Solid State Phenomena Vols. 124-126

Abstract: Niobium- and tantalum-containing mesoporous molecular sieves MCM-41 have been synthesized, and applied as a catalyst for vapor phase Beckmann rearrangement of cyclohexanone oxime to ε-caprolactam. NbMCM-41 catalyst exhibited high catalytic performance in the vapor phase Beckmann rearrangement of cyclohexanone oxime. The oxime conversions were almost 100% and the lactam selectivities were around 80%. The lactam selectivities of NbMCM-41 catalyst were higher than those of AlMCM-41 catalyst. However, TaMCM-41 catalyst exhibited lower catalytic performance than AlMCM-41 catalyst, and it was fast deactivated with time. These results may be due to the acidity difference among the catalysts. The results from NH3-TPD showed that NbMCM-41 catalyst possessed weak and medium acid sites, while TaMCM-41 catalyst possessed only very weak acid sites. AlMCM-41 catalyst also exhibited only weak acid sites.

Abstract: Silica supported nickel molybdenum phosphides (NiMoP/SiO2) were successfully prepared by temperature-programmed reduction (TPR) reaction of phosphorous-impregnated nickel molybdenum oxides (NiMoO4) precursors with hydrogen at relatively low temperatures (530 – 590 oC) and characterized by Fourier transform-Infrared spectrometry (FT-IR), X-ray diffraction (XRD), Electron probe microanalysis (EPMA) and Temperature-programmed reduction reaction (TPR). The process of solid transformation and properties of materials prepared from ammonium hydrogen phosphate (AMP)-impregnated samples were compared with those of phosphide made from phosphoric acid (PAC)-impregnated samples. Results show that the formation of a single NiMoP phase on silica significantly depends on reduction rates, phosphorous sources and phosphorous loadings. A single phase of NiMoP on SiO2 was particularly promoted at a below 5 oC/min of reduction rate and the starting molar ratio of Ni/Mo/P=1/1/1. A single phase of crystalline NiMoP on silica was produced from AMP-impregnated samples, while other phases of MoP, Ni2P, or NiMoP2 were appeared from PAC-impregnated samples with loading. The new phase of NiMoP2 was occurred with increasing phosphorous loading (above Ni/Mo/P=1/1/2.5) as a result of facilitated contact on the surface between the Ni-Mo bimetallic component and the phosphorous reagent

Abstract: Pt nano particles were synthesized on carbon nanotubes (CNTs) by chemical vapor deposition (CVD). (Trimethyl)methylcyclopentadienyl platinum (MeCpPtMe3) was used as Pt precursor, which was vaporized at 70oC and delivered to the pretreated CNTs at the reactor. The CVD was performed at various temperatures, 80~270oC with various gas flows. Consequently, Pt nano particles of 1~2 nm size were synthesized by CVD, which is much smaller than the Pt particles prepared by wet impregnation and by electrochemical deposition. The surface characterizations of Pt/CNT catalysts were performed by XRD, HR-TEM, CO chemisorption, etc.

Abstract: Surface characteristics of anodic titania formed by electrochemical method and effects of electrolytic mediums on microstructures of anodic TiO2 layer were investigated. The titania film formed in sulfuric acid or mixture electrolyte with sulfuric and phosphoric acids shows porous cell structures. But the films formed in sulfuric acid represent smaller cell structures than those formed in the mixture electrolyte, and the change in microstructural parameters is associated with electrolytes. However, when titanium substrate was anodized in HF, surface morphologies and structures of anodic titania film greatly changed, forming self-organized TiO2 nanotubes.

Abstract: Anodic oxide films were formed on titanium using an electrolyte solution containing phosphoric acid for dental implants by an electrochemical method. The parameters of the oxidation process were current density and electrolyte concentration. The micro structural morphology, surface roughness, thickness of the oxide layer and the behavior of voltage-time curves were examined. The results show that the surface roughness, porosity size and the thickness of the oxide layer showed similar trends as the process parameters were changed. The surface morphology of the samples was observed for different current densities at a constant electrolyte concentration. The pore size, thickness and roughness of the anodic oxide films are directly proportional to the maximum voltage and the slope of the voltage to time transient (dV/dt) curves during the growth of the galvanostatic anode oxide film on plate type Ti.

Abstract: In this study, we modified the surface of nanoporous carbons with carboxymethylated polyethyleneimine (CM-PEI) of a high charge density in order to increase the Pt loading on the nanoporous carbons in an aqueous solution. We carried out equilibrium adsorption tests of Pt(IV) on the pure nanoporous carbon and the CM-PEI-coated carbons and evaluated the adsorption isotherm on the CM-PEI-coated carbon using various isotherm models. It was found that the adsorption of Pt(IV) onto the CM-PEI-coated carbons obeys the Langmuir isotherm model.

Abstract: A first and efficient procedure has been developed for microwave-assisted transfer hydrogenation of ketones. Silica gel-supported ligand 2 has been prepared for the transfer hydrogenation. This immobilized ligand-Ru complex acted as an efficient catalyst for the hydrogen transfer reaction of ketones. The MW-assisted reactions using the supported ligand 2 could reach completion within 20~40 min.

Abstract: Coatings of hydroxyapatite (HA) on the porous-surfaced Ti compact have been conducted by electrostatic spray deposition (EDS). The precursor solution for the HA coating by ESD was prepared by mixing nano-scaled HA powder with ethyl alcohol. As-deposited HA films on the substrate were heat-treated (400 ~ 900 °C) and their physical characteristics were investigated by Scanning Electronic Microscopy (SEM), X-ray Diffractometer (XRD), and X-ray Photoelectronic Spectroscopy (XPS). As-deposited HA films were consisted of HA particles which were uniformly distributed on the Ti substrate, showing a porous structure. By heat treatment, HA particles were agglomerated each other and melted to form a highly dense and homogeneous coating layer consisted of equiaxed nano-scaled grains. HA coatings on the porous-surfaced Ti compact consisted of highly crystalline apatite phase with the Ca/P ratio of about 1.67 were successfully obtained by using ESD.

Abstract: The photo-catalytic hydroxylation of phenol with hydrogen peroxide was carried out over TS-1 and Ti-MCM-41 catalysts. For comparison, the dark (thermal)-catalytic hydroxylation of phenol was also performed. The difference in catalytic behaviors of TS-1 and Ti-MCM-41 and product distribution in both the reactions were investigated. The TS-1 and Ti-MCM-41 catalysts having the Si/Ti ratio of 50 were prepared by in-situ crystallization and characterized using XRD, UV-DRS. In the all reactions, the main products were catechol (CAT), hydroquinone (HQ) and benzoquinone (BQ). In dark (thermal)-reaction, TS-1 showed a higher catalytic activity than Ti- MCM-41. In photo-reaction, however, the activity of Ti-MCM-41 was comparable to that of TS-1. The conversion of phenol and the selectivity to CAT in the photo-catalytic reaction were higher than those in dark (thermal)-reaction. In the all reactions, the selectivity to CAT increased remarkably when the selectivities to HQ and BQ decreased with reaction time.

Abstract: Nickel oxide supported on zirconia and modified with MoO3 for acid catalysis was prepared by drying powdered Ni(OH)2-Zr(OH)4 with ammonium heptamolybdate aqueous solution, followed by calcining in air at high temperature. The characterization of prepared catalysts was performed using FTIR, Raman, XRD, and DSC. MoO3 equal to or less than 15 wt% was dispersed on the surface of catalyst as two-dimensional polymolybdate or monomolybdate, while for MoO3 above 15 wt%, crystalline orthorhombic phase of MoO3 was formed. The high acid strength and acidity were responsible for the Mo=O bond nature of the complex formed by the interaction between MoO3 and ZrO2. The catalytic activity for cumene dealkylation was correlated with the acidity of the catalyst measured by the ammonia chemisorption method