Acid-base properties of Cu<SUB>1-x</SUB>Co<SUB>x</SUB>Fe<SUB>2</SUB>O<SUB>4</SUB> ferrospinels: FTIR investigations

Systematic IR spectroscopic studies were undertaken to investigate the acid-base properties of Cu-Co ferrospinels Cu1-xCoxFe2O4 (x=0 to 1) employed in phenol methylation to produce 2,6-xylenol. The IR spectra of the ferrospinels reveal that Fe3+ and Co2+ ions are mainly responsible for the various hydroxy groups on the surface. Temperature dependent IR studies of pyridine adsorbed on spinels and on the spinel phase with deliberately added metal oxide exemplify the contribution of the metal ions and their coordination state towards Lewis acidity. IR studies of the spinel surface with adsorbed CO2 and adsorption studies of electron acceptors such as 7,7,8,8-tetracyanoquinodimethane, 2,3,5,6-tetrachloro-1-4-benzoquinone and p-dinitrobenzene were carried out to evaluate the nature of the basic sites and the strength and distribution of the electron donor sites present on the spinel surface. It was found that the acidity (basicity) of the Cu1-xCoxFe2O4 spinel system increases (decreases) from x=0 to 1. A correlation between acidity, basicity and catalytic performance reveals that an intermediate acid-base character enhances the phenol methylation activity

Catalytic mechanism of the dehydrogenation of ethylbenzene over Fe-Co/Mg(Al)O derived from hydrotalcites

Catalytic mechanism of ethylbenzene dehydrogenation over Fe-Co/Mg(Al)O derived from hydrotalcites has been studied based on the XAFS and XPS catalyst characterization and the FTIR measurements of adsorbed species. Fe-Co/Mg(Al)O showed synergy, whereas Fe-Ni/Mg(Al)O showed no synergy, in the dehydrogenation of ethylbenzene. Ni species were stably incorporated as Ni(2+) in the regular sites in periclase and spinel structure in the Fe-Ni/Mg(Al)O. Contrarily, Co species exists as a mixture of Co(3+)/Co(2+) in the Fe-Co/Mg(Al)O and was partially isolated from the regular sites in the structures with increasing the Co content. Co addition enhanced Lewis acidity of Fe(3+) active sites by forming Fe(3+)-O-Co(3+/2+)(1/1) bond, resulting in an increase in the activity. FTIR of ethylbenzene adsorbed on the Fe-Co/Mg(Al)O clearly showed formations of C-O bond and pi-adsorbed aromatic ring. This suggests that ethylbenzene was strongly adsorbed on the Fe(3+) acid sites via pi-bonding and the dehydrogenation was initiated by alpha-H(+) abstraction from ethyl group on Mg(2+)-O(2-) basic sites, followed by C-O-Mg bond formation. The alpha-H(+) abstraction by O(2-)(-Mg(2+)) was likely followed by beta-H abstraction, leading to the formations of styrene and H(2). Such catalytic mechanism by the Fe(3+) acid-O(2-)(-Mg(2+)) base couple and the Fe(3+)/Fe(2+) reduction-oxidation cycle was further assisted by Co(3+)/Co(2+), leading to a good catalytic activity for the dehydrogenation of ethylbenzene

A mechanistic approach to phenol methylation on Cu<SUB>1-x</SUB>Co<SUB>x</SUB>Fe<SUB>2</SUB>O<SUB>4</SUB>: FTIR study

The interaction of phenol, methanol, and possible reaction products of phenol methylation with the Cu<SUB>1-x</SUB>Co<SUB>x</SUB>Fe<SUB>2</SUB>O<SUB>4</SUB> system has been studied by FTIR spectroscopy in the temperature range between 373 and 623 K. The spectra obtained from the chemisorption of methanol onto Cu<SUB>1-x</SUB>Co<SUB>x</SUB>Fe<SUB>2</SUB>O<SUB>4</SUB> above 373 K indicate progressive oxidation to formate and/or dioxymethylene and then to CO, CO<SUB>2</SUB>, and H<SUB>2</SUB>. Phenol is predominantly adsorbed as phenolate species by the dissociative adsorption on an acid-base site and the phenyl ring of phenol is perpendicular to the catalyst surface, facilitating selective ortho methylation by methyl cations. Characteristic &#957;<SUB>C&#8212;O</SUB> bands observed for ortho-methylated phenols on the catalyst surface allow the identification of the same from the reaction mixture adsorbed on catalysts at 473 K, well below the optimum reaction temperature of 623 K, on Cu-containing catalysts. However, CoFe<SUB>2</SUB>O<SUB>4</SUB> shows little interaction of phenol with MeOH, when they are coadsorbed, and might be a limiting factor to the overall reaction. Coadsorption of acidity probes with phenol and methanol indicates that the same acid-base sites are responsible for the reaction. Methylated phenols show a weak interaction with the surface compared to phenol and are susceptible to desorption at reaction temperatures and thus facilitate efficient methylation

Ethylbenzene dehydrogenation over FeOx/(Mg,Zn)(Al)O catalysts derived from hydrotalcites:Role of MgO as basic sites

A series of Mg3-xZnxFe0.5Al0.5 mixed oxide catalysts derived from hydrotalcites were tested in the ethylbenzene dehydrogenation to styrene in He atmosphere at 550 °C. The catalysts were prepared by coprecipitation from the nitrates of metal components followed by calcination to mixed oxides at 550 °C. A part of Mg2+ in Mg 3Fe0.5Al0.5 mixed oxide was replaced with Zn2+ to test the effect of MgO as the support. The mixed oxides were composed of periclase and spinel-type compounds with a high surface area of 100-180m2gcat-1. Mössbauer and XPS measurements indicated the presence of Fe3+ on the catalysts and H2-TPR measurement suggested that the dehydrogenation reaction is catalyzed by the reduction-oxidation between Fe3+/Fe2+. The activity of Mg3-xZnxFe0.5Al0.5 mixed oxide decreased with increasing x, indicating an important role of MgO on the activity. Both CO2-TPD measurements as well as IR measurements of adsorbed CO2 clearly indicated the presence of basic sites of Mg 2+O2- on the catalysts. It seems that the combination of Mg2+O2- and Fe3+ was essential for the catalytic activity. It is concluded that the surface base sites generated on O2- bound Mg2+ near Fe3+ sites are responsible for H+-abstraction; the dehydrogenation of ethylbenzene was initiated by the H+ abstraction on Mg2+O2- basic sites, and accelerated by the reduction-oxidation of Fe3+/Fe2+ active species.</p