Liane M. Rossi

Magnetic nanomaterials in catalysis: advanced catalysts for magnetic separation and beyond

While magnetic separation techniques have long been in use, intensive research into superparamagnetic nanomaterials has accelerated the development of magnetically recoverable catalysts. Preparation techniques are currently undergoing rapid development and magnetic separation has been studied to facilitate the handling and recovery of enzyme, organo-, metal complex-, and nanoparticle-catalysts. In this article, we emphasize the preparation of support materials, because the choice of the correct support and the immobilization strategy are of primary importance in the development of high-quality magnetically recoverable catalysts. We summarize the representative methods for the synthesis of well-defined uncoated and coated magnetic nanomaterials. Recent scientific progress on the preparation of surface-modified magnetic nanomaterials and the most common synthetic approaches to attach or immobilize non-magnetic catalytic active phases onto magnetic nanomaterials were discussed. Moreover, better control and understanding of the magnetic properties is now an essential tool not only in selecting the best preparation route for recoverable catalysts, but also for designing reactors (e.g., magnetic fluidized-bed reactors) and for developing magnetic field-driven technologies (e.g., changes in the catalytic output operating under an applied magnetic field).

High performance magnetic separation of gold nanoparticles for catalytic oxidation of alcohols

We present the magnetic separation approach to facilitate the recovery of gold nanoparticle (AuNP) catalysts. The use of magnetically recoverable supports for the immobilization of AuNPs instead of traditional oxides, polymers or carbon based solids guarantees facile, clean, fast and efficient separation of the catalyst at the end of the reaction cycle. Magnetic separation can be considered an environmentally benign separation approach, since it minimizes the use of auxiliary substances and energy for achieving catalyst recovery. The catalyst preparation is based on the immobilization of Au3+ on the surface of core–shell silica-coated magnetite nanoparticles, followed by metal reduction using two different methods. AuNPs were prepared by thermal reduction in air and by hydrogen reduction at mild temperature. Interestingly, the mean particle size of the supported AuNPs was similar (ca. 5.9 nm), but the polydispersity of the samples is quite different. The catalytic activity of both catalysts in the aerobic oxidation of alcohols was investigated and a distinct selectivity for benzyl alcohol oxidation was observed.

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.

Ligand-Assisted Preparation of Palladium Supported Nanoparticles: a Step toward Size Control

Supported nanoparticles (SNPs) with narrow size distribution were prepared by H(2) reduction of Pd(2+) previously bound to ligand-modified silica surfaces. Interestingly, the size of the Pd(0) SNPs was tuned by the ligand grafted on the support surface. Amino- and ethylenediamino-functionalized supports formed Pd(0) SNPs of ca. 6 and 1 nm, respectively. The catalytic properties of both Pd(0) SNPs were investigated.

Magnetic properties of Fe3O4 nanoparticles coated with oleic and dodecanoic acids

Magnetic nanoparticles (NP) of magnetite (Fe3O4) coated with oleic acid (OA) and dodecanoic acid (DA) were synthesized and investigated through transmission electron microscopy (TEM), magnetization M, and ac magnetic susceptibility measurements. The OA coated samples were produced with different magnetic concentrations (78%, 76%, and 65%) and the DA sample with 63% of Fe3O4. Images from TEM indicate that the NP have a nearly spherical geometry and mean diameter ∼5.5 nm. Magnetization measurements, performed in zero-field cooled (ZFC) and field cooled processes under different external magnetic fields H, exhibited a maximum at a given temperature TB in the ZFC curves, which depends on the NP coating (OA or DA), magnetite concentration, and H. The temperature TB decreases monotonically with increasing H and, for a given H, the increase in the magnetite concentration results in an increase in TB. The observed behavior is related to the dipolar interaction between NP, which seems to be an important mechanism ...

Synthesis of supported metal nanoparticle catalysts using ligand assisted methods

The synthesis and characterization methods of metal nanoparticles (NPs) have advanced greatly in the last few decades, allowing an increasing understanding of structure-property-performance relationships. However, the role played by the ligands used as stabilizers for metal NPs synthesis or for NPs immobilization on solid supports has been underestimated. Here, we highlight some recent progress in the preparation of supported metal NPs with the assistance of ligands in solution or grafted on solid supports, a modified deposition-reduction method, with special attention to the effects on NPs size, metal-support interactions and, more importantly, catalytic activities. After presenting the general strategies in metal NP synthesis assisted by ligands grafted on solid supports, we highlight some recent progress in the deposition of pre-formed colloidal NPs on functionalized solids. Another important aspect that will be reviewed is related to the separation and recovery of NPs. Finally, we will outline our personal understanding and perspectives on the use of supported metal NPs prepared through ligand-assisted methods.

High performance gold nanorods and silver nanocubes in surface-enhanced Raman spectroscopy of pesticides.

The behavior of Au nanorods and Ag nanocubes as analytical sensors was evaluated for three different classes of herbicides. The use of such anisotropic nanoparticles in surface-enhanced Raman scattering (SERS) experiments allows the one to obtain the spectrum of crystal violet dye in the single molecule regime, as well as the pesticides dichlorophenoxyacetic acid (2,4-D), trichlorfon and ametryn. Such metallic substrates show high SERS performance at low analyte concentrations making them adequate for use as analytical sensors. Density functional theory (DFT) calculations of the geometries and vibrational wavenumbers of the adsorbates in the presence of silver or gold atoms were used to elucidate the nature of adsorbate-nanostructure bonding in each case and support the enhancement patterns observed in each SERS spectrum.

Ruthenium dioxide nanoparticles in ionic liquids: synthesis, characterization and catalytic properties in hydrogenation of olefins and arenes

A reacao de NaBH 4 com RuCl 3 dissolvido no liquido ionico 1-n-butil-3-metilimidazolio hexafluorfosfato (BMI.PF 6 ) e um metodo simples e reprodutivel para a sintese de nanoparticulas de RuO 2 estaveis com distribuicao estreita e diâmetro da particula entre 2-3 nm. As nanoparticulas de RuO 2 foram caracterizadas por XRD, XPS, EDS e TEM. Estas nanoparticulas mostraram alta atividade catalitica tanto na catalise heterogenea quanto na hidrogenacao bifasica liquido-liquido de olefinas e arenos sob condicoes moderadas de reacao. Experimentos de envenenamento com Hg(0) e CS 2 , e analises de XRD e TEM de particulas isoladas apos a catalise indicaram a formacao de nanoparticulas de Ru(0). As nanoparticulas podem ser reutilizadas em condicoes de catalise heterogenea ate 10 vezes na hidrogenacao de 1-hexeno rendendo um numero total de ciclos cataliticos de 175.000 para atomos de Ru expostos. The reaction of NaBH 4 with RuCl 3 dissolved in 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMI.PF 6 ) ionic liquid is a simple and reproducible method for the synthesis of stable RuO 2 nanoparticles with a narrow size distribution within 2-3 nm. RuO 2 nanoparticles were characterized by XRD, XPS, EDS and TEM. These nanoparticles showed high catalytic activity either in the solventless or liquid-liquid biphasic hydrogenation of olefins and arenes under mild reaction conditions. Hg(0) and CS 2 poisoning experiments and XRD and TEM analysis of particles isolated after catalysis indicated the formation of Ru(0) nanoparticles. The nanoparticles could be re-used in solventless conditions up to 10 times in the hydrogenation of 1-hexene yielding a total turnover number for exposed Ru atoms of 175,000.

Volcano-like Behavior of Au-Pd Core-shell Nanoparticles in the Selective Oxidation of Alcohols

Gold-palladium (AuPd) nanoparticles have shown significantly enhanced activity relative to monometallic Au and Pd catalysts. Knowledge of composition and metal domain distributions is crucial to understanding activity and selectivity, but these parameters are difficult to ascertain in catalytic experiments that have primarily been devoted to equimolar nanoparticles. Here, we report AuPd nanoparticles of varying Au:Pd molar ratios that were prepared by a seed growth method. The selective oxidation of benzyl alcohol was used as a model reaction to study catalytic activity and selectivity changes that occurred after varying the composition of Pd in bimetallic catalysts. We observed a remarkable increase in catalytic conversion when using a 10:1 Au:Pd molar ratio. This composition corresponds to the amount of Pd necessary to cover the existing Au cores with a monolayer of Pd as a full-shell cluster. The key to increased catalytic activity derives from the balance between the number of active sites and the ease of product desorption. According to density functional theory calculations, both parameters are extremely sensitive to the Pd content resulting in the volcano-like activity observed.