Oxidative activation of light alkanes on dense ionic oxygen conducting membranes

The oxidative dehydrogenation of ethane to ethylene (ODHE) has been studied in a catalytic membrane reactor (CMR) using a dense mixed ionic oxygen and electronic conducting perovskite membrane Ba0.5Sr0.5Co0.8Fe0.2O3-&. At 1080K, an ethylene yield of 66% was obtained with the bare membrane. After Pd cluster deposition, the ethylene yield reached 76% at 1050K. Ni cluster deposition led to a decrease of ethane conversion compared to the bare membrane without changing ethylene selectivity.

Effects of reaction conditions on the selective oxidation of propane to acrylic acid on Mo-V-Te-Nb oxides

An effective Mo-1 V(0.3)Te(0.23)Nb(0.12)Ox catalysts for the selective oxidation of propane to acrylic acid was successfully prepared by using rotavap method. The catalyst was characterized by XRD and shown to contain (V0.07Mo0.93)(5)O-14, (Nb0.09Mo0.91)O-2.8,3MoO(2)(.)Nb(2)O(5), Mo5TeO16 and/or TeMo4O13, Te4Nb2O13 and a new TeMO (TeVMoO or TeVNbMoO; M = Mo, V and Nb) crystalline phase as the major phase. Regardless of the intrinsic catalytic characteristics of the catalyst, the external reaction conditions would have strong effects on the catalytic performance for propane oxidation. So in this paper, the effects of reaction conditions were investigated and discussed, including temperature, space velocity, V(air)/V(C3H8) ratio and V(steam)/V(C3H8) ratio. A stability test was also carried out on Mo1V0.3Te0.23Nb0.12Ox catalyst. The experimental run was performed during 100 h under the optimized reaction conditions. During the 100 h of operation, propane conversion and acrylic acid selectivity remained at about 59 and 64%, respectively. (C) 2004 Elsevier B.V. All rights reserved.

Identifying the isolated transition metal ions/oxides in molecular sieves and on oxide supports by UV resonance Raman spectroscopy

Isolated transition metal ions/oxides in molecular sieves and on surfaces are a class of active sites for selective oxidation of hydrocarbons. Identifying the active sites and their coordination structure is vital to understanding their essential role played in catalysis and designing and synthesizing more active and selective catalysts. The isolated transition metal ions in the framework of molecular sieves (e.g., TS-1, Fe-ZSM-5, and V-MCM-41) or on the surface of oxides (e.g., MoO3/Al2O3 and TiO2/SiO2) were successfully identified by UV resonance Raman spectroscopy. The charge transfer transitions between the transition metal ions and the oxygen anions are excited by a UV laser and consequently the UV resonance Raman effect greatly enhances the Raman signals of the isolated transition metal ions. The local coordination of these ions in the rigid framework of molecular sieves or in the relatively flexible structure on the surface can also be differentiated by the shifts of the resonance Raman bands. The relative concentration of the isolated transition metal ion/oxides could be estimated by the intensity ratio of Raman bands. This study demonstrates that the UV resonance Raman spectroscopy is a general technique that can be widely applied to the in-situ characterization of catalyst synthesis and catalytic reactions. (C) 2003 Elsevier Science (USA). All rights reserved.

Specific Adsorption of Trace Amounts of Calcium and Strontium by Hydrous Oxides of Iron and Aluminum1

Freshly prepared Fe and Al hydrous oxide gels and the amorphous product of heating gibbsite selectively adsorbed traces of Ca and Sr from solutions containing a large excess (∼1M) of NaNO3. The fraction of the added Ca (Sr) adsorbed depended principally on the suspension pH, the amount of solid present, and to a lesser extent on the NaNO3 concentration. Significant Ca and Sr adsorption occurred on the Fe and Al gels, and heated gibbsite, at pH values below the points of zero charge (8.1, 9.4, and 8.3±0.1, respectively), indicating specific adsorption. The pH (± 0.10) at which 50% of the Ca was adsorbed (pH50) occurred at pH 7.15 for the Fe gel (0.093M Fe), 8.35 for the Al gel (0.093M Al), and 6.70 for the heated gibbsite (0.181M Al); for Sr, the pH50 values were 7.10, 9.00, and 6.45, respectively. For the Fe gel and heated gibbsite, an empirical model based on the law of mass action described the pH dependence of adsorption reasonably well and suggested that for each Ca or Sr fraction adsorbed, approximately one proton was released. Failure of the Al gel to fit this model may have resulted from its rapid aging.

Synthesis and luminescence properties of hybrid organic-inorganic transparent titania thin film activated by in-situ formed lanthanide complexes

Stable transparent titania thin films were fabricated at room temperature by combining thenoyltrifluoroacetone (TTFA)-modified titanium precursors with amphiphilic triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, P123) copolymers. The obtained transparent titania thin films were systematically investigated by IR spectroscopy, PL emission and excitation spectroscopy and transmission electron microscopy. IR spectroscopy indicates that TTFA coordinates the titanium center during the process of hydrolysis and condensation. Luminescence spectroscopy confirms the in-situ formation of lanthanide complexes in the transparent titania thin film.