Although previous researchers have found that FSM-16 (#16 Folded Sheet Mesoporous material) doped with chromium and related Cr-doped silica catalysts has shown great activity for the oxidative dehydrogenation of isobutane to isobutene, information on the nature of these catalysts is insufficient. For this study, three types of Crdoped silica catalysts were prepared by applying the template ion exchange method. CrOx/FSM-16 and CrOx/SiO 2 were used as references. These catalysts were used for oxidative dehydrogenation, which was then characterized via various techniques. The most active catalyst was Cr-doped silica, which did not have the hexagonal structure that is characteristic of mesoporous FSM-16. Various characterizations showed that the catalytic activity of the Cr-species, stemmed from a weak acidic nature and a redox nature that originated from the combination of silicate and a Cr cation, as opposed to the hexagonal structure and strong acidic nature of FSM-16.

Mesoporous silicas have shown promise as materials for solid catalysts or catalyst supports due to their unique characteristics. Metal-doped mesoporous silicas are known to be catalytically active in the oxidative dehydrogenation (ODH) of isobutane. However, heavy-metal-free mesoporous silicas have not been studied closely for their use as catalysts. In the present study, MCM-41 (#41 Mobil composition of matter) was acid-treated to enhance its catalytic activity, although pure MCM-41 was confirmed as catalytically inactive for the ODH of isobutane (isobutene yield = 0.9%). The pH of a slurry of as-synthesized MCM-41 was changed during acid treatment. A pH adjustment to 6.5 resulted in great improvement in catalytic activity (isobutene yield = 6.1%), but a pH adjustment to 4.5 resulted in insufficient improvement (isobutene yield = 4.5%). It was confirmed via XRD and N 2 adsorption-desorption measurement that the pH adjustment to 4.5 degraded the ordered structure of MCM-41. This degradation would be a crucial factor that would render acid treatment less effective. In addition to the acid treatment, Al doping to MCM-41 was conducted. Al doping also greatly enhanced the acidity and catalytic activity of MCM-41.

MCM-41 (#41 Mobil Composition of Matter) is a favorable material for heterogeneous reactions because of its unique porous structure. However, the catalytic activity of MCM-41 for the oxidative dehydrogenation (ODH) of isobutane to isobutene is known to be quite low. In the present study, a metal-doping method was employed to improve this catalytic activity. Doping of Cr, Co, Ni, or Mo into MCM-41 resulted in a great improvement in the catalytic activity. Since chromium-doped MCM-41 (Cr-MCM-41) showed the greatest catalytic activity among these catalysts, its redox property was further analyzed via XPS, XAFS and H 2-TPR techniques. The XPS spectrum of Cr-MCM-41 suggested that it has Cr 3+ and Cr 6+ species on its surface. Also, a pre-edge peak due to Cr 6+ species was confirmed in the XANES spectrum of Cr-MCM-41. In H 2-TPR measurement, Cr-MCM-41 was more reducible than crystalline Cr 2 O 3 , which showed low catalytic activity for the ODH of isobutane. The reducible Cr 6+ species on Cr-MCM-41 contributed to an improvement in the catalytic activity of MCM-41.

Catalytic activities of calcium hydroxyapatite (HAp) and β-type tricalcium phosphate (β-TCP) were examined for use in the oxidative dehydrogenation (ODH) of isobutane. β-TCP was catalytically inactive for the ODH of isobutane, but stoichiometric HAp afforded a high isobutene yield (5.6%). The isobutane conversion and isobutene selectivity of HAp depended on the atomic ratio of Ca/P. HAp with Ca/P = 1.67 showed the highest isobutene selectivity and isobutene yield among the HAp catalysts with different Ca/P ratios. The characterization of the acidic-basic properties showed that these properties affect the catalytic performance of HAp, and that its basicity is necessary for high catalytic activity. To improve the catalytic activities of calcium phosphates, they were impregnated with Cr. Despite a much lower surface area for β-TCP, Cr-impregnated β-TCP showed a higher isobutene yield (up to 8.4%) than that of Cr-impregnated HAp. The results of the XPS measurement showed that the Cr 3+ species on calcium phosphates, owing to basicity, worked as active sites in the ODH of isobutane.

The template ion exchange of chromium cations into FSM-16 (#16 Folded Sheets Mesoporous Materials) for 247 h resulted in a 2.89 wt % incorporation of those cations into the FSM-16, although only a 0.3 wt % incorporation had previously been reported. The XRD pattern of the resultant solid (Cr-FSM-16) showed that the hexagonal structure characteristic of FSM-16 remained after the 2.89 wt % incorporation of chromium cations. XPS could be used to detect the Cr 3+ and Cr 6+ species on the surface of Cr-FSM-16. A pre-edge peak that was due to a tetrahedrally coordinated Cr 6+ species was confirmed in the XANES spectrum of the Cr-FSM-16, which showed that the coordination state around some Cr species was similar to that around the Si species in FSM-16. With the increase in the amount of chromium cations in FSM-16, its catalytic activity and stability during the oxidative dehydrogenation of isobutane were evidently improved.

In this study, wet impregnation method and solgel technique were used to prepare CoMo-based catalysts supported on two types of porous silicas containing calcium phosphate. The prepared catalysts were characterized using various techniques, such as N 2 adsorptiondesorption measurement, scanning electron microscope, X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), differential thermal analysis, and X-ray photoelectron spectroscopy. The catalysts were tested for ammonia decomposition to produce CO x-free hydrogen. The results of the XRD and FT-IR measurements elucidated that the crystal structure of calcium phosphate on the silica supports was attributed to calcium hydroxyapatite (HAp). The addition of calcium phosphate changed the porous structures of the catalysts, and decreased their BET surface areas and total pore volumes. Furthermore, the catalytic activity of the CoMo-based catalysts was influenced by the amount of calcium phosphate added. It was observed that the ammonia conversion at 873 K was increased by a maximum of 12.6% when 0.5 wt% of calcium phosphate was added to the catalyst, while a further addition of calcium phosphate beyond 1.0 wt% inhibited the ammonia conversion. From this study, it was concluded that HAp could work as a promoter for ammonia decomposition.

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