Quantum chemical studies of zeolite proton catalyzed reactions

Theoretical chemistry applied to zeolite acid catalysis is becoming an important tool in the understanding of the adsorption and interaction of guest molecules with the zeolitic lattice. Especially the understanding of the mechanisms by which zeolite catalyzed chemical reactions proceed becomes possible. It is shown here that the old interpretation of carbonium and carbenium ions as intermediates for zeolite catalyzed reactions has to be replaced by a new approach in terms of positively charged transition states that are strongly stabilized by the zeolitic lattice. The large deprotonation energy of the acidic zeolite is overcome by stabilization of the intermediate or transition state positive charge by the negative charge left in the lattice. The zeolitic sites responsible for the adsorption and/or reaction of guest molecules are the Brønsted-acid and Lewis-base sites. We also show that different transition states are responsible for different kinds of reactions, such as cracking, dehydrogenation, etc.     

IR在胎面胶中的应用

具有高含量3，4-结构的IR能特别有效地提高高性能轮胎的湿抓着力。因此，可以通过调整炭黑和BR用量来提高轮胎的磨耗和滚动阻力性能，同时保持优异的湿抓着性能。     

The benefit of detergent enzymes under changing washing conditions

The influence of two commercial proteolytic enzymes, Maxatase® and PB-92, were studied viz á viz changing phosphate content and washing conditions. (Maxatase® is a registered trademark of Gist-Brocades N.V.; PB-92 will be sold under the trademark Maxacal^TM.) In the USA and Western Europe, detergent phosphate content is decreasing because of environmental considerations/legislation. Washing conditions are changing towards lower temperatures be-cause of the increased use of synthetic fibers and the need to con-serve energy. Both Maxatase and PB-92 are shown to improve sig-nificantly the performance of US detergents, even at temperatures as low as 70 F. This conclusion is based on Terg-O-Tometer tests on EMPA 116 cloth using US detergents and presoak products.     

Polysulphone and poly(phenylene sulphide) blends: 1. Thermal characterization and phase morphology

The phase behaviour and morphology of injection moulded specimens of polysulphone (PSF) and poly(phenylene sulphide) (PPS) blends were studied by differential scanning calorimetry (d.s.c.), dynamical mechanical thermal analysis (d.m.t.a.) and transmission electron microscopy (TEM). The blends are phase separated regardless of the blend composition as revealed by d.s.c., d.m.t.a. and TEM. Upon annealing at 160°C for 2 h, d.m.t.a. results indicate that the PPS phase remains in the amorphous state at compositions <10%. At compositions between 20 and 35%, the PPS appears to be dispersed in a mixed mode of amorphous and crystalline domains. Above 35% the PPS phase appears to become fully crystallized upon annealing of the blends. At 10% PPS, TEM results showed 35–200 nm size dispersion both in the as-moulded and in the annealed specimens. At 20% the PPS phase varied widely in size, from 35 nm to tens of micrometres but remained as an included phase. TEM also revealed a compound morphology of the included phase at a composition of 50 wt% of each component.     

Application of K2CO3 catalysts in the coal gasification process using nuclear heat

Conventional gasification processes use coal not only as feedstock to be gasified but also for supply of energy for reaction heat, steam production, and other purposes. With a nuclear high temperature reactor (HTR) as a source for process heat, it is possible to transform the whole of the coal feed into gas. This concept offers advantages over existing gasification processes: saving of coal, as more gas can be produced from coal; less emission of pollutants, as the HTR is used for the production of steam and electricity instead of a coal-fired boiler; and a lower production cost for the gas. However, the process has the disadvantage that the temperature is limited to the outlet temperature (950 °C max) of the helium cooling gas of the HTR. Therefore the possibility of catalytic steam gasification was examined. Model calculations based on experimental results show that use of 3–4 wt% relative to coal of K²CO³ catalyst increases the throughput of a large scale nuclear gasification plant by ≈65%, while gas production costs decrease by ≈15%. Corrosion by catalysts is not significant at low concentration (< 5 wt%) and low temperature (< 900 °C).     

Ion-dipole interactions between adsorbed CO and support cations in Pt/K-LTL

The adsorption of carbon monoxide on a non-acidic Pt/K-LTL catalyst has been studied by diffuse reflectance and transmission IR spectroscopy. The CO spectrum is strongly dependent on the experimental conditions. Adsorption on the small Pt clusters in the presence of water gives linear-CO bands between 2060 and 1990 cm^–1 and a bridging-CO band around 1800 cm^–1. In the absence of water, the linear bands are red shifted to about 1940 and 1720 cm^–1, respectively. The frequency shift is attributed to an ion-dipole interaction between adsorbed CO and support cations. The ion-dipole interaction is screened by the adsorbed water leading to a smaller red shift in the CO stretching frequency.     

Intrinsic reactivity of gold nanoparticles: Classical, semi-empirical and DFT studies

Gold nanoparticles used in most experiments (1–10 nm) in gold catalysis show varying degrees of reactivity, with particles below 5 nm generally being more reactive. The origin of this activity is a subject of a number of model experiments and theoretical studies on either clusters of a few atoms in size or extended surfaces (smooth or stepped). In the work described here, a classical theory for the variation of the metal workfunction with cluster size, Extended Hückel Theory (EHT) calculations combined with DFT calculations, as well as a carbon monoxide (CO) chemisorption model are combined to develop a relationship between metal particle size and the particle's reactivity towards CO. For gold, it is shown that while the contribution of the d-band hybridization energy to the total CO chemisorption energy is unfavourable for bulk gold, this is not true for gold particles below 5–6 nm. That is, the d-band hybridization energy is negative for small gold particles. This is believed to be explanation of the onset of high reactivity for small gold particles.     

Opportunities for public water utilities in the market of energy from water

An inventory is made of the possibilities to recover sustainable energy from the water cycle by identifying different water flows in a municipal environment as a sustainable energy source. It is discussed what role public water utilities should play in the market of energy from water. This is done for Waternet, the public water utility of Amsterdam, by describing experiences on two practical applications for aquifer thermal energy storage and energy recovery from drinking water. The main conclusion is that public water utilities can substantially contribute to the production of sustainable energy, especially by making use of heat and cold from the water cycle. Public water utilities have the opportunity to both regulate and enter the market for energy from water.     

Delineating Boundaries for Imprecise Regions

In geographic information retrieval, queries often name geographic regions that do not have a well-defined boundary, such as “Southern France.” We provide two algorithmic approaches to the problem of computing reasonable boundaries of such regions based on data points that have evidence indicating that they lie either inside or outside the region. Our problem formulation leads to a number of subproblems related to red-blue point separation and minimum-perimeter polygons, many of which we solve algorithmically. We give experimental results from our implementation and a comparison of the two approaches. This research is supported by the EU-IST Project No. IST-2001-35047 (SPIRIT) and by grant WO 758/4-2 of the German Research Foundation (DFG).     

Supervisory control of modular systems with global specification languages

The paper presents sufficient conditions for modular (supervisory) control synthesis to equal global control synthesis. In modular control synthesis a supervisory control is synthesized for each module separately and the supervisory control consists of the parallel composition of the modular supervisory controls. The general case of the specification that is indecomposable and not necessarily contained in the plant language, which is often the case in practice, is considered. The usual assumption that all shared events are controllable is relaxed by introducing two new structural conditions relying on the global mutual controllability condition. The novel concept used as a sufficient structural condition is strong global mutual controllability. The main result uses a weaker condition called global mutual controllability together with local consistency of the specification. An example illustrates the approach.