Why Au and Cu Are More Selective Than Pt for Preferential Oxidation of CO at Low Temperature

Self-consistent, periodic density functional theory (DFT) calculations and micro-kinetic modeling are used to compare selectivity for the preferential oxidation of CO (PROX) with respect to H₂ based on studies of elementary reaction steps on the (111) facet of Au, Cu and Pt. The first step of H oxidation (OH formation) has a higher activation barrier than the second step (H₂O formation) on all three metal surfaces, indicating that OH formation competes with CO oxidation for the removal of trace amounts of CO from a typical reformate gas. The activation energy barrier for CO oxidation is found to be 0.18eV on Au(111), 0.82eV on Cu(111) and 0.96eV on Pt(111), whereas the barrier for OH formation is 0.90, 1.28 and 0.83eV respectively. A micro-kinetic model based on the DFT results shows that trends in the selectivity of these metals at different temperatures is due to (i) differences in the rate constants of the competitive CO and H oxidation reactions, and (ii) differences in the CO and H surface coverages. Our results explain why Au and Cu are more selective PROX catalysts compared to Pt at low temperatures. At higher temperatures, Pt and Cu lose some of their selectivity to CO oxidation, whereas the selectivity on Au decreases substantially primarily because of the significantly weaker CO adsorption.     

Monitoring cognitive disturbance in delirium with the ten-point clock test

Isolated bilateral pleural effusion with mediastinal compression leading to hydropic change of the fetus is unusual, and carries a high risk of perinatal death. This condition can be reversed in utero by performing ultrasound-guided shunting surgery. We describe a hydropic fetus at 30 weeks' gestation with rapid recurrence of pleural effusion after thoracentesis. The pleural effusion and hydrops resolved within 1 week after ultrasound-guided thoracoamniotic shunt and the fetal lungs were restored to their normal size. The fetus was born at 35 weeks' gestation and had an uneventful postnatal course. The technique of restoring cardiopulmonary function in utero through intrathoracic decompression offers a valuable alternative to repetitive prenatal thoracentesis or preterm delivery of fetuses with hydrops caused by bilateral pleural effusion.     

Synthesis of carbon nanosheets by inductively coupled radio-frequency plasma enhanced chemical vapor deposition

An ultrathin sheet-like carbon nanostructure, carbon nanosheet, has been effectively synthesized with CH₄ diluted in H₂ by an inductively coupled radio-frequency plasma enhanced chemical vapor deposition. Nanosheets were obtained without catalyst over a wide range of deposition conditions and on a variety of substrates, including metals, semiconductors and insulators. Scanning electron microscopy shows that the sheet-like structures stand on edge on the substrate and have corrugated surfaces. The sheets are 1 nm or less in thickness and have a defective graphite structure. Raman spectra show typical carbon features with D and G peaks at 1350 and 1580 cm⁻¹, respectively. The intensity ratio of these two peaks, I(D)/I(G), increases with methane concentration or substrate temperature, indicating that the crystallinity of the nanosheets decreases. Infrared and thermal desorption spectroscopies reveal hydrogen incorporation into the carbon nanosheets.     

Design of experiments (DOE) technique for microwave/millimeter wave flip‐chip optimization

We present a design of experiments (DOE) technique for microwave/millimeter wave flip‐chip characterization and optimization. Two optimization approaches, signal bump misalignment and transmission line compensation, are combined together for optimal performance for high frequency operation. First, the design of experiments method is presented and its advantages are emphasized. Then, the two techniques are combined together in a factorial experiment with the purpose of optimizing the return loss to any desired frequency. The experiment is based on test structure fabrication and measurements. The one‐factor‐at‐a‐time strategy shows that return loss performance is increased with the misalignment values and decreased with compensation for the frequency range of interest. However, the statistical analysis revealed that the optimal performance is achieved for maximum compensation, and minimum misalignment. The optimal structure is measured from 1 to 75 GHz and shows return loss better than 17 dB. The method can be extended to include more optimization factors in different analysis intervals. Copyright © 2003 John Wiley & Sons, Ltd.     

The application of a computerised videokeratography (CVK) based contact lens fitting software programme on irregularly shaped corneal surfaces.

PURPOSE: To explore the success of the application of a computerised videokeratography (CVK) software system for the fitting of rigid gas permeable (RGP) contact lenses (CLs) on irregular corneal surfaces and compare it to the standard diagnostic fitting procedure. METHODS: This was a comparative prospective study, over a 1-year period (2004-2005). It included 41 RGP CL wearers (68 eyes) with irregular corneal surfaces. Of these, 51 (75%) had keratoconus, 7 (10%) corneal scarring (infectious or traumatic), 6 (6.82%) corneal transplants, 2 (2.9%) astigmatism, and 2 (2.9%) aphakia. Each eye was being re-fitted with a new RGP CL based on a topographical measurement in conjunction with a CL fitting software programme. The performance of the CLs was evaluated regarding visual outcome, fitting characteristics, and efficiency of the fitting procedure. RESULTS: Of the 68 eyes, 53 (77.94%) chose the CL fitted using the CVK software system, 9 (13.24%) chose the CL fitted using the standard procedure, and 6 (8.82%) showed no preference for either CL. There was a statistically significant improvement regarding visual outcome [contrast sensitivity at the spatial frequencies of 0.66 (p=0.029), 3.40 (p=0.008), and 17 (p=0.032), subjective vision (p=0.009)], fitting characteristics [grading scale (p=0.00), lens comfort (p=0.00) and daily wearing time (p=0.002)], and efficiency [number of trial lenses required (p=0.00)] with the CL fitted using the CVK software system. Correlating factors for the likely preference for the CL fitted using the CVK software system were subjective vision (p=0.004), lens comfort (p=0.009), and convenience of the fitting procedure (p=0.023). CONCLUSION: The application of a CVK software system for the fitting procedure of RGP CLs on irregular corneal surfaces was a safe procedure and shown to be more successful and efficient than the standard diagnostic fitting method.     

Chloroform Hydrodechlorination on Palladium Surfaces: A Comparative DFT Study on Pd(111), Pd(100), and Pd(211)

Topics in Catalysis - Palladium has been shown to be an effective catalyst for chloroform hydrodechlorination, which serves as a promising treatment method for industrial chloroform waste. To...     

Effects of operating temperature on electrical parameters in ananalog process

The variation of basic MOS device properties with operating temperature is examined. These devices include both n-channel and p-channel transistors, resistors, junction diodes, and precision capacitors. The theory of such variations is briefly examined, and fits to empirical expressions are graphically derived. Implications of such variations are briefly explored     

A Pipeline Technique for Dynamic Data Transfer on a Multiprocessor Grid

This paper describes a pipeline technique which is used to redistribute data on a multiprocessor grid during runtime. The main purposes of the algorithm are to minimize the data transfer time, prevent congestion on the ports of the receiving processors, and minimize the number of idle processors. One of the key ideas for this algorithm is the creation of processor classes, firstly introduced by Desprez et al. [IEEE Transactions on Parallel and Distributed Systems 9(2):102 (1998).] Based on the idea of classes, we create the pipeline tasks used to organize the redistribution of data. Our experimental results show that this pipeline technique can significantly reduce the amount of time required to complete a dynamic data transfer task.