temperatures was investigated by X-ray diffraction (XRD), associated to Rietveld refinements, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). (C) 2002 Elsevier B.V. Ltd. All rights reserved.

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.

Nanopartículas de CeO2 modificadas com Er obtidas pelo método hidrotermal microondas: estudo fotoluminescente

The development of nanostructured materials have aroused great interest of the industries all over the country, since they enable the development of devices that can be used as gate insulators on silicon transistors, electrochromic devices, solid electrolyte oxygen sensors and as a photoluminescent materials . In this project, it is proposed to investigate the optical properties of CeO2 modified with rare earth Er processed in hydrothermal-microwave. The synthesis of one-dimensional nanostructures (1D) was measured from dilute aqueous solutions of acids and salts of starting reagents in the presence of chemical basis, after these aqueous solutions were processed on hydrothermal-microwave to particle growth. The particles obtained after processing were characterized by X-ray Diffraction, Rietveld Analysis and Raman Spectroscopy. The particle morphology was observed by scanning electron microscopy with field emission gun. The synthesis of 1D nanostructures are evaluated for different surfactants and starting precursors (ceria different salts), pH, temperature and pressure which can modify the morphology of the nanostructures. Combining laboratory experiments and theoretical calculations it was desired to understand the organization of the nanoparticles and their resulting structure. Strict control of chemical homogeneity, crystal structure, microstructure and interaction of the CeO2 cluster with different surfactants using the Hartree-Fock method, was intended to obtain properties compatible with their use in catalysts and optical devices. The use of mineralizer agent KOH and 8 minutes of processing time synthesis conditions were chosen to evaluate the effect of Er dopant. It has been proved that this doping with rare earth increases the photoluminescent properties of the compound obtained without change the structural and morphological propreties of ceria