Different mechanisms for the formation of acetaldehyde and ethanol on the Rh-based catalysts

Different mechanisms for the formation of acetaldehyde and ethanol on the Rh-based catalysts were investigated by the TPR (temperature programmed reaction) method, and the active sites were studied by CO-TPD, TPSR (temperature programmed surface reaction of preadsorbed CO by H-2) and XPS techniques. The TPR results indicated that ethanol and acetaldehyde might be formed through different intermediates, whereas ethanol and methanol might result from the same intermediate. Results of CO-TPD, TPSR, and XPS showed that on the Rh-based catalyst, the structure of the active sites for the formation of C-2-oxygenates is ((RhxRhy+)-Rh-0)-O-Mn+ (M=Mn or Zr, x>>y, 2 less than or equal ton less than or equal to4). The tilt-adsorbed CO species is the main precursor for CO dissociation and the precursor for the formation of ethanol and methanol. Most of the linear and geminal adsorbed CO species desorbed below 500 K. Based on the suggested model of the active sites, detailed mechanisms for the formation of acetaldehyde and ethanol are proposed. Ethanol is formed by direct hydrogenation of the tilt-adsorbed CO molecules, followed by CH2 insertion into the surface CH2-O species and the succeeding hydrogenation step. Acetaldehyde is formed through CO insertion into the surface CH3-Rh species followed by hydrogenation, and the role of the promoters was to stabilize the intermediate of the surface acetyl species. (C) 2000 Academic Press.

Sparsely Faceted Arrays: A Mechanism Supporting Parallel Allocation, Communication, and Garbage Collection

Conventional parallel computer architectures do not provide support for non-uniformly distributed objects. In this thesis, I introduce sparsely faceted arrays (SFAs), a new low-level mechanism for naming regions of memory, or facets, on different processors in a distributed, shared memory parallel processing system. Sparsely faceted arrays address the disconnect between the global distributed arrays provided by conventional architectures (e.g. the Cray T3 series), and the requirements of high-level parallel programming methods that wish to use objects that are distributed over only a subset of processing elements. A sparsely faceted array names a virtual globally-distributed array, but actual facets are lazily allocated. By providing simple semantics and making efficient use of memory, SFAs enable efficient implementation of a variety of non-uniformly distributed data structures and related algorithms. I present example applications which use SFAs, and describe and evaluate simple hardware mechanisms for implementing SFAs. Keeping track of which nodes have allocated facets for a particular SFA is an important task that suggests the need for automatic memory management, including garbage collection. To address this need, I first argue that conventional tracing techniques such as mark/sweep and copying GC are inherently unscalable in parallel systems. I then present a parallel memory-management strategy, based on reference-counting, that is capable of garbage collecting sparsely faceted arrays. I also discuss opportunities for hardware support of this garbage collection strategy. I have implemented a high-level hardware/OS simulator featuring hardware support for sparsely faceted arrays and automatic garbage collection. I describe the simulator and outline a few of the numerous details associated with a "real" implementation of SFAs and SFA-aware garbage collection. Simulation results are used throughout this thesis in the evaluation of hardware support mechanisms.

UV Raman spectroscopic study on the synthesis mechanism of zeolite X

The synthesis of zeolite X is characterized by UV Raman spectroscopy, NMR spectroscopy, and X-ray diffraction. UV Raman spectra of the liquid phase of the synthesis system indicate that AI(OH); species are incorporated into silicate species, and the polymeric silicate species are depolymerized into monomeric silicate species during the early stage of zeolite formation. An. intermediate species possessing Raman bands at 307, 503, 858 and 1020 cm(-1) is detected during the crystallization ill the solid phase transformation. The intermediate species is attributed to the beta cage, the secondary building unit of zeolite X. A model for the formation of zeolite X is proposed, which involves four-membered rings connecting to each other via six-membered ring to form beta cages, then the beta cages interconnect via double six-membered rings to form the framework of zeolite X. (C) 2001 Elsevier Science B.V. All rights reserved.

Analysis of the mechanism and regulation of lactose transport and metabolism in Clostridium acetobutylicum ATCC 824.

Although the acetone-butanol-ethanol (ABE) fermentation of Clostridium acetobutylicum is currently uneconomic, the ability of the bacterium to metabolise a wide range of carbohydrates offers the potential for revival based on the use of cheap, low grade substrates. We have investigated the uptake and metabolism of lactose, the major sugar in industrial whey waste, by C. acetobutylicum ATCC 824. Lactose is taken up via a phosphoenolpyruvate (PEP)-dependent phosphotransferase system (PTS) comprising both soluble and membrane-associated components, and the resulting phosphorylated derivative is hydrolysed by a phospho--galactosidase. These activities are induced during growth on lactose, but are absent in glucose-grown cells. Analysis of the C. acetobutylicum genome sequence identified a gene system, lacRFEG, encoding a transcriptional regulator of the DeoR family, IIA and IICB components of a lactose PTS, and phospho--galactosidase. During growth in medium containing both glucose and lactose, C. acetobutylicum exhibited a classical diauxic growth, and the lac operon was not expressed until glucose was exhausted from the medium. The presence upstream of lacR of a potential catabolite responsive element (cre) encompassing the transcriptional start site is indicative of the mechanism of carbon catabolite repression characteristic of low-GC Gram-positive bacteria. A pathway for the uptake and metabolism of lactose by this industrially important organism is proposed.