Electrooxidation of methanol in an alkaline fuel cell: determination of the nature of the initial adsorbate

It is essential to correctly determine the nature of the initial adsorbate in order to calculate the pathway for any given reaction. Recent literature provides conflicting information on the first step in the methanol decomposition pathway. This work sets out to establish what role the solution and the surface have to play in the initial adsorption-deprotonation process. Density functional theory (DFT) calculations, in combination with a cluster-continuum model approach are used to resolve the nature of the adsorbing species. We show that methanol is the dominant species in solution over methoxide, and also has a smaller barrier to adsorption. The nature of the surface species is revealed to be a methanol-OH complex.

A new look at dual-hop relaying: Performance limits with hardware impairments

Physical transceivers have hardware impairments that create distortions which degrade the performance of communication systems. The vast majority of technical contributions in the area of relaying neglect hardware impairments and, thus, assume ideal hardware. Such approximations make sense in low-rate systems, but can lead to very misleading results when analyzing future high-rate systems. This paper quantifies the impact of hardware impairments on dual-hop relaying, for both amplify-and-forward and decode-and-forward protocols. The outage probability (OP) in these practical scenarios is a function of the effective end-to-end signal-to-noise-and-distortion ratio (SNDR). This paper derives new closed-form expressions for the exact and asymptotic OPs, accounting for hardware impairments at the source, relay, and destination. A similar analysis for the ergodic capacity is also pursued, resulting in new upper bounds. We assume that both hops are subject to independent but non-identically distributed Nakagami-m fading. This paper validates that the performance loss is small at low rates, but otherwise can be very substantial. In particular, it is proved that for high signal-to-noise ratio (SNR), the end-to-end SNDR converges to a deterministic constant, coined the SNDR ceiling, which is inversely proportional to the level of impairments. This stands in contrast to the ideal hardware case in which the end-to-end SNDR grows without bound in the high-SNR regime. Finally, we provide fundamental design guidelines for selecting hardware that satisfies the requirements of a practical relaying system.

The Role of Water and Adsorbed Hydroxyls on Ethanol Electrochemistry on Pd: New Mechanism, Active Centers and Energetics for Direct Ethanol Fuel Cell Running in Alkaline Medium

First principles calculations with molecular dynamics are
utilized to simulate a simplified electrical double layer formed in the
active electric potential region during the electrocatalytic oxidation of
ethanol on Pd electrodes running in an alkaline electrolyte. Our
simulations provide an atomic level insight into how ethanol oxidation
occurs in fuel cells: New mechanisms in the presence of the simplified
electrical double layer are found to be different from the traditional
ones; through concerted-like dehydrogenation paths, both acetaldehyde
and acetate are produced in such a way as to avoid a variety of
intermediates, which is consistent with the experimental data obtained
from in situ FTIR spectroscopy. Our work shows that adsorbed OH on
the Pd electrode rather than Pd atoms is the active center for the
reactions; the dissociation of the C−H bond is facilitated by the
adsorption of an OH− anion on the surface, resulting in the formation
of water. Our calculations demonstrate that water dissociation rather than H desorption is the main channel through which
electrical current is generated on the Pd electrode. The effects of the inner Helmholtz layer and the outer Helmholtz layer are
decoupled, with only the inner Helmholtz layer being found to have a significant impact on the mechanistics of the reaction. Our
results provide atomic level insight into the significance of the simplified electrical double layer in electrocatalysis, which may be
of general importance.

The origin of high activity but low CO2 selectivity on binary PtSn in the direct ethanol fuel cell

The most active binary PtSn catalyst for direct ethanol fuel cell applications has been studied at 20 ^oC and 60 ^oC, using variable temperature electrochemical in-situ FTIR. In comparison with Pt, binary PtSn inhibits ethanol dissociation to CO(a), but promotes partial oxidation to acetaldehyde and acetic acid. Increasing the temperature from 20 ^oC to 60 ^oC facilitates both ethanol dissociation to CO(a) and their further oxidation to CO₂, leading to an increased selectivity towards CO₂; however, acetaldehyde and acetic acid are still the main products. Potential-dependent phase diagrams for surface oxidants of OH(a) formation on Pt(111), Pt(211) and Sn modified Pt(111) and Pt(211) surfaces have been determined using density functional theory (DFT) calculations. It is shown that Sn promotes the formation of OH(a) with a lower onset potential on the Pt(111) surface, whereas an increase in the onset potential is found on modification of the (211) surface. In addition, Sn inhibits the Pt(211) step edge with respect to ethanol C-C bond breaking compared with that found on the pure Pt, which reduces the formation of CO(a). Sn was also found to facilitate ethanol dehydrogenation and partial oxidation to acetaldehyde and acetic acid which, combined with the more facile OH(a) formation on the Pt(111) surface, gives us a clear understanding of the experimentally determined results. This combined electrochemical in-situ FTIR and DFT study, provides, for the first time, an insight into the long-term puzzling features of the high activity but low CO₂ production found on binary PtSn ethanol fuel cell catalysts.

NSUN4 Is a Dual Function Mitochondrial Protein Required for Both Methylation of 12S rRNA and Coordination of Mitoribosomal Assembly

Biogenesis of mammalian mitochondrial ribosomes requires a concerted maturation of both the small (SSU) and large subunit (LSU). We demonstrate here that the m(5)C methyltransferase NSUN4, which forms a complex with MTERF4, is essential in mitochondrial ribosomal biogenesis as mitochondrial translation is abolished in conditional Nsun4 mouse knockouts. Deep sequencing of bisulfite-treated RNA shows that NSUN4 methylates cytosine 911 in 12S rRNA (m5C911) of the SSU. Surprisingly, NSUN4 does not need MTERF4 to generate this modification. Instead, the NSUN4/MTERF4 complex is required to assemble the SSU and LSU to form a monosome. NSUN4 is thus a dual function protein, which on the one hand is needed for 12S rRNA methylation and, on the other hand interacts with MTERF4 to facilitate monosome assembly. The presented data suggest that NSUN4 has a key role in controlling a final step in ribosome biogenesis to ensure that only the mature SSU and LSU are assembled.

Improved APF strategies for dual-arm local motion planning

Manipulator motion planning is a classic problem in robotics, with a number of complete solutions available for their motion in controlled (industrial) environments. Owing to recent technological advances in the field of robotics, there has been a significant development of more complex robots with high-fidelity sensors and more computational power. One such example has been a rise in the production of humanoid robots equipped with dual-arm manipulators which require complex motion planning algorithms. Also, the technological advances have resulted in a shift from using manipulators in strictly controlled environments, to investigating the deployment of manipulators in dynamic or unknown environments. As a result, a greater emphasis has been put on the development of local motion planners, which can provide real-time solutions to these problems. Artificial Potential Fields (APFs) is one such popular local motion planning technique, which can be applied to manipulator motion planning, however, the basic algorithm is severely prone to local minima problems. Here, two modified APF-based strategies for solving the dual-arm motion planning task in unknown environments are proposed. Both techniques make use of configuration sampling and subgoal selection to assist the APFs in avoiding these local minima scenarios. Extensive simulation results are presented to validate the efficacy of the proposed methodology.