Cooperative effects of H+ and H- hydrido carbonyl ruthenium derivatives; role of homogeneous and heterogeneous protonic and lewis acids in catalytic hydrocarbonylation reactions

The role played by H+ hydrido iodocarbonyl and H- hydrido carbonyl ruthenium catalysts in the different catalytic steps of hydroformylation and hydroesterification of olefins, and in the homologation of alcohols has been investigated. The H- hydrido carbonyl species are mainly involved in the activation of olefins and in the hydrogenation of the acyl intermediates to aldehydes and alcohols, whereas the H+ hydrido iodocarbonyl derivatives are involved in the activation of alcohols and other oxygenated substrates, and in their carbonylation to esters. The cooperation between the two species, possible under particular reaction conditions, results in an improvement of the selectivity towards homologation (carbonylation plus hydrogenation) products. Heterogeneous Lewis acid promoters, easily recyclable from the reaction mixture, have also been successfully used in the hydrocarbonylation of alcohols, resulting in an increase of the carbonylation and homologation products. A reaction pathway in agreement with the experimental results is discussed. © 1989.

Structural study of copper oxide supported on a ceria-modified titania catalyst system

A structural study of CuO supported on a CeO2-TiO2 system was undertaken using X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) techniques. The results of XRD revealed the presence of only two phases, TiO2 anatase and CeO2 cerianite. A trend towards smaller TiO2 crystallites was observed when cerium content increased. When the amount of cerium increased, Ti K-edge XANES analysis showed an increasing distortion of Ti sites. The results of Ce LIII-edge EXAFS showed that Ce atoms are coordinated by eight oxygen atoms at 2.32 Å. For the sample containing a small amount of cerium, the EXAFS analysis indicated that the local structure around Ce atoms was highly distorted. The catalysts presented quite different Cu K-edge XANES spectra compared to the spectra of the CuO and Cu2O reference compounds. The Cu-O mean bond length was close to that of the CuO and the Cu atoms in the catalysts are surrounded by approximately four oxygen atoms in their first shell. Copper supported on the ceria-modified titania support catalysts displayed a better performance in the methanol dehydrogenation when compared to copper supported only on titania or on ceria. © 2002 Plenum Publishing Corporation.

Produção de biodiesel etílico utilizando óxidos mistos derivados de hidróxidos duplos lamelares como catalisadores

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Influência de elementos terras raras nas propriedades catalíticas de óxidos derivados de hidrotalcitas para produção de biodiesel etílico

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Óxidos derivados de hidromagnesitas e hidrotalcitas modificadas como catalisadores heterogêneos na síntese de biodiesel etílico

Pós-graduação em Química - IBILCE