THENNER SILVA RODRIGUES
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Artigo IPEN-doc 25155 Sub-15 nm CeO2 nanowires as an efficient nonnoble metal catalyst in the room-temperature oxidation of aniline2018 - 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.Artigo IPEN-doc 25045 Ni supported Ce0.9Sm0.1O2-δ nanowires2019 - 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.Artigo IPEN-doc 24862 Marrying SPR excitation and metal–support interactions2018 - GEONMONOND, RAFAEL S.; QUIROZ, JHON; ROCHA, GUILHERME F.S.R.; OROPEZA, FREDDY E.; RANGEL, CLARA J.; RODRIGUES, THENNER S.; HOFMANN, JAN P.; HENSEN, EMIEL J.M.; ANDO, ROMULO A.; CAMARGO, PEDRO H.C.Plasmonic catalysis takes advantage of the surface plasmon resonance (SPR) excitation to drive or accelerate chemical transformations. In addition to the plasmonic component, the control over metal–support interactions in these catalysts is expected to strongly influence the performances. For example, CeO2 has been widely employed towards oxidation reactions due to its oxygen mobility and storage properties, which allow for the formation of Ce3+ sites and adsorbed oxygen species from metal–support interactions. It is anticipated that these species may be activated by the SPR excitation and contribute to the catalytic activity of the material. Thus, a clear understanding of the role played by the SPR-mediated activation of surface oxide species at the metal–support interface is needed in order to take advantage of this phenomenon. Herein, we describe and quantify the contribution from active surface oxide species at the metal–support interface (relative to O2 from air) to the activities in green SPR-mediated oxidation reactions. We employed CeO2 decorated with Au NPs (Au/CeO2) as a model plasmonic catalyst and the oxidation of p-aminothiophenol (PATP) and aniline as proof-of-concept transformations. We compared the results with SiO2 decorated with Au NPs (Au/SiO2), in which the formation of surface oxide species at the metal–support interface is not expected. We found that the SPR-mediated activation of surface oxide species at the metal–support interface in Au/CeO2 played a pivotal role in the detected activities, being even higher than the contribution coming from the activation of O2 from air.