Mechanistic aspects of the water–gas shift reaction on alumina-supported noble metal catalysts: In situ DRIFTS and SSITKA-mass spectrometry studies

Steady-state isotopic transient kinetic analysis (SSITKA) experiments coupled with mass spectrometry were performed for the first time to study essential mechanistic aspects of the water–gas shift (WGS) reaction over alumina-supported Pt, Pd, and Rh catalysts. In particular, the concentrations (μmol g⁻¹) of active intermediate species found in the carbon-path from CO to the CO₂ product gas (use of ¹³CO), and in the hydrogen-path from H₂O to the H₂ product gas (use of D₂O) of the reaction mechanism were determined. It was found that by increasing the reaction temperature from 350 to 500 °C the concentration of active species in both the carbon-path and hydrogen-path increased significantly. Based on the large concentration of active species present in the hydrogen-path (OH/H located on the alumina support), the latter being larger than six equivalent monolayers based on the exposed noble metal surface area (θ > 6.0), the small concentration of OH groups along the periphery of metal-support interface, and the significantly smaller concentration (μmol g⁻¹) of active species present in the carbon-path (adsorbed CO on the noble metal and COOH species on the alumina support and/or the metal-support interface), it might be suggested that diffusion of OH/H species on the alumina support towards catalytic sites present in the hydrogen-path of reaction mechanism might be considered as a slow reaction step. The formation of labile OH/H species is the result of dissociative chemisorption of water on the alumina support, where the role of noble metal is to activate the CO chemisorption and likely to promote formate decomposition into CO₂ and H₂ products. It was found that there is a good correlation between the surface concentration and binding energy of CO on the noble metal (Pt, Pd or Rh) with the activity of alumina-supported noble metal towards the WGS reaction.     

Low-temperature H2-SCR of NO on a novel Pt/MgO-CeO2 catalyst

The selective catalytic reduction of NO by H₂ under strongly oxidizing conditions (H₂-SCR) in the low-temperature range of 100–200 °C has been studied over Pt supported on a series of metal oxides (e.g., La₂O₃, MgO, Y₂O₃, CaO, CeO₂, TiO₂, SiO₂ and MgO-CeO₂). The Pt/MgO and Pt/CeO₂ solids showed the best catalytic behavior with respect to N₂ yield and the widest temperature window of operation compared with the other single metal oxide-supported Pt solids. An optimum 50 wt% MgO-50wt% CeO₂ support composition and 0.3 wt% Pt loading (in the 0.1–2.0 wt% range) were found in terms of specific reaction rate of N₂ production (mols N₂/g_cat s). High NO conversions (70–95%) and N₂ selectivities (80–85%) were also obtained in the 100–200 °C range at a GHSV of 80,000 h⁻¹ with the lowest 0.1 wt% Pt loading and using a feed stream of 0.25 vol% NO, 1 vol% H₂, 5 vol% O₂ and He as balance gas. Addition of 5 vol% H₂O in the latter feed stream had a positive influence on the catalytic performance and practically no effect on the stability of the 0.1 wt% Pt/MgO-CeO₂ during 24 h on reaction stream. Moreover, the latter catalytic system exhibited a high stability in the presence of 25–40 ppm SO₂ in the feed stream following a given support pretreatment. N₂ selectivity values in the 80–85% range were obtained over the 0.1 wt% Pt/MgO-CeO₂ catalyst in the 100–200 °C range in the presence of water and SO₂ in the feed stream. The above-mentioned results led to the obtainment of patents for the commercial exploitation of Pt/MgO-CeO₂ catalyst towards a new NO_x control technology in the low-temperature range of 100–200 °C using H₂ as reducing agent. Temperature-programmed desorption (TPD) of NO, and transient titration of the adsorbed surface intermediate NO_x species with H₂ experiments, following reaction, have revealed important information towards the understanding of basic mechanistic issues of the present catalytic system (e.g., surface coverage, number and location of active NO_x intermediate species, NO_x spillover).     

Towards social behavior in virtual-agent navigation

We present Social Groups and Navigation (SGN), a method to simulate the walking behavior of small pedestrian groups in virtual environments. SGN is the first method to simulate group behavior on both global and local levels of an underlying planning hierarchy. We define quantitative metrics to measure the coherence and the sociality of a group based on existing empirical data of real crowds. SGN does not explicitly model coherent and social formations, but it lets such formations emerge from simple geometric rules. In addition to a previous version, SGN also handles group-splitting to smaller groups throughout navigation as well as social sub-group behavior whenever a group has to temporarily split up to re-establish its coherence. For groups of four, SGN generates between 13% and 53% more socially-friendly behavior than previous methods, measured over the lifetime of a group in the simulation. For groups of three, the gain is between 15% and 31%, and for groups of two, the gain is between 1% and 4%. SGN is designed in a flexible way, and it can be integrated into any crowd-simulation framework that handles global path planning and any path following as separate steps. Experiments show that SGN enables the simulation of thousands of agents in real time.     

Elastic block ciphers: method, security and instantiations

We introduce the concept of an elastic block cipher which refers to stretching the supported block size of a block cipher to any length up to twice the original block size while incurring a computational workload that is proportional to the block size. Our method uses the round function of an existing block cipher as a black box and inserts it into a substitution- permutation network. Our method is designed to enable us to form a reduction between the elastic and the original versions of the cipher. Using this reduction, we prove that the elastic version of a cipher is secure against key-recovery attacks if the original cipher is secure against such attacks. We note that while reduction-based proofs of security are a cornerstone of cryptographic analysis, they are typical when complete components are used as sub-components in a larger design. We are not aware of the use of such techniques in the case of concrete block cipher designs. We demonstrate the general applicability of the elastic block cipher method by constructing examples from existing block ciphers: AES, Camellia, MISTY1, and RC6. We compare the performance of the elastic versions to that of the original versions and evaluate the elastic versions using statistical tests measuring the randomness of the ciphertext. We also use our examples to demonstrate the concept of a generic key schedule for block ciphers.

Predicting Greek adolescents’ intentions to smoke: A focus on normative processes.

Objective: To examine the effects of normative influences on adolescent smoking in Greece, a country with weak social norms against smoking and relatively ineffective tobacco control policies. Design: A cross-sectional survey methodology was employed, and a representative sample of Greek high school students was recruited (N = 1,920, M age = 14 years). Main Outcome Measures: Normative beliefs, attitudes, perceived behavioral control, self-esteem, and intentions to smoke. Results: Multiple-regression and mediation analyses were conducted. The effects of public smoking on intentions to smoke were mediated by beliefs of perceived prevalence of smoking among peers, subjective norms, and situational temptations. Self-esteem significantly moderated the effects of subjective norms on intentions to smoke. Conclusions: Prosmoking norms in one’s environment become internalized into biased normative beliefs about smoking, and increase susceptibility to smoke under social pressure. The effect of subjective norms on intentions to smoke was stronger among adolescents with low self-esteem, suggesting that self-esteem may act as a vulnerability factor in the process of smoking initiation. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Reconfiguration of carrier assignment in cellular networks

We consider the problem of updating nominal carrier assignments in cellular networks, which dymamically operate with channel borrowing and reassignments, to match the timevarying offered traffic demands encountered on these systems. Assuming an existing assignment of nominal carriers and the new requirements in each cell, we formulate the problem of obtaining a new assignment such that the number of carriers required to meet the total traffic demand as well as the number of different assignments between the old and the new allocation are minimized. We introduce two approaches to obtain this new assignment. One approach treats the two objectives independently and is applicable to problems with cochannel interference constraints only. This approach produces a new assignment optimized with respect to the first goal, and then rearranges the frequencies of this new allocation so that the number of different assignments with respect to the previous allocation is minimum. A second approach aims at satisfying both goals at the same time and is applicable to problems with any type of interference constraints. The main advantage of this approach is the introduction of a single window parameter which can control the assignments produced, by favoring one goal at the expense of the other. We study several transition scenarios in macrocellular and microcellular environments, and show that in the majority of cases these objectives are conflicting, and that reconfiguration strongly depends on the amount of change of the traffic requirements.     

COVERAGE: detecting and reacting to worm epidemics using cooperation and validation

Cooperative defensive systems communicate and cooperate in their response to worm attacks, but determine the presence of a worm attack solely on local information. Distributed worm detection and immunization systems track suspicious behavior at multiple cooperating nodes to determine whether a worm attack is in progress. Earlier work has shown that cooperative systems can respond quickly to day-zero worms, while distributed detection systems allow detectors to be more conservative (i.e., paranoid) about potential attacks because they manage false alarms efficiently. In this paper we present our investigation into the complex tradeoffs in such systems between communication costs, computation overhead, accuracy of the local tests, estimation of viral virulence, and the fraction of the network infected before the attack crests. We evaluate the effectiveness of different system configurations in various simulations. Our experiments show that distributed algorithms are better able to balance effectiveness against worms and viruses with reduced cost in computation and communication when faced with false alarms. Furthermore, cooperative, distributed systems seem more robust against malicious participants in the immunization system than earlier cooperative but non-distributed approaches.     

The Effects of P-Poisoning of CexZr1−xO2 on the Transient Oxygen Storage and Release Kinetics

The present work reports on the investigation of the effects of chemical poisoning of Ce_xZr_1?xO₂ solids by phosphorous (P) on the kinetics of oxygen storage and release (OSR) of the thus derived P-contaminated solids, as a function of Ce_xZr_1?xO₂ solid composition (x = 0.3, 0.5 and 0.7) for the first time. Phosphorous deposition on the surface of Ce_xZr_1?xO₂ particles followed by calcination in air at 850 °C forms nano-crystals of CePO₄, which lead to a drastic decrease in the population of surface and subsurface reactive and mobile oxygen species due to the formation of P–O–Ce bonding. The concentration (μmol/g) of exchangeable ¹⁶O in the solid with ¹⁸O from the gas phase was found to increase, and the degree of reduction in the Oxygen Storage Capacity (OSC) to decrease with increasing Ce content in the Ce_xZr_1?xO₂ solid after P-poisoning. The increase in the Ce content of Ce_xZr_1?xO₂ makes its OSR properties more resistant against P-poisoning due to the increasing number of poison-free Ce atoms, which are able to participate in the Ce³⁺ ? Ce⁴⁺ redox cycle.