Nitric oxide reduction and carbon monoxide oxidation over carbon-supported copper-chromium catalysts

Carbon supported copper-chromium catalysts are shown to be very active for both the reduction of nitric oxide with carbon monoxide and the oxidation of carbon monoxide with oxygen. Mixed copper-chromium oxide active phases have good activity in the simultaneous removal of nitric oxide and carbon monoxide from exhaust gases. The influence of several catalyst variables has been investigated. The activity per volume of catalyst increases with increasing loading, while the intrinsic activity shows a maximum around C/M=100−50. An optimum catalyst for nitric oxide reduction and carbon monoxide oxidation has a copper/chromium ratio of 2/1. The apparent activation energy for the carbon monoxide oxidation over carbon supported copper-chromium catalysts is 77 kJ/mol, suggesting that the Cu---O bond rupture is the rate-limiting process. The reduction of nitric oxide takes place at higher temperatures. Since all catalysts have a low selectivity for molecular nitrogen formation at lower temperatures, the dissociation of nitric oxide is probably rate determining, resulting in a slightly reduced catalyst system. In an excess of carbon monoxide the reaction is first-order in nitric oxide and zero-order in carbon monoxide. Moisture inhibits the reaction by reversible competitive adsorption, whereas carbon dioxide does not. Oxygen completely inhibits the reduction of nitric oxide due to the more rapid reoxidation of the catalytic sites compared to nitric oxide. Therefore, the reduction of nitric oxide takes place only when all oxygen has been converted and, hence, is shifted to higher temperatures. As a possible consequence, the production of nitrous oxide is reduced. Nitric oxide and molecular oxygen react preferentially with carbon monoxide, so, in an excess of oxidizing component, gasification of the carbon support occurs at higher temperatures after carbon monoxide has been completely consumed.     

Zeolite based films, membranes and membrane reactors: Progress and prospects

The integration of reaction and separation in catalytic membrane reactors has received increasing attention during the past 30 years. The combination promises to deliver more compact and less capital-intensive processes with substantial savings in energy consumption. With the advent of new inorganic materials and processing techniques, there has been renewed interest in exploiting the benefits of membranes in many industrial applications. Zeolite membranes, however, have only recently been considered for catalytic membrane reactor applications. Despite the significant recent interest in these types of membranes there are relatively few reports of the application of such membranes in high-temperature catalytic membrane reactor applications. This can be attributed to a number of limitations that still need to be addressed such as the relatively high price of membrane units, the difficulty of controlling the membrane thickness, permeance, high-temperature sealing, reproducibility and the dilemma of upscaling. A number of research efforts, with some degree of success have been directed to finding solutions to the remaining challenges. This review makes a critical assessment of what has been achieved in the past few years in terms of hurdles that still stand in the way of the successful implementation of zeolite membrane reactors in industry.     

Sensitive and Reversible Detection of Methanol and Water Vapor by In Situ Electrochemically Grown CuBTC MOFs on Interdigitated Electrodes

The in situ electrochemical growth of Cu benzene‐1,3,5‐tricarboxylate (CuBTC) metal–organic frameworks, as an affinity layer, directly on custom‐fabricated Cu interdigitated electrodes (IDEs) is described, acting as a transducer. Crystalline 5–7 µm thick CuBTC layers are grown on IDEs consisting of 100 electrodes with a width and a gap of both 50 µm and a height of 6–8 µm. These capacitive sensors are exposed to methanol and water vapor at 30 °C. The affinities show to be completely reversible with higher affinity toward water compared to methanol. For exposure to 1000 ppm methanol, a fast response is observed with a capacitance change of 5.57 pF at equilibrium. The capacitance increases in time followed diffusion‐controlled kinetics (k = 2.9 mmol s^?0.5 g^?1_CuBTC). The observed capacitance change with methanol concentration follows a Langmuir adsorption isotherm, with a value for the equilibrium affinity K _e = 174.8 bar^?1. A volume fraction f _MeOH = 0.038 is occupied upon exposure to 1000 ppm of methanol. The thin CuBTC affinity layer on the Cu‐IDEs shows fast, reversible, and sensitive responses to methanol and water vapor, enabling quantitative detection in the range of 100–8000 ppm.     

Quenched phosphorescence detection in cyclodextrin-based electrokinetic chromatography

Quenched phosphorescence detection is a sensitive detection method recently introduced in capillary zone electrophoresis. It is based on the dynamic quenching interaction of the analytes (quenchers) with a phosphorophore, 1-bromo-4-naphthalenesulfonate (BrNS), present in the separation buffer. In this study, it is shown that this detection method can also be used in cyclodextrin-based electrokinetic chromatography (CD-EKC) despite the presence in the buffer solution of cyclodextrins, which are known to reduce the luminescence quenching rate constants. Experiments indicate that BrNS mainly resides in the aqueous phase, while the analytes are distributed between both phases. In principle, the observed quenching might arise from the interaction of BrNS with uncomplexed as well as complexed analytes. However, from the dependence of the fractional quenching on the capacity factor (the normalized fractional quenching was found to be equal to the fraction of analyte in the aqueous phase), it was concluded that only aqueous-phase quenching contributes significantly to the observed quenching. Nevertheless, separation and detection can be regarded as fully compatible, because the capacity factors encountered in CD-EKC are generally low (in this study they ranged from about 0.1 to 2.5). Indeed, with nitroaromatic compounds as the target analytes, limits of detection in the 10(-8) M range were achieved.     

A New Implementation of Automath

This paper presents aut, a modern Automath checker. It is a straightforward re-implementation of the Zandleven Automath checker from the seventies. It was implemented about five years ago, in the programming language C. It accepts both the AUT-68 and AUT-QE dialects of Automath. This program was written to restore a damaged version of Jutting's translation of Landau's Grundlagen. Some notable features: It is fast. On a 1 GHz machine it will check the full Jutting formalization (736 K of nonwhitespace Automath source) in 0.6 seconds. Its implementation of -terms does not use named variables or de Bruijn indices (the two common approaches) but instead uses a graph representation. In this representation variables are represented by pointers to a binder. The program can compile an Automath text into one big Automath single line-style -term. It outputs such a term using de Bruijn indices. (These -terms cannot be checked by modern systems like Coq or Agda, because the -typed -calculi of de Bruijn are different from the -typed -calculi of modern type theory.)The source of aut is freely available on the Web at the address .     

Developing a schematic petrogenetic transect for a contact aureole using field spectrometry; a case study in Los Santos,Salamanca Province,central-western Spain

Much work has been done in construction of petrogenetic grids for regional-scale metamorphic terrains, but low-pressure assemblages, such as contact aureoles, have been relatively ignored. This study has focused on developing a petrogenetic transect for a granitic aureole using a portable field spectrometer. Distribution of mineral assemblages, their modes, metamorphic zones, paragenetic sequences and isograds were mapped along a 4 km long transect. The transect starts at the fresh granite and cuts through the metamorphic contact aureole into the host rocks. Metamorphic reactions responsible for mineral changes were also defined. The method demonstrated potential in mineral mapping and the results could be used to support other methods like hyperspectral image analysis.     

Generality and legibility in mobile manipulation

This article investigates methods for achieving more general manipulation capabilities for mobile manipulation platforms, which produce legible behavior in human living environments. To achieve generality and legibility, we combine two control mechanisms. First of all, experience- and observation-based learning of skills is applied to routine tasks, so that the repetitive and stereotypical character of everyday activity is exploited. Second, we use planning, reasoning, and search for novel tasks which have no stereotypical solution. We apply these ideas to the learning and use of action-related places, to the model-based visual recognition and localization of objects, and the learning and application of reaching strategies and motions from humans. We demonstrate the integration of these mechanisms into a single low-level control system for autonomous manipulation platforms.     

Detection of pre-defined boundaries between hydrothermal alteration zones using rotation-variant template matching

A new method for the detection of pre-defined boundaries in single-band image data that uses a rotation-variant template matching (RTM) algorithm is presented. This algorithm matches a miniature image of a pre-defined boundary to image data at various orientations. The image pixels that match boundary criteria are reported in output imagery together with the rotation angle of the template. The method is applied to identify boundaries between hydrothermal alteration zones in processed airborne hyperspectral imagery, based on the presence of white mica minerals. Results show that boundaries identified with RTM are relatively free of noise and more coherent than those identified with, for instance, image slicing techniques. Identified boundaries can be used for image segmentation. The output of the RTM algorithm also provides information on the type of boundary, whether it is crisp or gradual. This information can be used to better characterize mineral variation in the alteration halo associated with fossil hydrothermal systems.     

Benefit of Microscopic Diffusion Measurement for the Characterization of Nanoporous Materials

Detailed knowledge of the transport properties of nanoporous materials is a prerequisite for their complete characterization and optimum technological exploitation. One of the best ways to attain this information is provided by the “microscopic” techniques of diffusion measurement, in particular by the pulsed field gradient technique of NMR and by interference microscopy and IR microscopy. Starting with the measuring principles, the various types of evidence as accessible by these techniques are illustrated. A large variety of host‐guest systems with both ordered and random pore networks have been studied, from microporous up to macroporous materials. The information obtained concerns diffusivities in the various pore domains, extra resistances at the interfaces between them and the associated exchange rates.