Local environment of Fe dopants in nanoscale Fe : CeO(2-x) oxygen storage material.

Nanoscale Fe : CeO2-x oxygen storage material for the process of chemical looping has been investigated by advanced transmission electron microscopy and electron energy-loss spectroscopy before and after a model looping procedure, consisting of redox cycles at heightened temperature. Separately, the activity of the nanomaterial has been tested in a toluene total oxidation reaction. The results show that the material consists of ceria nanoparticles, doped with single Fe atoms and small FeOx clusters. The iron ion is partially present as Fe(3+) in a solid solution within the ceria lattice. Furthermore, enrichment of reduced Fe(2+) species is observed in nanovoids present in the ceria nanoparticles, as well as at the ceria surface. After chemical looping, agglomeration occurs and reduced nanoclusters appear at ceria grain boundaries formed by sintering. These clusters originate from surface Fe(2+) aggregation, and from bulk Fe(3+), which "leaks out" in reduced state after cycling to a slightly more agglomerated form. The activity of Fe : CeO2 during the toluene total oxidation part of the chemical looping cycle is ensured by the dopant Fe in the Fe1-xCexO2 solid solution, and by surface Fe species. These measurements on a model Fe : CeO2-x oxygen storage material give a unique insight into the behavior of dopants within a nanosized ceria host, and allow to interpret a plethora of (doped) cerium oxide-based reactions.

Ab initio reaction path analysis of benzene hydrogenation to cyclohexane on Pt(111).

First-principles density functional theory calculations were performed to obtain detailed insight into the mechanism of benzene hydrogenation over Pt(111). The results indicate that benzene hydrogenation follows a Horiuti-Polanyi scheme which involves the consecutive addition of hydrogen adatoms. A first-principles-based reaction path analysis indicates the presence of a dominant reaction path. Hydrogenation occurs preferentially in the meta position of a methylene group. Cyclohexadiene and cyclohexene are expected to be at best minor products, since they are not formed along the dominant reaction path. The only product that can desorb is cyclohexane. Along the dominant reaction path, two categories of activation energies are found: lower barriers at approximately 75 kJ/mol for the first three hydrogenation steps, and higher barriers of approximately 88 kJ/mol for steps four and six, where hydrogen can only add in the ortho position of two methylene groups. The highest barrier at 104 kJ/mol is calculated for the fifth hydrogenation step, which may potentially be the rate-determining step. The high barrier for this step is likely the result of a rather strong C-H...Pt interaction in the adsorbed reactant state (1,2,3,5-tetrahydrobenzene) which increases the barrier by approximately 15 kJ/mol. Benzene and hydrogen are thought to be the most-abundant reaction intermediates.

Pore mouth versus intracrystalline adsorption of isoalkanes on ZSM-22 and ZSM-23 zeolites under vapour and liquid phase conditions.

Methylbranched C5-C9 alkanes do not adsorb in the intracrystalline void space of ZSM-23, neither from the vapour nor the liquid phase, but are adsorbed in ZSM-22, if only from the liquid phase, and this despite the small difference in pore size.

The alkaline anthraquinone-2-sulfonate-H2O2-catalyzed oxidative degradation of lactose: an improved Spengler-Pfannenstiel oxidation.

The alkali-catalyzed oxidative degradation of lactose (1) to potassium O-beta-D-galactopyranosyl-(1----3)-D-arabinonate (2) has been studied and compared with that of D-glucose to D-arabinonate and D-galactose to D-lyxonate. A mechanism for the degradation of 1 catalyzed by alkali only is presented and discussed, taking into consideration the main reaction products. Increasing the reaction temperature from 293 to 318 K resulted in a drastic decrease of the selectivity for 2. Increasing the oxygen pressure from 1 to 5 bar did not significantly influence the selectivity. The overall reaction kinetics followed first-order behavior with respect to lactose, D-glucose, or D-galactose. The simultaneous addition of catalytic, equimolar amounts of sodium 2-anthraquinonemonosulfonate and H2O2 showed a pronounced effect on the selectivity. A reaction mechanism for this type of alkali-catalyzed oxidative degradation of carbohydrates is presented and discussed. Lactose could be oxidized up to almost complete conversion with a selectivity of 90-95% (mol/mol), whereas D-glucose was oxidized to D-arabinonate with a selectivity of 98%. This increased selectivity was maintained at temperatures from 293 up to 323 K, allowing a reduction of the batch time necessary for almost complete conversion from 50 to 1.5 h. The overall reaction kinetics still followed first-order behavior with respect to lactose, D-glucose or D-galactose. The apparent activation energy amounted to 114 +/- 2 kJ mol-1 for lactose, to 109 +/- 2 kJ mol-1 for D-glucose, and to 104 +/- 9 kJ mol-1 for D-galactose.

The effect of bismuth on the selective oxidation of lactose on supported palladium catalysts.

The selective oxidation of lactose by molecular oxygen has been studied in a batch reactor containing an aqueous slurry of 0.5 kmol m-1 reactant and 1.0 kg m-3 catalyst. The in situ Bi promotion of a commercial Pd-C catalyst resulted in 100% selectivity to sodium lactobionate up to conversions of 95% in the pH range 7-10 and at temperatures up to 333 K. Performing the reaction under such conditions that the oxygen transfer to the liquid phase was rate-controlling allowed the production of sodium lactobionate in high yields in approximately 1 h. A maximum initial reaction-rate of 0.47 mol kg-1 s-1 was found at a molar Bi to Pd ratio of 0.50-0.67. Fifteen batches of lactose were oxidized with the same charge of catalyst without significant loss in initial activity or selectivity. Such other aldoses as maltose, glucose, and galactose could be oxidized analogously with similar selectivities.