Jean C. S. Costa

Chemical analysis of polycyclic aromatic hydrocarbons by surface-enhanced Raman spectroscopy.

The use of surface-enhanced Raman spectroscopy (SERS) for trace determination of polycyclic aromatic hydrocarbons (PAHs) is described. This paper focuses on the development of SERS-active substrates that are specific for the characterization and spectroscopic study of PAHs. The SERS-active substrates are based on thin gold films evaporated on a glass surface previously treated with a mercaptoalkylsilane. SERS of PAHs was investigated over uncoated gold island films and over such films coated with a self-assembled monolayer (SAM) of 1-propanethiol. Adsorption of PAHs on a plain SERS-active Au-film led to a surface-induced decomposition of PAHs, due to catalytic properties of nanostructured gold. Thus, the functionalization of the SERS-active substrates by means of SAM was done aiming at a specific chemical interaction toward PAHs. Thus, in addition to preventing decomposition of the PAHs, the coating also concentrates the hydrophobic PAHs close enough to the SERS-active interface. Results show that high sensitivity, SERS-active nanostructured gold substrates that show selectivity towards PAHs were obtained, with the following properties: strong intensification of the Raman signal, reproducibility, and stability over time. The employed methodology enables the observation of excellent Raman spectra of PAHs in aqueous environment at ppm levels.

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.

Silver–gold nanotubes containing hot spots on their surface: facile synthesis and surface-enhanced Raman scattering investigations

We report the synthesis of silver–gold nanotubes containing hot spots along their surface. The Ag–Au nanotubes exhibited exceptional SERS properties compared to silver nanowires, enabling the detection of crystal violet in the 10−10 M regime, as well as 9-nitroanthracene and benzo[a]pyrene at 3.3 × 10−7 M.

Rhodium Nanoparticles as Precursors for the Preparation of an Efficient and Recyclable Hydroformylation Catalyst

Despite all the advances in the application of nanoparticle (NP) catalysts, they have received little attention in relation to the hydroformylation reaction. Herein, we present the preparation of a hydroformylation catalyst through the immobilization of air‐stable rhodium NPs onto a magnetic support functionalized with chelating phosphine ligands, which serves as an alternative to air‐sensitive precursors. The catalyst was active in hydroformylation and could be used in successive reactions with negligible metal leaching. The interaction between the rhodium NPs and the diphenylphosphine ligand was evidenced by an enhancement in the Raman spectrum of the ligand. Changes occurred in the Raman spectrum of the catalyst recovered after the reaction, which suggests that the rhodium NPs are precursors of active molecular species that are formed in situ. The supported catalyst was active for successive reactions even after it was exposed to air during the recycling runs and was easily recovered through magnetic separation.

Support Functionalization with a Phosphine‐Containing Hyperbranched Polymer: A Strategy to Enhance Phosphine Grafting and Metal Loading in a Hydroformylation Catalyst

We present the design of a hydroformylation catalyst through the immobilization of air‐stable Rh nanoparticles (NPs) on a magnetic support functionalized with a hyperbranched polymer that bears terminal phosphine groups. The catalyst modification with the hyperbranched polymer improved the metal–support interaction, the metal loading, and the catalytic activity. The catalyst was active for the hydroformylation of natural products, such as estragole, and could be used in successive reactions with negligible metal leaching. The phosphine grafting played a key role in the recyclability of Rh NPs under hydroformylation conditions. The catalytic activity was maintained in successive reactions, even if the catalyst was exposed to air during each recovery procedure. The modification of the support with hyperbranched polyester allowed us either to increase the number of Rh active species or to obtain more active Rh species on the catalyst surface.

Strontium and Nickel Heterogeneous Catalysts for Biodiesel Production from Macaw Oil

It is presented herein heterogeneous catalysts comprised of strontium and nickel oxides synthesized using a coprecipitation method. They were applied for the preparation of biodiesel from macaw palm oil. The catalysts were characterized by X-ray diffraction (XRD), adsorption and desorption of nitrogen by Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halenda (BJH) methods, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and differential thermogravimetric analysis (TG-DTA). The conversion was determined by gas chromatography with flame detector (GC-FID). The best activity was obtained when the catalyst was calcined at 1100 °C for 3 hours. The highest conversion was reached (97%) when the following conditions were used: 5 hours, 2% of metal loading, 65 °C and oil/alcohol molar ratio of 1:9.