Lucas L. R. Vono

Superparamagnetic nanoparticle-supported palladium: a highly stable magnetically recoverable and reusable catalyst for hydrogenation reactions

Here we present a magnetically recoverable palladium catalyst prepared by immobilization of palladium over silica-coated magnetite nanoparticles. The catalyst reduced by molecular hydrogen contains palladium nanoparticles well distributed and stabilized in the magnetizable support surfaces and converts cyclohexene to cyclohexane under mild reaction conditions (75 °C and 6 atm) with TOF of 11 500 h−1. The catalyst was easily recovered with a permanent magnet in the reactor wall and reused for up to 20 recycles of 2500 TON each without any significant loss in catalytic activity, demonstrating an efficient recycling process for hydrogenation reactions.

Protoporphyrin IX Nanoparticle Carrier: Preparation, Optical Properties, and Singlet Oxygen Generation

The present study is focused on developing a nanoparticle carrier for the photosensitizer protoporphyrin IX for use in photodynamic therapy. The entrapment of protoporphyrin IX (Pp IX) in silica spheres was achieved by modification of Pp IX molecules with an organosilane reagent. The immobilized drug preserved its optical properties and the capacity to generate singlet oxygen, which was detected by a direct method from its characteristic phosphorescence decay curve at near-infrared and by a chemical method using 1,3-diphenylisobenzofuran to trap singlet oxygen. The lifetime of singlet oxygen when a suspension of Pp IX-loaded particles in acetonitrile was excited at 532 nm was determined as 52 micros, which is in good agreement with the value determined for methylene blue in acetonitrile solution under the same conditions. The Pp IX-loaded silica particles have an efficiency of singlet oxygen generation (eta Delta) higher than the quantum yield of free porphyrins. This high efficiency of singlet oxygen generation was attributed to changes on the monomer-dimer equilibrium after photosentisizer immobilization.

Recent advances in the development of magnetically recoverable metal nanoparticle catalysts

O objetivo deste Account e fornecer uma visao geral de nossas atividades atuais de pesquisa, as quais envolvem a sintese e modificacao de nanomateriais superparamagneticos para aplicacao na area de separacao magnetica e catalise. Primeiramente, uma introducao ao magnetismo e a separacao magnetica e feita. Em seguida, estrategias sinteticas que tem sido desenvolvidas para gerar nanoparticulas superparamagneticas revestidas esfericamente por silica e outros oxidos, com destaque a sistemas bem caracterizados e preparados por metodologias que geram amostras de elevada qualidade e que, a principio, podem ser produzidas em maior escala, sao discutidas. Uma serie de catalisadores magneticamente recuperaveis preparados em nosso grupo de pesquisa pela combinacao unica de suportes superparamagneticos e nanoparticulas metalicas e destacada. Este Account e concluido com observacoes pessoais e perspectivas neste campo de pesquisa. The aim of this Account is to provide an overview of our current research activities on the design and modification of superparamagnetic nanomaterials for application in the field of magnetic separation and catalysis. First, an introduction of magnetism and magnetic separation is done. Then, the synthetic strategies that have been developed for generating superparamagnetic nanoparticles spherically coated by silica and other oxides, with a focus on well characterized systems prepared by methods that generate samples of high quality and easy to scale-up, are discussed. A set of magnetically recoverable catalysts prepared in our research group by the unique combination of superparamagnetic supports and metal nanoparticles is highlighted. This Account is concluded with personal remarks and perspectives on this research field.

Easy Access to Metallic Copper Nanoparticles with High Activity and Stability for CO Oxidation.

Copper catalysts are very promising, affordable alternatives for noble metals in CO oxidation; however, the nature of the active species remains unclear and differs throughout previous reports. Here, we report the preparation of 8 nm copper nanoparticles (Cu NPs), with high metallic content, directly deposited onto the surface of silica nanopowders by magnetron sputtering deposition. The as-prepared Cu/SiO2 contains 85% Cu0 and 15% Cu2+ and was enriched in the Cu0 phase by H2 soft pretreatment (96% Cu0 and 4% Cu2+) or further oxidized after treatment with O2 (33% Cu0 and 67% Cu2+). These catalysts were studied in the catalytic oxidation of CO under dry and humid conditions. Higher activity was observed for the sample previously reduced with H2, suggesting that the presence of Cu-metal species enhances CO oxidation performance. Inversely, a poorer performance was observed for the sample previously oxidized with O2. The presence of water vapor caused only a small increase in the temperature require for the reaction to reach 100% conversion. Under dry conditions, the Cu NP catalyst was able to maintain full conversion for up to 45 h at 350 °C, but it deactivated with time on stream in the presence of water vapor.

Taking advantage of a terpyridine ligand for the deposition of Pd nanoparticles onto a magnetic material for selective hydrogenation reactions

A hybrid terpyridine ligand was designed to functionalize a magnetic support constituted of magnetite cores surrounded by a silica shell with the aim of improving the stabilization of supported-palladium nanoparticles for the later application of the obtained composite nanomaterial in hydrogenation catalysis. The preparation of the nanomaterial was performed by direct decomposition of the organometallic complex [Pd2(dba)3] on the terpyridine-modified magnetic support providing well-dispersed Pd NPs of 2.5 ± 0.6 nm mean size. This new nanomaterial is a highly active catalyst for the hydrogenation of cyclohexene under mild conditions reaching turnover frequencies up to ca. 58 000 h−1 or 129 000 h−1 when corrected for surface Pd atoms. Furthermore, in the hydrogenation of β-myrcene, this nanocatalyst is highly selective for the formation of monohydrogenated compounds. When compared to a similar nanocatalyst consisting of palladium nanoparticles supported on an amino-modified magnetic support or on Pd/C, the activity and selectivity of the nanocatalyst are largely increased. These results show how the design of an appropriate hybrid ligand used to functionalize the support can strongly influence the catalytic properties of supported metal nanoparticles.

Polymer versus phosphine stabilized Rh nanoparticles as components of supported catalysts: implication in the hydrogenation of cyclohexene model molecule

The solution synthesis of rhodium nanoparticles (Rh NPs) was achieved from the organometallic complex [Rh(η3-C3H5)3] under mild reaction conditions in the presence of a polymer (PVP), a monophosphine (PPh3) and a diphosphine (dppb) as a stabilizer, leading to very small Rh NPs of 2.2, 1.3 and 1.7 nm mean size, with PVP, PPh3 and dppb, respectively. The surface properties of these nanoparticles were compared using a model catalysis reaction namely, hydrogenation of cyclohexene, first under colloidal conditions and then under supported conditions after their immobilization onto an amino functionalized silica-coated magnetite support. PVP-stabilized Rh NPs were the most active catalyst whatever the catalytic conditions as a result of a strong coordination of the phosphine ligands at the metal surface that blocks some surface atoms even after several recycles of the supported nanocatalysts and limit the reactivity of the metallic surface.

Separation technology meets green chemistry: development of magnetically recoverable catalyst supports containing silica, ceria, and titania

Abstract Magnetic separation can be considered a green technology because it is fast, efficient, consumes low energy, and minimizes the use of solvents and the generation of waste. It has been successfully used in laboratory scale to facilitate supported catalysts’ handling, separation, recovery, and recycling. Only few materials are intrisically magnetic, hence the application of magnetic materials as catalyst supports has broaden the use of magnetic separation. Iron oxides, silica-coated iron oxides, and carbon-coated-cobalt are among the most studied catalyst supports; however, other metal oxide coatings, such as ceria and titania, are also very interesting for application in catalysis. Here we report the preparation of magnetically recoverable magnetic supports containing silica, ceria, and titania. We found that the silica shell protects the iron oxide core and allows the crystalization of ceria and titania at high temperature without compromising the magnetic properties of the catalyst supports.