Vasile I. Parvulescu

Catalytic NOx Abatement Systems for Mobile Sources: From Three-Way to Lean Burn after-Treatment Technologies

Catalytic NOx Abatement Systems for Mobile Sources: From Three-Way to Lean Burn after-Treatment Technologies Pascal Granger* and Vasile I. Parvulescu* Unit e de Catalyse et de Chimie du Solide, UMR CNRS 8181, University of Lille 1, 59655 Villeneuve d’Ascq, France Department of Organic Chemistry, Biochemistry and Catalysis, University of Bucharest, Romania, 412 Regina Elisabeta Boulevard, Bucharest 030016, Romania

Sunflower and rapeseed oil transesterification to biodiesel over different nanocrystalline MgO catalysts

The catalytic activity for the production of biodiesel with three morphologically different nanocrystalline MgO materials prepared using simple, green and reproducible methods was investigated. The nanocrystalline samples studied were MgO(111) nanosheets (MgO (I)), conventionally prepared MgO (MgO (II)) and aerogel prepared MgO (MgO (III)). The methods to produce the catalysts included: (a) 4-methoxy-benzyl alcohol templated sol-gel process followed by supercritical drying and calcination in air at 773 K (MgO (I)), (b) from a commercial MgO that was boiled in water, followed by drying at 393 K, and dehydration under vacuum at 773 K (MgO (II)), and (c) viahydrolysis of Mg(OCH3)2 in a methanol–toluene mixture, followed by supercritical solvent removal with the formation of a Mg(OH)2 aerogel that was dehydrated under vacuum at 773 K (MgO (III)). These catalysts were characterized by TEM, DRIFT, and DR-UV-Vis and tested in the transesterification of sunflower and rapeseed vegetable oils at low temperatures, under different experimental conditions: autoclave, microwave and ultrasound. Working with these materials under microwave conditions provided higher conversions and selectivities to methylesters compared to autoclave or ultrasound conditions. Under ultrasound, a leaching of the magnesium has been evidenced as a direct consequence of a saponification reaction. These systems also allow working with much lower ratios of methanol to vegetable oil than reported in the literature for other heterogeneous systems. The activation temperature providing the most active catalysts was found to vary depending on the exposed facet: for MgO(111) structures (i.e.MgO (I)) this was 773 K, while for MgO (110) and (100) (i.e.MgO (II) and MgO (III)) this was 583 K.

Degradation of pharmaceutical compound pentoxifylline in water by non-thermal plasma treatment.

The decomposition of a model pharmaceutical compound, pentoxifylline, in aqueous solution was investigated using a dielectric barrier discharge (DBD) in coaxial configuration, operated in pulsed regime, at atmospheric pressure and room temperature. The solution was made to flow as a film over the surface of the inner electrode of the plasma reactor, so the discharge was generated at the gas-liquid interface. Oxygen was introduced with a flow rate of 600sccm. After 60min plasma treatment 92.5% removal of pentoxifylline was achieved and the corresponding decomposition yield was 16g/kWh. It was found that pentoxifylline degradation depended on the initial concentration of the compound, being faster for lower concentrations. Faster decomposition of pentoxifylline could be also achieved by increasing the pulse repetition rate, and implicitly the power introduced in the discharge, however, this had little effect on the decomposition yield. The degradation products were investigated by liquid chromatography-mass spectrometry technique (LC-MS). The evolution of the intermediates during plasma treatment showed a fast increase in the first 30min, followed by a slower decrease, so that these products are almost completely removed after 120min treatment time.

Degradation of antibiotics in water by non-thermal plasma treatment

The decomposition of three β-lactam antibiotics (amoxicillin, oxacillin and ampicillin) in aqueous solution was investigated using a dielectric barrier discharge (DBD) in coaxial configuration. Solutions of concentration 100 mg/L were made to flow as a film over the surface of the inner electrode of the plasma reactor, so the discharge was generated at the gas-liquid interface. The electrical discharge was operated in pulsed regime, at room temperature and atmospheric pressure, in oxygen. Amoxicillin was degraded after 10 min plasma treatment, while the other two antibiotics required about 30 min for decomposition. The evolution of the degradation process was continuously followed using liquid chromatography-mass spectrometry (LC-MS), total organic carbon (TOC) and chemical oxygen demand (COD) analyses.

Green synthesis of carbamates from CO2, amines and alcohols

Various carbamates can be prepared in a halogen-free way starting from cheap and readily available reagents such as amines, alcohols and carbon dioxide. Basic catalysts were able to convert both linear and branched aliphatic amines to the corresponding carbamates with good yields, in mild reaction conditions (2.5 MPa CO2) and even in the absence of dehydrating agents.

Degradation of pharmaceutical compounds in water by non-thermal plasma treatment

Pharmaceutical compounds became an important class of water pollutants due to their increasing consumption over the last years, as well as due to their persistence in the environment. Since conventional waste water treatment plants are unable to remove certain non-biodegradable pharmaceuticals, advanced oxidation processes was extensively studied for this purpose. Among them, non-thermal plasma was also recently investigated and promising results were obtained. This work reviews the recent research on the oxidative degradation of pharmaceuticals using non-thermal plasma in contact with liquid. As target compounds, several drugs belonging to different therapeutic groups were selected: antibiotics, anticonvulsants, anxiolytics, lipid regulators, vasodilatators, contrast media, antihypertensives and analgesics. It was found that these compounds were removed from water relatively fast, partly degraded, and partly even mineralized. In order to ensure the effluent is environmentally safe it is important to identify the degradation intermediates and to follow their evolution during treatment, which requires complex chemical analysis of the solutions. Based on this analysis, degradation pathways of the investigated pharmaceuticals under plasma conditions were suggested. After sufficient plasma treatment the final organic by-products present in the solutions were mainly small molecules in an advanced oxidation state.

Synthesis of symmetrical or asymmetrical urea compounds from CO2via base catalysis

Using Cs+ base catalysts and N-methylpyrrolidone as the solvent, both symmetrical and asymmetrical urea derivatives are prepared in good yields directly from CO2 and amines, in the absence of any dehydrating agents.

Graphenes in the absence of metals as carbocatalysts for selective acetylene hydrogenation and alkene hydrogenation

Catalysis makes possible a chemical reaction by increasing the transformation rate. Hydrogenation of carbon-carbon multiple bonds is one of the most important examples of catalytic reactions. Currently, this type of reaction is carried out in petrochemistry at very large scale, using noble metals such as platinum and palladium or first row transition metals such as nickel. Catalysis is dominated by metals and in many cases by precious ones. Here we report that graphene (a single layer of one-atom-thick carbon atoms) can replace metals for hydrogenation of carbon-carbon multiple bonds. Besides alkene hydrogenation, we have shown that graphenes also exhibit high selectivity for the hydrogenation of acetylene in the presence of a large excess of ethylene.

Ru-based magnetic nanoparticles (MNP) for succinic acid synthesis from levulinic acid

Ru(III)/functionalized silica-coated magnetic nanoparticles (Ru(III)-MNP) were proven to be a highly active, selective and easily recoverable catalyst for the oxidation of levulinic acid to succinic acid under green conditions.

Surface versus volume effects in luminescent ceria nanocrystals synthesized by an oil-in-water microemulsion method

Pure and europium (Eu(3+)) doped cerium dioxide (CeO(2)) nanocrystals have been synthesized by a novel oil-in-water microemulsion reaction method under soft conditions. In-situ X-ray diffraction and RAMAN spectroscopy, high-resolution transmission electron microscopy, UV/Vis diffuse-reflectance and Fourier transform infrared spectroscopy as well as time-resolved photoluminescence spectroscopy were used to characterize the nanaocrystals. The as-synthesized powders are nanocrystalline and have a narrow size distribution centered on 3 nm and high surface area of ~250 m(2) g(-1). Only a small fraction of the europium ions substitutes for the bulk, cubic Ce(4+) sites in the europium-doped ceria nanocrystals. Upon calcination up to 1000 °C, a remarkable high surface area of ~120 m(2) g(-1) is preserved whereas an enrichment of the surface Ce(4+) relative to Ce(3+) ions and relative strong europium emission with a lifetime of ~1.8 ms and FWHM as narrow as 10 cm(-1) are measured. Under excitation into the UV and visible spectral range, the europium doped ceria nanocrystals display a variable emission spanning the orange-red wavelengths. The tunable emission is explained by the heterogeneous distribution of the europium dopants within the ceria nanocrystals coupled with the progressive diffusion of the europium ions from the surface to the inner ceria sites and the selective participation of the ceria host to the emission sensitization. Effects of the bulk-doping and impregnation with europium on the ceria host structure and optical properties are also discussed.