Recent advances on the use of active anodes in environmental electrochemistry

Active anodes, especially those consisting of metal mixed oxides (MMOs) containing Ru and/or Ir oxides, have been applied in the treatment of wastewater, especially when chloride ions are present. Their characteristics continuously drive the study of applications of these materials, be they in the degradation of different organic molecules, the preparation of new electrode materials and in the association of various processes to increase pollutant removal. Thus, this brief review aims to present some of the recent advances in the application of active anode materials in environmental electrochemistry. Focussing on the 2018–2020 period, it is possible to note many applied studies, using commercially available materials, covering a wide range of target pollutants. Still other studies aim to modify the catalyst surfaces to increase the mineralization capacity, and the use of these anodes in the production of free chlorine species to mediate indirect organic reduction is observed.     

Microextraction of metal ions based on solidification of a floating drop: Basics and recent updates

This review provides a comprehensive evaluation of solidified floating organic drop microextraction (SFODME) procedures for metal ions preconcentration and their contributions to green chemistry. In this article we focused on the modifications that have been performed in the recent years to improve this environmentally friendly procedure. Among the most important of these modifications are the inclusion of ultrasonic energy, vortex and air agitation to enhance the dispersion process. The article also discussed new challenges in the procedure by using more ecofriendly solvents as extractants such as ionic liquids, deep eutectic. and supramolecular solvents. The coupling of SFODME with solid phase extraction increases selectivity and efficiency of the preconcentration procedure.     

Fused vs. spiro: Kinetic,not thermodynamic preference may direct the reaction of α-carbonyl oxonium ylides

Rh(II)-catalyzed decomposition of certain cyclic α-diazocarbonyl compounds in the presence of cyclic ethers has been shown to give bicyclic ring expansion products. These are thought to arise from a [1,4]-alkyl shift toward the carbonyl oxygen atom and are in contrast with the recently observed spirocyclic products of a Stevens-type [1,2]-alkyl shift within the postulated oxonium ylide intermediate. Quantum chemical calculations performed at the B3LYP/6-31G* level of theory showed that the former reaction pathway (toward fused bicycles) is kinetically preferred.     

Spectroscopic characterization of core and shell regions in monolayer protected gold nanoparticles

We report studies on the structure of the metallic core and the alkyl cap layer in monolayer protected gold nanoparticles having sizes down to 1.6 nm. These particles are obtained by laser ablating gold targets in alkane-thiol solutions at different concentrations. The electronic structure of gold core and the vibrational properties of the capping hydrocarbon chains reveal effects connected with the nanosized nature of the particles.     

Zone specificity in low energy electron stimulated desorption of Cl from reconstructed Si(1 1 1)-7 × 7:Cl surfaces

Diffraction in electron stimulated desorption has revealed a propensity for Cl⁺ desorption from rest atom vs. adatom areas and unfaulted vs. faulted zones of Cl-terminated Si(1 1 1)-(7 × 7) surfaces. We associate the 15 eV ± 1 eV threshold with ionization of Si-Cl σ-bonding surface states and formation of screened two-hole states with Si 3s character. Similar specificity is observed from A and B reconstructions. This can be due to reduced screening in unfaulted regions and increased hole localization in Si back-bonds within faulted regions.     

Structural and electronic properties of graphite layers grown on SiC(0 0 0 1)

Photoelectron spectroscopy, low-energy electron diffraction, and scanning probe microscopy were used to investigate the electronic and structural properties of graphite layers grown by solid state graphitization of SiC(0 0 0 1) surfaces. The process leads to well-ordered graphite layers which are rotated against the substrate lattice by 30°. On on-axis 6H-SiC(0 0 0 1) substrates we observe graphitic layers with up to several 100 nm wide terraces. ARUPS spectra of the graphite layers grown on on-axis 6H-SiC(0 0 0 1) surfaces are indicative of a well-developed band structure. For the graphite/n-type 6H-SiC(0 0 0 1) layer system we observe a Schottky barrier height of ?_B,n = 0.3 ± 0.1 eV. ARUPS spectra of graphite layers grown on 8° off-axis oriented 4H-SiC(0 0 0 1) show unique replicas which are explained by a carpet-like growth mode combined with a step bunching of the substrate.     

Silicon-Based Integrated Optic Pressure Sensor Using Intermodal Interference between TM-Like and TE-Like Modes

In this paper, a silicon-based integrated optic pressure sensor using an intermodal interference between the fundamental TM-like and TE-like modes is described. The sensor consists of a micromachined rectangular diaphragm and a straight polystyrene optical waveguide passing over the diaphragm. Its sensitivity is theoretically known to be strongly dependent on the position of the waveguide over the diaphragm. To experimentally investigate such dependence, we fabricated a sensor with a 1.2 mm ×10 mm ×20 μm diaphragm, over which waveguides were placed at 50 μm intervals. The measured phase sensitivity was 98 mrad/kPa for the waveguide nearest to the diaphragm edge. The measurement was also carried out for the other waveguides. As theoretically expected, the largest sensitivity was obtained for the waveguide nearest to the edge.     

An AFM, XPS and electrochemical study of molecular electroactive monolayers formed by wet chemistry functionalization of H-terminated Si(1 0 0) with vinylferrocene

Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η⁵-C₅H₅)Fe²⁺(η⁵-C₅H₄)-CH₂-CH₂-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe³⁺ at the expenses of Fe²⁺ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO⁻ groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe³⁺ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing.     

Reciprocating sliding wear behavior of laser-clad small amplitude Mo2Ni3Si/NiSi metal silicide composite coatings

Mo₂Ni₃Si/NiSi metal silicide composite coatings with a fine microstructure consisting of Mo₂Ni₃Si primary dendrites and the interdendritic Mo₂Ni₃Si/NiSi eutectics were fabricated on austenitic stainless steel AISI 321 by laser cladding process. Small amplitude reciprocating sliding wear resistance of the coatings is evaluated as functions of normal load and slip amplitude and the wear mechanisms were discussed based on worn surface morphology observations. Results showed that the Mo₂Ni₃Si/NiSi coatings have excellent small amplitude reciprocating sliding wear resistance.     

Towards molecular-scale electronics and biomolecular self-assembly

This paper provides an overview of recent research developments in the field of nanoelectronics with organic materials such as carbon nanotubes and DNA-templated nanowires. Carbon nanotubes and gold electrodes are chemically functionalized in order to contact carbon nanotubes by self-assembly. The transport properties of these nanotubes are dominated by charging effects and display clear Coulomb blockade behaviour. A different approach towards nanoscale electronics is based on the molecular recognition properties of biomolecules such as DNA. As an example, DNA is stretched between electrodes using a molecular combing technique. A two-step metallization procedure leads to the formation of highly conductive gold nanowires.