Evidence for perimeter sites over SmOx-modified Rh(100) surface by CO chemisorption

SmOx modified Rh(l 0 0) surfaces have been in-situ prepared by depositing metallic Sin and subsequently oxidizing under controlled conditions, and the interaction between the lanthanide oxide and transition metal has been characterized by means of X-ray photoelectron spectroscopy (XPS) and high-resolution electron-energy-loss spectroscopy (HREELS) as well as thermal desorption spectroscopy (TDS). As evidenced, the adsorption of CO on the modified surfaces shows some different features to the original surface of Rh(l 00). The covering of SmOx blocks some sites on the surface and consequently suppresses adsorption of the typical CO species with an uptake at about 500 K, while a novel desorption peak centered at 260 K emerges in the CO TDS. Correspondingly, the XP spectrum exhibits a new C Is peak at 287.9 eV and 0 Is peak at 532.6 eV. The intensity of the low temperature peak varies with the coverage of SmOx, which shows an actual correlation to the perimeter sites of SmOx particles on the surface. (C) 2004 Elsevier B.V. All rights reserved.

Preparation of palladium membrane over porous stainless steel tube modified with zirconium oxide

A palladium membrane has been prepared by electroless plating on the surface of a porous stainless steel tube. Since the large surface pores of the tube are obstacle for preparation of a defect-free palladium film on the surface, zirconium oxide particles were deposited inside the pores. The mean thickness of the resulting Pd membrane on the modified tube was ca. 10 mum. It is suggested that the permeability of hydrogen is partly governed by gas diffusion in the pores. (C) 2004 Elsevier B.V. All rights reserved.

The effect of acidity on olefin aromatization over potassium modified ZSM-5 catalysts

The transformation of olefin to aromatics over ZSM-5 catalysts with different K-loadings has been investigated both in a continuous flow fixed-bed reactor and in a pulse microreactor. Investigation of variation of olefin aromatization activity with K-loadings shows that strong acid sites are indispensable for the converting of olefin to aromatics. As intermediates of olefin aromatization process, butadiene and cyclopentene not only show much higher aromatization activity than mono-olefins, but also can be transformed into aromatics over relatively weak acid sites of K/ZSM-5. A proposal is put forward, stating that among all the steps experienced in olefins aromatization, the formation of diene or cycloolfin from mono-olefins through hydrogen transfer is the key step and can be catalyzed by strong acid sites.

Synthesis and surface characteristics of zirconia and modified zirconia: Performance of CO hydrogenation

ZrO2-A and ZrO2-B catalysts were prepared by two different coprecipitation methods and their performance of CO hydrogenation was studied. The results indicated that ZrO2 and Li-, Pd- and Mn-modified ZrO2 catalysts exhibited good selectivity and high STY to higher alcohols. The surface characteristics of ZrO2-A and ZrO2-B samples were investigated by means of BET, NH3-TPD, XRD and UV Raman technique. The tetragonal zirconia on the surface region of ZrO2-A and Li-Pd-Mn/ZrO2-A catalysts may be responsible for the high selectivity towards ethanol, while the monoclinic zirconia on the surface of ZrO2-B and Li-Pd-Mn/ZrO2-B catalysts may be crucial to the high isobutanol selectivity.

Activated carbons chemically modified by concentrated H2SO4 for the adsorption of the pollutants from wastewater and the dibenzothiophene from fuel oils

The surface properties, porosities, and adsorption capacities of activated carbons (AC) are modified by the oxidation treatment using concentrated H2SO4 at temperatures 150-270 degreesC. The modified AC was characterized by N-2 adsorption, base titration, FTIR, and the adsorption of iodine, chlorophenol, methylene blue, and dibenzothiophene. The treatment of AC with concentrated H2SO4 at 250 degreesC greatly increases the mesoporous volume from 0.243 mL/g to 0.452 mL/g, specific surface areas from 393 m(2)/g to 745 m(2)/g, and acidic surface oxygen complexes from 0.071 meq/g to 1.986 meq/g as compared with the unmodified AC. The base titration results indicate that the amount of acidic surface oxygen groups on the modified AC increases with increasing the treatment temperatures and carboxyls and phenols are the most abundant carbon-oxygen functional groups. The carboxyl groups, COO- species, and hydroxyl groups are detected mainly for the sample treated at 250 degreesC. The mesoporous properties of the AC modified by concentrated H2SO4 were further tested by the adsorption of methylene blue and dibenzothiophene. The AC modified by concentrated H2SO4 at 250 degreesC has much higher adsorption capacities for large molecules (e.g., methylene blue and dibenzothiophene) than the unmodified AC but less adsorption capacities for small molecules (e.g., iodine). The adsorption results from aqueous solutions have been interpreted using Freundlich adsorption models.

On configuration of exchanged La3+ on ZSM-5: A theoretical approach to the improvement in hydrothermal stability of La-modified ZSM-5 zeolite

Density functional calculations have been employed to investigate the locating and binding of lanthanum cation, i.e., La(OH)(2)(+), on HZSM-5 zeolite. Through geometry optimization, it was determined that lanthanum ions are favorably accommodated in the two 6-T rings of the straight channels (Clusters 1 and 2, see Sec. III A for details). Cluster 1 was found to exist in prior to Cluster 2 due to the preference of Al substitution in the T11 site (Cluster 1) rather than in the T8 site (Cluster 2). Geometry-optimization of Cluster 1 containing another two lanthanide ions Nd3+ and Yb3+ was also carried out and it was found that a monotonic decrease in Ln-O bond length will take place as the atomic number increases, conforming well to the rule of lanthanide contraction. Some of the optimized parameters are comparable to the corresponding experimental values in Y zeolite, which confirms that the optimized configurations are acceptable. The average frequencies of hydroxyls attached to La3+ or Yb3+ in Cluster 1 fall at 3609.16 and 3579.76 cm(-1), respectively, with the gap of these two frequencies close to that in the sodalite cage of Y zeolite. Compared to H-form zeolite, the charges on both Al and O atoms in Ln-ZSM-5 zeolite show an obvious increase, which will undoubtedly lead to a stronger mutual interaction and hence enhance the stability of the [AlO4](-) anion. Moreover, the Ln(OH)(2)(+) seem to have thickened the zeolite framework, which can effectively retard the process of dealumination. Through the evaluation of the possibility for dimer formation, it turned out that when the exchange degree arrived to approximately 0.28, lanthanum monomers began to aggregate into dimers, and were completely converted into dimers when the exchange degree approached 0.60. (C) 2003 American Institute of Physics.