Electrodeposited lead dioxide coatings

Lead dioxide coatings on inert substrates such as titanium and carbon now offer new opportunities for a material known for 150 years. It is now recognised that electrodeposition allows the preparation of stable coatings with different phase structures and a wide range of surface morphologies. In addition, substantial modification to the physical properties and catalytic activities of the coatings are possible through doping and the fabrication of nanostructured deposits or composites. In addition to applications as a cheap anode material in electrochemical technology, lead dioxide coatings provide unique possibilities for probing the dependence of catalytic activity on layer composition and structure (critical review, 256 references)

Solid electrochemical mass spectrometry (SEMS) for investigation of supported metal catalysts under high vacuum

A new experimental set-up, coupling electrochemistry and mass spectroscopic techniques, for the investigation of a solid electrochemical cell under high vacuum conditions (HV) is presented. Two configurations are realized allowing the investigation of both the electrochemical and electrocatalytical behavior of a thin Pt layer on yttria stabilized zirconia (YSZ). We can readily select the atmosphere down to 10(-6) Pa partial pressure and determine the response of the system in less than 1 s. Under HV conditions, YSZ appears electrochemically active and we have identified, in the cathodic potential domain, the reduction/oxidation process of zirconia and in the anodic domain, the platinum oxidation/reduction and the oxygen evolution reactions. In a catalytic active gas mixture, despite the Faradaic enhancement of the CO oxidation observed over Pt/YSZ during an anodic polarization, an intriguing sustainable enhanced Pt/YSZ catalyst activity is achieved after current interruption

Investigation of the Pt/YSZ interface at low oxygen partial pressure by solid electrochemical mass spectroscopy under high vacuum conditions

The Pt/YSZ interface was investigated at low oxygen partial pressure under high vacuum (HV) conditions at 400 A degrees C. Two different electrochemical techniques were coupled to mass spectrometric gas analysis using a new solid electrochemical mass spectrometric monitoring device. Under cathodic polarization, the lack of oxygen in the gas phase induces the reduction of the YSZ solid electrolyte which acts as oxygen source for the formation of O2- ions migrating to the anode. Under anodic polarization, both platinum oxidation and oxygen evolution reaction are identified. PtO (x) is formed at both the Pt/YSZ and the Pt/gas interface according to two different mechanisms. At the Pt/YSZ interface, PtO (x) formation is an electrochemical process following a parabolic growth law, while the presence of PtO (x) at the Pt/gas interface is related to the diffusion of PtO (x) formed at the triple phase boundary towards the Pt/gas interface. It is proposed that the side oxygen evolution reaction stabilizes thermodynamically the PtO (x) diffusion toward the gas exposed interface during the anodic polarization

Electro-oxidation of cyanide on active and non-active anodes: Designing the electrocatalytic response of cobalt spinels

[EN] The feasibility of the electrochemical technologies for wastewater treatment greatly relies on the design of efficient but inexpensive electrocatalysts. It is generally accepted that the so-called ¿non-active¿ anodes (like the boron-doped diamond (BDD) or SnO2-based anodes), producing highly oxidizing hydroxyl radicals, are the most promising candidates for pollutants abatement. In this work, the electrocatalytic performance of various cobalt oxides, pure and doped with Cu or Au, for CN¿ oxidation has been studied and compared with that of conventional graphite, BDD, SnO2-Sb and SnO2-Sb-Pt. The metal oxide electrodes were prepared by thermal decomposition of the salt precursors onto Ti. For the M-doped Co3O4 electrodes, the nominal M/Co ratios were Cu/ Co=0.07¿1.00; and Au/Co=0.05¿0.20. The electrodes were characterized by different techniques (XRD, SEM, EDX, XPS) and their electrocatalytic response was studied by cyclic voltammetry and galvanostatic electrolysis in a H-type cell in aqueous 0.1M NaOH. The obtained results show that the nature of the dopant plays a key role on the electrocatalytic behavior of cobalt spinels. Thus, while Cu catalyzes the CN¿ electro-oxidation, Au declines it. This is explained by the fact that, unlike Au (which segregates as Au-rich particles), Cu is effectively incorporated into the spinel structure by forming a solid solution (CuxCo3-xO4). In this solid solution, atomic scale Cu(spinel)-CN¿ specific interactions occur to catalyze the reaction, whereas in segregated Au particles the oxidation is hindered probably by a too-strong adsorption of cyanide and/or its inaccessibility to oxide active sites. Electrolysis runs have revealed that ¿active¿ over-saturated Cu-doped spinels (Cu/Co=1.00) exhibit higher current efficiencies than conventional graphite and ¿non-active¿ BDD and SnO2-based anodes. Hence, we hereby demonstrate that an inexpensive ¿active¿ electrocatalyst can show even higher efficiency than the most powerful BDD anode. These results highlight the significance of anode design in the application of the electrochemical technique for wastewater treatment.Financial support from the Spanish Ministerio de Economia y Competitividad and FEDER funds (MAT2016-76595-R, IJCI-2014-20012) is gratefully acknowledgedBerenguer, R.; Quijada, C.; La Rosa-Toro, A.; Morallón, E. (2019). Electro-oxidation of cyanide on active and non-active anodes: Designing the electrocatalytic response of cobalt spinels. Separation and Purification Technology. 208:42-50. https://doi.org/10.1016/j.seppur.2018.05.024S425020

Insight on the fundamentals of advanced oxidation processes. Role and review of the determination methods of reactive oxygen species

Advanced oxidation processes (AOPs) have known increased application to treat wastewaters containing recalcitrant compounds that are hardly degraded by conventional technologies. AOPs are characterized by the formation of strong oxidants such as hydroxyl radicals, superoxide anions, hydroperoxyl radicals and singlet oxygen, which react with the contaminant, contributing to its degradation. This paper provides an overview of the determination methods of reactive oxygen species, ROS, in the application of AOPs; the methods developed in the available literature for the detection and quantification of ROS are reviewed as a first step in the assessment and detailed description of the mechanisms involved in the oxidation reactions, focusing on the critical analysis of the main strengths and weaknesses presented by the probe molecules employed in the evaluated studies.This research was supported by the Ministry of Economy and Competitiveness (MINECO/SPAIN) and European Regional Development Fund (ERDF) under the project CTQ2011-25262