Cathodic corrosion: Part 1. Mechanism of corrosion via formation of metal anions in aqueous medium

In this paper we describe an unusual electrochemical phenomenon, namely cathodic corrosion of platinum. We show that all existing models of cathodic corrosion are inconsistent with our experimental observations. Therefore, we present a new model of cathodic corrosion, which is based on the assumption that metal anions are formed at the electrode surface during the corrosion process. These anionic species function as precursors for the formation of the final product of cathodic corrosion–metal nanoparticles

Cathodic corrosion: Part 2. Properties of nanoparticles synthesized by cathodic corrosion

We demonstrate how cathodic corrosion in concentrated aqueous solutions enables one to prepare nanoparticles of various metals and metal alloys. Using various characterization methods we show that the composition of nanoparticles remains that of the starting material, and the resulting size distribution remains rather narrow. For the case of platinum we show how the size and possibly even the shape of the nanoparticles can be easily controlled by the parameters of corrosion. Finally, we discuss the advantages of using the nanoparticles prepared by cathodic corrosion for applications in (electro-)catalysis

SINR Analysis of Opportunistic MIMO-SDMA Downlink Systems with Linear Combining

Opportunistic scheduling (OS) schemes have been proposed previously by the authors for multiuser MIMO-SDMA downlink systems with linear combining. In particular, it has been demonstrated that significant performance improvement can be achieved by incorporating low-complexity linear combining techniques into the design of OS schemes for MIMO-SDMA. However, this previous analysis was performed based on the effective signal-to-interference ratio (SIR), assuming an interference-limited scenario, which is typically a valid assumption in SDMA-based systems. It was shown that the limiting distribution of the effective SIR is of the Frechet type. Surprisingly, the corresponding scaling laws were found to follow $\epsilon\log K$ with $0<\epsilon<1$, rather than the conventional $\log\log K$ form. Inspired by this difference between the scaling law forms, in this paper a systematic approach is developed to derive asymptotic throughput and scaling laws based on signal-to-interference-noise ratio (SINR) by utilizing extreme value theory. The convergence of the limiting distribution of the effective SINR to the Gumbel type is established. The resulting scaling law is found to be governed by the conventional $\log\log K$ form. These novel results are validated by simulation results. The comparison of SIR and SINR-based analysis suggests that the SIR-based analysis is more computationally efficient for SDMA-based systems and it captures the asymptotic system performance with higher fidelity.Comment: Proceedings of the 2008 IEEE International Conference on Communications, Beijing, May 19-23, 200

Electronic shell effects and the stability of alkali nanowires

Experimental conductance histograms for Na nanowires are analyzed in detail and compared to recent theoretical results on the stability of cylindrical and elliptical nanowires, using the free-electron model. We find a one-to-one correspondence between the peaks in the histograms and the most stable nanowire geometries, indicating that several of the commonly observed nanowires have elliptical cross sections

Anisotropic etching of platinum electrodes at the onset of cathodic corrosion

Catalysis and Surface Chemistr

Quantum size effects in Pb islands on Cu(111): Electronic-structure calculations

The appearance of "magic" heights of Pb islands grown on Cu(111) is studied by self-consistent electronic structure calculations. The Cu(111) substrate is modeled with a one-dimensional pseudopotential reproducing the essential features, i.e. the band gap and the work function, of the Cu band structure in the [111] direction. Pb islands are presented as stabilized jellium overlayers. The experimental eigenenergies of the quantum well states confined in the Pb overlayer are well reproduced. The total energy oscillates as a continuous function of the overlayer thickness reflecting the electronic shell structure. The energies for completed Pb monolayers show a modulated oscillatory pattern reminiscent of the super-shell structure of clusters and nanowires. The energy minima correlate remarkably well with the measured most probable heights of Pb islands. The proper modeling of the substrate is crucial to set the quantitative agreement.Comment: 4 pages, 4 figures. Submitte

Subsurface Oxygen on Pt(111) and Its Reactivity for CO Oxidation

Catalysis and Surface Chemistr

Towards unified understanding of conductance of stretched monatomic contacts

When monatomic contacts are stretched, their conductance behaves in qualitatively different ways depending on their constituent atomic elements. Under a single assumption of resonance formation, we show that various conductance behavior can be understood in a unified way in terms of the response of the resonance to stretching. This analysis clarifies the crucial roles played by the number of valence electrons, charge neutrality, and orbital shapes.Comment: 2 figure

Quantum interference structures in the conductance plateaus of gold nanojunctions

The conductance of breaking metallic nanojunctions shows plateaus alternated with sudden jumps, corresponding to the stretching of stable atomic configurations and atomic rearrangements, respectively. We investigate the structure of the conductance plateaus both by measuring the voltage dependence of the plateaus' slope on individual junctions and by a detailed statistical analysis on a large amount of contacts. Though the atomic discreteness of the junction plays a fundamental role in the evolution of the conductance, we find that the fine structure of the conductance plateaus is determined by quantum interference phenomenon to a great extent.Comment: 4 pages, 4 figure

Electron-Transport Properties of Na Nanowires under Applied Bias Voltages

We present first-principles calculations on electron transport through Na nanowires at finite bias voltages. The nanowire exhibits a nonlinear current-voltage characteristic and negative differential conductance. The latter is explained by the drastic suppression of the transmission peaks which is attributed to the electron transportability of the negatively biased plinth attached to the end of the nanowire. In addition, the finding that a voltage drop preferentially occurs on the negatively biased side of the nanowire is discussed in relation to the electronic structure and conduction.Comment: 4 pages, 6 figure