THENNER SILVA RODRIGUES

THENNER SILVA RODRIGUES

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Controlling the sintering of ceria by shape-controlled synthesis of nanoparticles
2019 - FONSECA, FABIO C.; MACHADO, MARINA F.S.; MORAES, LETICIA P.R.; RODRIGUES, THENNER S.; KABIR, AHSANUL; MARANI, DEBORA; VAN NONG, NGO; ESPOSITO, VINCENZO
The influence of surface energy of Gd-doped CeO2 nanometric crystals with different morphologies on mass diffusion mechanisms is studied. Depending on the starting morphology (nanocubes, nanorods, and random nanoparticles) extremely different microstructures, ranging from rapidly densified to thermodynamically stable porous structures. We investigate Gd-doped ceria (10% molar, GDC) both for its relevance in several chemical, environmental and energy technologies, and because the extensive knowledge on diffusion effects ruling this compound. We synthesized GDC as nanocubes (NC) and nanorods (NR) by a hydrothermal method whereas randomly oriented nanoparticles (RD) were obtained by co-precipitation. All samples were measured as single phase GDC powders with narrow nanoparticle size distributions. The high surface area NR exhibit lower green density as compared to NC. Dilatometric analyses revealed that NR have a pronounced linear retraction starting at low temperatures (~200°C) with maximum sintering activity at ~1100°C. High surface energy in NRs leads to a rapid rod to sphere transformation as well as to a rapid densification despite relatively low green density. On the other hand, the solid state diffusion in NCs is significantly inhibited, as confirmed by the highly porous microstructure of sintered samples. The results indicated the possibility of controlling microstructure of GDC by defining the shape of nanoparticles for different application in which dense or stable pores are required.
Lowering the sintering temperature of a SOFC by morphology control of the electrolyte powder
2019 - MACHADO, M.; MORAES, L.P.R.; RODRIGUES, L.N.; RODRIGUES, T.S.; FONSECA, F.C.
Solid oxide fuel cells are fabricated by two-step sintering at low temperature by controlling the morphology of the gadolinium-doped cerium oxide (GDC) electrolyte powders. The GDC electrolyte was synthesized by a hydrothermal route to obtain highly reactive nanorods that can fully densify at temperatures around 1150 °C. The developed system consists of the GDC electrolyte support, lanthanum strontium cobalt ferrite (LSCF) cathode and Ni/GDC anode. The electrolyte support was prepared by uniaxial die pressing and sintered at 1150 °C, and fuel cells were obtained by co-sintering electrode layers at the same temperature. The performance of the cell was evaluated in hydrogen at intermediate temperatures (IT). The experimental results indicate that high-performance IT-SOFC can be obtained at low sintering temperatures by controlling the morphology of electrolyte powder.
Tuning diffusion paths in shaped ceria nanocrystals
2019 - ESPOSITO, VINCENZO; KABIR, AHSANUL; ROSA, MASSIMO; NONG, NGO V.; RODRIGUES, THENNER S.; RODRIGUES, LAYS N.; MACHADO, MARINA F.S.; MORAES, LETICIA P.R.; MARANI, DEBORA; FONSECA, FABIO C.
Mass diffusion controls material structuring from the atomic to the macro-scale defining properties and functionalities. We show here that surface energy in Ce0.9Gd0.1O3-d shaped nanocrystals, i.e. nanocubes, nanorods and spherical nanoparticles, can control solid state diffusion mechanisms over a long range, leading to extreme microstructural diversity.
Ethanol steam reforming
2019 - RODRIGUES, THENNER S.; SILVA, FELIPE A. e; CANDIDO, EDUARDO G.; SILVA, ANDERSON G.M. da; GEONMONOND, RAFAEL dos S.; CAMARGO, PEDRO H.C.; LINARDI, MARCELO; FONSECA, FABIO C.
We reported herein a systematic investigation on how the nature of the support affected the catalytic performances of Rh nanoparticles. The prepared catalysts were denoted as Rh/MxOy, where M corresponded to Ce, Ti, Si, Zn, and Al, and Rh was Rh3+ reduction to Rh nanoparticles on the surface of oxides. This strategy was performed in a single step using urea as a mediator and in the absence of any other stabilizer or capping agent. The Rh nanoparticles displayed relatively similar sizes, shapes, and uniform distribution over the supports, differing only in terms of the nature of the support. This strongly affected the metal–support interaction between Rh nanoparticles and the respective oxides, leading to significant differences in their catalytic performances toward the ethanol steam reforming. Here, not only the catalytic activity (in terms of ethanol conversion) was affected, but both the selectivity and stability were also influenced by the nature of the oxide support. Interestingly, the reaction paths as well as the deactivation profile were completely changed as function of the employed support. Such differences were associated with differences in the oxygen storage, oxygen mobility, and acidity/basicity of the supports. We believe that our results can contribute to the development and understanding of Rh-supported catalysts for the applications toward gas-phase transformations such as the ethanol steam reforming reaction.
Sub-15 nm CeO2 nanowires as an efficient nonnoble metal catalyst in the room-temperature oxidation of aniline
2018 - SILVA, ANDERSON G.M. da; BATALHA, DANIEL C.; RODRIGUES, THENNER S.; CANDIDO, EDUARDO G.; LUZ, SULUSMON C.; FREITAS, ISABEL C. de; FONSECA, FABIO C.; OLIVEIRA, DANIELA C. de; TAYLOR, JASON G.; TORRESI, SUSANA I.C. de; CAMARGO, PEDRO H.C.; FAJARDO, HUMBERTO V.
We described herein the facile synthesis of sub-15 nm CeO2 nanowires based on a hydrothermal method without the use of any capping/stabilizing agent, in which an oriented attachment mechanism took place during the CeO2 nanowire formation. The synthesis of sub-15 nm CeO2 nanowires could be achieved on relatively large scales (∼2.6 grams of nanowires per batch), in high yields (>94%), and at low cost. To date, there are only a limited number of successful attempts towards the synthesis of CeO2 nanowires with such small diameters, and the reported protocols are typically limited to low amounts. The nanowires displayed uniform shapes and sizes, high surface areas, an increased number of oxygen defects sites, and a high proportion of Ce3+/Ce4+ surface species. These features make them promising candidates for oxidation reactions. To this end, we employed the selective oxidation of aniline as a model transformation. The sub-15 nm CeO2 nanowires catalyzed the selective synthesis of nitrosobenzene (up to 98% selectivity) from aniline at room temperature using H2O2 as the oxidant. The effect of solvent and temperature during the catalytic reaction was investigated. We found that such parameters played an important role in the control of the selectivity. The improved catalytic activities observed for the sub-15 nm nanowires could be explained by: i) the uniform morphology with a typical dimension of 11 ± 2 nm in width, which provides higher specific surface areas relative to those of conventional catalysts; ii) the significant concentration of oxygen vacancies and high proportion of Ce3+/Ce4+ species at the surface that represent highly active sites towards oxidation reactions; iii) the crystal growth along the (110) highly catalytically active crystallographic directions, and iv) the mesoporous surface which is easily accessible by liquid substrates. The results reported herein demonstrated high activities under ambient conditions, provided novel insights into selectivities, and may inspire novel metal oxide-based catalysts with desired performances.
Synthesis of highly dispersed gold nanoparticles on Al2O3, SiO2, and TiO2 for the solvent-free oxidation of benzyl alcohol under low metal loadings
2019 - GUALTEROS, JESUS A.D.; GARCIA, MARCO A.S.; SILVA, ANDERSON G.M. da; RODRIGUES, THENNER S.; CANDIDO, EDUARDO G.; SILVA, FELIPE A. e; FONSECA, FABIO C.; QUIROZ, JHON; OLIVEIRA, DANIELA C. de; TORRESI, SUSANA I.C. de; MOURA, CARLA V.R. de; CAMARGO, PEDRO H.C.; MOURA, EDMILSON M. de
We reported the organic template-free synthesis of gold (Au) nanoparticles (NPs) supported on TiO2, SiO2, and Al2O3 displaying uniform Au sizes and high dispersions over the supports. The Au-based catalysts were prepared by a deposition– precipitation method using urea as the precipitating agent. In the next step, the solvent-free oxidation of benzyl alcohol was investigated as model reaction using only 0.08–0.05 mol% of Au loadings and oxygen (O2) as the oxidant. Very high catalytic performances (TOF up to 443,624 h-1) could be achieved. Specifically, we investigated their catalytic activities, selectivity, and stabilities as well as the role of metal–support interactions over the performances. The conversion of the substrate was found to be associated with the nature of the employed support as the Au NPs presented similar sizes in all materials. A sub-stoichiometric amount of base was sufficient for the catalyst activation and the observation of the catalysts profile over the time enable insights on their recyclability performances. We believe this reported method represents a facile approach for the synthesis of uniform Au-supported catalysts displaying high performances.
Ni supported Ce0.9Sm0.1O2-δ nanowires
2019 - RODRIGUES, THENNER S.; MOURA, ARTHUR B.L. de; SILVA, FELIPE A. e; CANDIDO, EDUARDO G.; SILVA, ANDERSON G.M. da; OLIVEIRA, DANIELA C. de; QUIROZ, JHON; CAMARGO, PEDRO H.C.; BERGAMASCHI, VANDERLEI S.; FERREIRA, JOAO C.; LINARDI, MARCELO; FONSECA, FABIO C.
We reported herein the synthesis in high yields (> 97%) of Ce0.9Sm0.1O2-δ nanowires displaying well-defined shape, size, and composition by a simple, fast, and low-cost two-step hydrothermal method. The Ce0.9Sm0.1O2-δ nanowires synthesis was followed by the wet impregnation of Ni without the utilization of any stabilizing agent. The Ni/Ce0.9Sm0.1O2-δ nanowires showed higher surface area, high concentration of oxygen vacancies at surface, and finely dispersed Ni particles with significantly higher metallic surface area as compared with catalysts prepared from commercial materials with similar compositions. Such unique and improved properties are reflected on the catalytic performance of the Ni/Ce0.9Sm0.1O2-δ nanowires towards ethanol steam reforming. The nanowires exhibited high yields for hydrogen production (∼60% of selectivity) and an exceptional stability with no loss of activity after 192 h of reaction at 550 °C. The reported results provide insights and can inspire highyield production of nanostructured catalysts displaying controlled and superior properties that enable practical applications in heterogeneous catalysis.
Hardwired for success
2017 - RODRIGUES, THENNER S.; MOURA, ARTHUR B.; SILVA, FELIPE A. e; CANDIDO, EDUARDO G.; BERGAMASCHI, VANDERLEI S.; FERREIRA, JOAO C.; LINARDI, MARCELO; FONSECA, FABIO C.
CeO2-based nanomaterials have been extensively employed in catalysis and industry, showing excellent performances towards a variety of applications. In the past few decades, great developments have been reported associating the properties of nanostructured CeO2 with its catalytic performances. Thus, an intense research in this field have been performed in order to increasingly improve the performances of these nanomaterials such as the precise control over their structures, morphologies, compositions, among others. We propose herein, the synthesis of a novel well-defined Sm2O3-doped CeO2 nanowires decorated with nickel nanoparticles as a novel catalyst with outstanding performance towards ethanol steam reforming (ESR). In order to address these challenges, we were inspired by a well-established hydrothermal method for the synthesis of CeO2 nanowires. Herein, through simple modifications in the original protocol allowed us the obtaining in high yield (97%) extremely well-defined CeO2-Sm2O3 nanowires exhibiting uniform distributions in lengths and diameters. XRD results (Figure 1A) suggested the introduction of Sm species into the CeO2 crystal lattices, in which the quantitative Sm3+(aq) conversion achieved 10 mol%, as corroborated by ICP-OES analysis. The resulting CeO2-Sm2O3 nanowires were then employed as support for the Ni incorporation (1 wt%) by a wet impregnation approach, and the obtained catalyst (Figure 1B) was evaluated towards the ESR displaying an exceptional stability even after 100 hours of process at 550 °C. More specifically, 100 % of ethanol conversion was observed with the formation of only H2 and CO2 (ESR products) and CO and CH4 as byproducts (both in low concentrations), indicating a good selectivity for ESR compared to the most recent literature. The characterization data for the Ni/CeO2-Sm2O3 nanowires after catalytic experiment (Figure 1C) indicated that, even after 100 hours at 550 °C, no loss of shape was observed as well as no carbon structures formation justifying the exceptional observed stability.