Oxygen evolution at ultrathin nanostructured Ni(OH)2 layers deposited on conducting glass

Ultrathin and transparent nanostructured Ni(OH)2 films were deposited on conducting glass (F:SnO2) by a urea-based chemical bath deposition method. By controlling the deposition time, the amount of deposited Ni(OH)2 was varied over 7 orders of magnitude. The turnover number for O2 generation, defined as the number of O2 molecules generated per catalytic site (Ni atom) and per second, increases drastically as the electrocatalyst amount decreases. The electrocatalytic activity of the studied samples (measured as the current density at a certain potential) increases with the amount of deposited Ni(OH)2 until a saturation value is already obtained for a thin film of around 1 nm in thickness, composed of Ni(OH)2 nanoplatelets lying flat on the conductive support. The deposition of additional amounts of catalyst generates a porous honeycomb structure that does not improve (only maintains) the electrocatalytic activity. The optimized ultrathin electrodes show a remarkable stability, which indicates that the preparation of highly transparent electrodes, efficient for oxygen evolution, with a minimum amount of nickel is possible.

Synthetic Boron-Doped Diamond Electrodes for Electrochemical Water Treatment

Boron-doped diamond electrodes have emerged as anodic material due to their high physical, chemical and electrochemical stability. These characteristics make it particularly interesting for electrochemical wastewater treatments and especially due to its high overpotential for the Oxygen Evolution Reaction. Diamond electrodes present the maximum efficiency in pollutant removal in water, just limited by diffusion-controlled electrochemical kinetics. Results are presented for the elimination of benzoic acid and for the electrochemical treatment of synthetic tannery wastewater. The results indicate that diamond electrodes exhibit the best performance for the removal of total phenols, COD, TOC, and colour.

Asymmetric hybrid capacitors based on activated carbon and activated carbon fibre–PANI electrodes

Composites consisting of polyaniline (PANI) coatings inside the microporosity of an activated carbon fibre (ACF) were prepared by electrochemical and chemical methods. Electrochemical characterization of both composites points out that the electrodes with polyaniline show a higher capacitance than the pristine porous carbon electrode. These materials have been used to develop an asymmetric capacitor based on activated carbon (AC) as negative electrode and an ACF–PANI composite as positive electrode in H2SO4 solution as electrolyte. The presence of a thin layer of polyaniline inside the porosity of the activated carbon fibres avoids the oxidation of the carbon material and the oxygen evolution reaction is produced at more positive potentials. This capacitor was tested in a maximum cell voltage of 1.6 V and exhibited high energy densities, calculated for the unpackaged active materials, with values of 20 W h kg−1 and power densities of 2.1 kW kg−1 with excellent cycle lifetime (90% during the first 1000 cycles) and high coulombic efficiency.

Pt- and Ru-Doped SnO2–Sb Anodes with High Stability in Alkaline Medium

Different Pt- and Ru-doped Ti/SnO2–Sb electrodes were synthesized by thermal decomposition. The effect of the gradual substitution of Sb by Ru in the nominal composition on the physicochemical and electrochemical properties were evaluated. The electrochemical stability of the electrodes was estimated from accelerated tests at 0.5 A cm–2 in 1 M NaOH. Both as-synthesized and deactivated electrodes were thoroughly characterized by scanning electron microscopy (SEM), energy-dispersive X-ray microanalysis (EDX), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction analysis (XRD). The incorporation of a small amount (about 3 at. %) of both Pt and Ru into the SnO2–Sb electrodes produced a 400-times increase in their service life in alkaline medium, with no remarkable change in the electrocatalysis of the oxygen evolution reaction (OER). It is concluded that the deactivation of the electrodes is promoted by alkaline dissolution of metal species and coating detachment at high potentials. The introduction of Pt has a coating compacting effect, and Ru(IV), at low amounts until 9.75 at. %, replaces the Sn(IV) cations in the rutile-like SnO2 structure to form a solid solution that strongly increases the stability of the electrodes. The observed Ru segregation and decreased stability for larger Ru contents (x > 9.75 at. %), together with the selective dissolution of Ru after deactivation, suggest that the formation of a homogeneous (RuδSn1−δ)O2 single-phase is crucial for the stabilization of these electrodes.

Electrochemical generation of oxygen-containing groups in an ordered microporous zeolite-templated carbon

Zeolite templated carbon (ZTC) was electrochemically oxidized under various conditions, and its chemistry and structural evolution were compared to those produced by conventional chemical oxidation. In both oxidation methods, a general loss of the original structure regularity and high surface area was observed with increasing amount of oxidation. However, the electrochemical method showed much better controllability and enabled the generation of a large number of oxygen functional groups while retaining the original structure of the ZTC. Unlike chemical treatments, highly microporous carbons with an ordered 3-D structure, high surface area (ranging between 1900 and 3500 m2/g) and a large number of oxygen groups (O = 11,000–3300 μmol/g), have been prepared by the electrochemical method. Some insights into the electrooxidation mechanism of carbon materials are proposed from the obtained polarization curves, using ZTC as a model carbon material.

Probing the Electrocatalytic Oxygen Reduction Reaction Reactivity of Immobilized Multicopper Oxidase CueO

The bioelectrocatalytic (oxygen reduction reaction, ORR) properties of the multicopper oxidase CueO immobilized on gold electrodes were investigated. Macroscopic electrochemical techniques were combined with in situ scanning tunneling microscopy (STM) and surface-enhanced Raman spectroscopy at the ensemble and at the single-molecule level. Self-assembled monolayer of mercaptopropionic acid, cysteamine, and p-aminothiophenol were chosen as redox mediators. The highest ORR activity was observed for the protein attached to amino-terminated adlayers. In situ STM experiments revealed that the presence of oxygen causes distinct structure and electronic changes in the metallic centers of the enzyme, which determine the rate of intramolecular electron transfer and, consequently, affect the rate of electron tunneling through the protein. Complementary Raman spectroscopy experiments provided access for monitoring structural changes in the redox state of the type 1 copper center of the immobilized enzyme during the CueO-catalyzed oxygen reduction cycle. These results unequivocally demonstrate the existence of a direct electronic communication between the electrode substrate and the type 1 copper center.

Kinetic Analysis and Pollutant Evolution During Thermal Degradation of Printed Circuit Boards Considering the Effect of Metals

Paper submitted to the 7th International Symposium on Feedstock Recycling of Polymeric Materials (7th ISFR 2013), New Delhi, India, 23-26 October 2013.

Paleogene evolution of the External Betic Zone and geodynamic implications

Interdisciplinary studies combining field data (geological and tectonic mapping, lithostratigraphic reconstructions, lithofacies characterization, correlations and sampling) and laboratory analyses (biostratigraphy, chronostratigraphy, clay mineralogy and sandstone petrography) of eight Senonian-Paleogene successions from the Sierra de La Pila and Sierra de El Carche areas (Murcia province, SE Spain) belonging to the External Betic Zone are presented. Field evidence of tectonic activity (slumps, olistostromes, syn-genetic folds, lateral variability, changes in thicknesses, para- and unconformity boundaries, stratigraphic gaps, shallowing upward trends to emersion, etc.) was found in several Paleogene intervals. The results enable a better reconstruction of the stratigraphic architecture and chronostratigraphy of the Paleogene record, highlighting in particular: facies evolution, discontinuities, depositional sequences (Middle-Upper Maastrichtian, Upper Paleocene-Middle Eocene, Oligocene-Lower Aquitanian), environmental evolution (homogeneous conditions during the Late Cretaceous and successive realm diversification from platform to slope to basin) and correlations, along the Prebetic to Subbetic transition, which is a key sector to understand the northeastward variations of the South Iberian margin. A conclusive paleogeographic and geodynamic evolutionary model for the study area is proposed, hypothesizing that Paleogene compressive tectonics affected the eastern External Betic Zone. In addition, correlations with successions from the western External Betic Zone evidenced asynchronous deformation from east to west along the internalmost External Betic Zone. Moreover, a comparison with the external Tunisian Tell enables the recognition of similar sedimentarytectonic events, imposing new constraints in the Paleogene geodynamic reconstruction throughout the western Tethys.

Functionalization of carbon nanotubes using aminobenzene acids and electrochemical methods. Electroactivity for the oxygen reduction reaction

Functionalized carbon nanotubes (CNTs) using three aminobenzene acids with different functional groups (carboxylic, sulphonic, phosphonic) in para position have been synthesized through potentiodynamic treatment in acid media under oxidative conditions. A noticeable increase in the capacitance for the functionalized carbon nanotubes mainly due to redox processes points out the formation of an electroactive polymer thin film on the CNTs surface along with covalently bonded functionalities. The CNTs functionalized using aminobenzoic acid rendered the highest capacitance values and surface nitrogen content, while the presence of sulfur and/or phosphorus groups in the aminobenzene structure yielded a lower functionalization degree. The oxygen reduction reaction (ORR) activity of the functionalized samples was similar to that of the parent CNTs, independently of the functional group present in the aminobenzene acid. Interestingly, a heat treatment in N2 atmosphere with a very low O2 concentration (3125 ppm) at 800 °C of the CNTs functionalized with aminobenzoic acid produced a material with high amounts of surface oxygen and nitrogen groups (12 and 4% at., respectively), that seem to modulate the electron-donor properties of the resulting material. The onset potential and limiting current for ORR was enhanced for this material. These are promising results that validates the use of electrochemistry for the synthesis of novel N-doped electrocatalysts for ORR in combination with adequate heat treatments.

The Early Miocene “Bisciaro volcaniclastic event” (northern Apennines, Italy): a key study for the geodynamic evolution of the central-western Mediterranean

The Early Miocene Bisciaro Fm., a marly limestone succession cropping out widely in the Umbria–Romagna–Marche Apennines, is characterized by a high amount of volcaniclastic content, characterizing this unit as a peculiar event of the Adria Plate margin. Because of this volcaniclastic event, also recognizable in different sectors of the central-western Mediterranean chains, this formation is proposed as a “marker” for the geodynamic evolution of the area. In the Bisciaro Fm., the volcaniclastic supply starts with the “Raffaello” bed (Earliest Aquitanian) that marks the base of the formation and ends in the lower portion of the Schlier Fm. (Late Burdigalian–Langhian p.p.). Forty-one studied successions allowed the recognition of three main petrofacies: (1) Pyroclastic Deposits (volcanic materials more than 90 %) including the sub-petrofacies 1A, Vitroclastic/crystallo-vitroclastic tuffs; 1B, Bentonitic deposits; and 1C, Ocraceous and blackish layers; (2) Resedimented Syn-Eruptive Volcanogenic Deposits (volcanic material 30–90 %) including the sub-petrofacies 2A, High-density volcanogenic turbidites; 2B, Low-density volcanogenic turbidites; 2C, Crystal-rich volcanogenic deposits; and 2D, Glauconitic-rich volcaniclastites; (3) Mixing of Volcaniclastic Sediments with Marine Deposits (volcanic material 5–30 %, mixed with marine sediments: marls, calcareous marls, and marly limestones). Coeval volcaniclastic deposits recognizable in different tectonic units of the Apennines, Maghrebian, and Betic Chains show petrofacies and chemical–geochemical features related to a similar calc-alkaline magmatism. The characterization of this event led to the hypothesis of a co-genetic relationship between volcanic activity centres (primary volcanic systems) and depositional basins (depositional processes) in the Early Miocene palaeogeographic and palaeotectonic evolution of the central-western Mediterranean region. The results support the proposal of a geodynamic model of this area that considers previously proposed interpretations.

3D geometry of growth strata in a fault-propagation fold: insights into space–time evolution of the Crevillente Fault (Abanilla-Alicante sector), Betic Cordillera, Spain

This work presents a 3D geometric model of growth strata cropping out in a fault-propagation fold associated with the Crevillente Fault (Abanilla-Alicante sector) from the Bajo Segura Basin (eastern Betic Cordillera, southern Spain). The analysis of this 3D model enables us to unravel the along-strike and along-section variations of the growth strata, providing constraints to assess the fold development, and hence, the fault kinematic evolution in space and time. We postulate that the observed along-strike dip variations are related to lateral variation in fault displacement. Along-section variations of the progressive unconformity opening angles indicate greater fault slip in the upper Tortonian–Messinian time span; from the Messinian on, quantitative analysis of the unconformity indicate a constant or lower tectonic activity of the Crevillente Fault (Abanilla-Alicante sector); the minor abundance of striated pebbles in the Pliocene-Quaternary units could be interpreted as a decrease in the stress magnitude and consequently in the tectonic activity of the fault. At a regional scale, comparison of the growth successions cropping out in the northern and southern limits of the Bajo Segura Basin points to a southward migration of deformation in the basin. This means that the Bajo Segura Fault became active after the Crevillente Fault (Abanilla-Alicante sector), for which activity on the latter was probably decreasing according to our data. Consequently, we propose that the seismic hazard at the northern limit of the Bajo Segura Basin should be lower than at the southern limit.

Carbon and nitrogen limitation increase chitosan antifungal activity in Neurospora crassa and fungal human pathogens

Chitosan permeabilizes plasma membrane and kills sensitive filamentous fungi and yeast. Membrane fluidity and cell energy determine chitosan sensitivity in fungi. A five-fold reduction of both glucose (main carbon (C) source) and nitrogen (N) increased 2-fold Neurospora crassa sensitivity to chitosan. We linked this increase with production of intracellular reactive oxygen species (ROS) and plasma membrane permeabilization. Releasing N. crassa from nutrient limitation reduced chitosan antifungal activity in spite of high ROS intracellular levels. With lactate instead of glucose, C and N limitation increased N. crassa sensitivity to chitosan further (4-fold) than what glucose did. Nutrient limitation also increased sensitivity of filamentous fungi and yeast human pathogens to chitosan. For Fusarium proliferatum, lowering 100-fold C and N content in the growth medium, increased 16-fold chitosan sensitivity. Similar results were found for Candida spp. (including fluconazole resistant strains) and Cryptococcus spp. Severe C and N limitation increased chitosan antifungal activity for all pathogens tested. Chitosan at 100 μg ml-1 was lethal for most fungal human pathogens tested but non-toxic to HEK293 and COS7 mammalian cell lines. Besides, chitosan increased 90% survival of Galleria mellonella larvae infected with C. albicans. These results are of paramount for developing chitosan as antifungal.

Role of the interfacial water structure on electrocatalysis: Oxygen reduction on Pt(1 1 1) in methanesulfonic acid

Most of electrocatalytic reactions occur in an aqueous environment. Understanding the influence of water structure on reaction dynamics is fundamental in electrocatalysis. In this work, the role of liquid water structure on the oxygen reduction at Pt(1 1 1) electrode is analyzed in methanesulfonic (MTSA) and perchloric acids. This is because these different anions can exert a different influence on liquid water structure. Results reveal a lower ORR electrode activity in MTSA than in HClO4 solutions and they are discussed in light of anion's influence on water structural ordering. From them, the existence of an outer-sphere, rate determining, step in the ORR mechanism is suggested.

Semivolatile and Volatile Compound Evolution during Pyrolysis and Combustion of Colombian Coffee Husk

Thermal characterization of coffee husk (Coffea arabica) from Colombian coffee has been studied. Different products, mostly volatile and semivolatile compounds, were analyzed, paying special attention to 16 polycyclic aromatic hydrocarbons (PAHs) classified by the United States Environmental Protection Agency (U.S. EPA) as priority pollutants, frequently used for checking toxicity in environmental samples. A fixed amount of raw material was exposed to different excess air ratios (λ = 0–2.33) and nominal temperature of 1123 K in a horizontal quartz reactor. The results show that coffee husk is a promising biomass for energetic exploitation with reduced formation of PAHs in a low air excess ratio. This implies reduction of carcinogenic potential in the limited presence of oxygen, demonstrated by calculating the carcinogenic potential (KE) for each experimental condition. Most volatile and semivolatile compounds followed different trends, with the oxygen presence prevailing their decomposition with increasing the air excess ratio.