Ad-atoms and their enhancement effects on Pt activity for formic acid oxidation

Formic acid oxidation has been widely studied at Pt as a model reaction to understand fundamental aspects of electrocatalytic reactions in fuel cells. Electrocatalytic oxidation of formic acid takes place through two parallel pathways (direct and indirect). The indirect pathway proceeds via CO as an intermediate, which is known to be responsible for the poisoning of Pt and its consequent decrease in activity. Surface modification of Pt with ad-atoms is known to hinder this poisoning and promote the direct pathway. The incorporation of polymers (polyaniline, polycarbazole, polyindole) as supports also increases activity. Irreversibly adsorbed Sb and Bi on Pt are known to show high electrocatalytic activity for formic acid oxidation. This work presents the dependence of Sb and Bi irreversible adsorption on immersion time, metal solution concentration and pH. The activity of Sb and Bi modified Pt was correlated against immersion time and percent coverage of Pt by ad-atoms. Polyaniline support effects in combination with a Bi modified Pt catalyst showed enhancement in oxidation current compared to Pt-Bi.

Effects of various salt purity levels on lipid oxidation and sensory characteristics of ground turkey and pork

Salt use in meat products is changing. Consumers desire sea salt which may also contain trace metals and the government is demanding a reduction in sodium. Therefore a need exists to understand how varying impurity levels in salt affect meat quality. This study evaluated the effects of various salt preparations on lipid oxidation, sensory characteristics, protein extractability, and bind strength of ground turkey and pork. This study was a completely randomized design with 5 treatment groups and 6 replications in 2 species. Ground, turkey and pork meat was formulated into one hundred and fifty gram patties with sodium chloride (1%) containing varying amounts of metal impurities (copper, iron, and manganese). Samples were randomly assigned to frozen storage periods of 0, 3, 6, and 9 weeks. After storage, samples were packaged in PVC overwrap and stored under retail display for 5 days. Samples were evaluated for proximate analysis to ensure the fat content was similar for all of the starting material.Thiobarbituric acid reactive substances (TBARS) were determined on raw and cooked samples to evaluate lipid oxidation. A trained six member sensory panel evaluated the samples at each storage period for saltiness, off flavor, and oxidized odor. Break strength was conducted using a Texture Analyzer and compared with salt soluble proteins (increasing salt concentrations) to evaluate protein extractability characteristics. Statistical analyses were conducted using the MIXED procedure of SAS within repeated measures over time where appropriate. No significant differences were observed among the salt treatments for raw and cooked TBARS when the control group was removed (P>0.05). Sensory panelists detected increased levels of off flavor and oxidized odor over the entire storage duration. Less force was required to break the patties from the control group when compared with the salt treatments (P<0.05). As salt concentration increased salt-soluble protein extraction increased, but there was no effect of salt type. Overall, no meaningful statistical differences among the various salt treatments were observed for all of the parameters evaluated for turkey and pork. Salt at a 1% inclusion rate containing varying levels of copper, iron, and manganese impurities in ground turkey thigh meat and ground pork served as a prooxidant. However, if a meat processor uses a 1% inclusion rate of salt in turkey and pork regardless of impurities included, it is unlikely that differences in shelf life or protein functionality would be observed.

Oxygen-Nonstoichiometric YBaCo4O7+δ as a Catalyst in H2O2 Oxidation of Cyclohexene

Here we present oxygen-nonstoichiometric transition metal oxides as highly prominent candidates to catalyze the industrially important oxidation reactions of hydrocarbons when hydrogen peroxide is employed as an environmentally benign oxidant. The proof-of-concept data are revealed for the complex cobalt oxide, YBaCo4O7+δ (0 < δ < 1.5), in the oxidation process of cyclohexene. In the 2-h reaction experiments YBaCo4O7+δ was found to be significantly more active (>60 % conversion) than the commercial TiO2 catalyst (<20 %) even though its surface area was less than one tenth of that of TiO2. In the 7-h experiments with YBaCo4O7+δ, 100 % conversion of cyclohexene was achieved. Immersion calorimetry measurements showed that the high catalytic activity may be ascribed to the exceptional ability of YBaCo4O7+δ to dissociate H2O2 and release active oxygen to the oxidation reaction.

Heavy metal release due to aging effect during zero valent iron nanoparticles remediation

Zero valent iron nanoparticles (nZVI) represent a promising agent for environmental remediation. Nevertheless, their application presents some limitations regarding their rapid oxidation and aggregation in the media. The aim of this study was to determine the effect that nZVI aging has in heavy metal remediation in water. Contaminants studied were Zn, Cd, Ni, Cu and Cr, which are typical elements found in ground and wastewater. Results show a high contaminant removal capacity by the nZVI in the first 2 h of reaction. Nevertheless, for longer reaction times, some of the metal ions that had already been adsorbed in the nZVI were delivered to the water. Cd and Ni show the maximum delivery percentages (65 and 27% respectively after 21 days of contact time). The starting delivery time was shortened when applying lower nZVI amounts. No re-dissolution of Cr was observed in any circumstance because it was the only element incorporated into the nanoparticles core, as TEM images showed. Contaminant release from nZVI is probably due to nanoparticles oxidation caused by aging, which produced a pH decrease and nZVI surface crystallization.

Enhanced oxidation activity from modified ceria: MnOx-ceria, CrOx-ceria and Mg doped VOx-ceria

Ceria is an important component of catalysts for oxidation reactions that proceed through the Mars-van Krevelen mechanism, promoting activity. A paradigm example of this is the VOx–CeO2 system for oxidative dehydrogenation reactions, where vanadium oxide species are supported on ceria and a special synergy between them is behind the enhanced activity: reduction of the catalyst is promoted by ceria undergoing reduction. This leads to favourable oxygen vacancy formation and hydrogen adsorption energies—useful descriptors for the oxidation activity of VOx–CeO2 catalysts. In this paper, we examine if this promoting effect on ceria-based catalysts holds for other metal oxide modifiers and we investigate MnOn– and CrOn–CeO2(111) (n = 0 − 4) as examples. We show, combining density functional theory calculations and statistical thermodynamics that similarly to the vanadia modifier, the stable species in each case is MnO2– and CrO2–CeO2. Both show favourable energetics for oxygen vacancy formation and hydrogen adsorption, indicating that VO2–CeO2 is not the only system of this type that can have an enhanced activity for oxidation reactions. However, the mechanism involved in each case is different: CrO2–CeO2 shows similar properties to VO2–CeO2 with ceria reduction upon oxygen removal stabilising the 5+ oxidation state of Cr. In contrast, with MnO2–CeO2, Mn is preferentially reduced. Finally, a model system of VO2–Mg:CeO2 is explored that shows a synergy between VO2 modification and Mg doping. These results shed light on the factors involved in active oxidation catalysts based on supported metal oxides on ceria that should be taken into consideration in a rational design of such catalysts.

Design principles for maximizing photovoltage in metal-oxide-protected water-splitting photoanodes

Metal oxide protection layers for photoanodes may enable the development of large-scale solar fuel and solar chemical synthesis, but the poor photovoltages often reported so far will severely limit their performance. Here we report a novel observation of photovoltage loss associated with a charge extraction barrier imposed by the protection layer, and, by eliminating it, achieve photovoltages as high as 630mV, the maximum reported so far for water-splitting silicon photoanodes. The loss mechanism is systematically probed in metal-insulator-semiconductor Schottky junction cells compared to buried junction p(+) n cells, revealing the need to maintain a characteristic hole density at the semiconductor/insulator interface. A leaky-capacitor model related to the dielectric properties of the protective oxide explains this loss, achieving excellent agreement with the data. From these findings, we formulate design principles for simultaneous optimization of built-in field, interface quality, and hole extraction to maximize the photovoltage of oxide-protected water-splitting anodes.

Engineering interfacial silicon dioxide for improved metal-insulator-semiconductor silicon photoanode water splitting performance

Silicon photoanodes protected by atomic layer deposited (ALD) TiO2 show promise as components of water splitting devices that may enable the large-scale production of solar fuels and chemicals. Minimizing the resistance of the oxide corrosion protection layer is essential for fabricating efficient devices with good fill factor. Recent literature reports have shown that the interfacial SiO2 layer, interposed between the protective ALD-TiO2 and the Si anode, acts as a tunnel oxide that limits hole conduction from the photoabsorbing substrate to the surface oxygen evolution catalyst. Herein, we report a significant reduction of bilayer resistance, achieved by forming stable, ultrathin (<1.3 nm) SiO2 layers, allowing fabrication of water splitting photoanodes with hole conductances near the maximum achievable with the given catalyst and Si substrate. Three methods for controlling the SiO2 interlayer thickness on the Si(100) surface for ALD-TiO2 protected anodes were employed: (1) TiO2 deposition directly on an HF-etched Si(100) surface, (2) TiO2 deposition after SiO2 atomic layer deposition on an HF-etched Si(100) surface, and (3) oxygen scavenging, post-TiO2 deposition to decompose the SiO2 layer using a Ti overlayer. Each of these methods provides a progressively superior means of reliably thinning the interfacial SiO2 layer, enabling the fabrication of efficient and stable water oxidation silicon anodes.

Investigation of gold-based catalysts for liquid phase oxidation of glucose to glucaric acid

Glucaric acid (GA) is one of the building block chemicals derived from sugar biomass with higher added value. Nowadays, GA is produced by oxidation of glucose (Glu) with either stoichiometric oxidants (HNO3), or by means of electrochemical or biochemical synthesis. However, these processes show drawbacks from either the environmental or economic viewpoint. For this reason, gold nanoparticles (Au NPs) supported on activated carbon (AC) have been studied as catalysts for the oxidation of Glu, using O2 as oxidant in the presence of a base. Using sol immobilization technique, Au NPs have been supported on AC following different experimental procedures. UV-Vis spectroscopy, XRD, TEM and TG analysis were utilized in the characterization of the catalysts. The operational conditions were optimized obtaining 24% of yield of GA, 37% to GO and 27% to byproducts in 1 h, 1000 rpm, 10 bar of O2 and Glu:Au:NaOH molar ratio of 1000:1:3000. Under such conditions, catalysts show relatively high Glu conversion (≥82%) with different GA yields. GO+GA yield is around 58-61%. Therefore, the oxidation reaction was performed at 15 min where Au/AC PVA0 reached the highest yield of GA (16%) and Au/AC PVA2.4 gave the lowest (8%). It is evident that the presence of PVA influences to a higher degree the reaction rate than the Au NPs size. Hence, the effect of different heat treatments where applied for the removal of PVA: washing with water at 60℃ or heat treatment (120-250℃) with Air/H2. Washing treatment and heat treatment at 120℃ with Air/H2 may have resulted in the mildest treatments for the removal of PVA. Finally, two different supports have been used in order to study the effect of metal-support interaction in the immobilization of Au NPs: ZrO2 and AC. Au/AC catalyst demonstrated a higher conversion of GO to GA at short reaction times (15.1% yield GA) compared to Au/ZrO2 (2.4% yield GA).

3D electrocatalysts for the selective glucose oxidation

Nowadays, one of the most important scientific and environmental concern is to reduce global dependence on fossil fuels. The use of lignocellulosic biomass makes it possible to produce important platform molecules such as D-glucose, which is used to synthesize high value-added chemical products such as gluconic acid (GO) and glucaric acid (GA). Moreover, the electrocatalytic oxidation of glucose shows advantages compared to the classical synthesis route, such as the use of non-toxic reactants and milder conditions, making the process greener and more sustainable. In this work, electrocatalysts based on open-cell Ni metal foams were investigated for the glucose electrooxidation. They were used as supplied, oxidized at 500°C and 600°C, and after electrodeposition of Ni(OH)2. The electrocatalysts were characterized by cyclic voltammetry in NaOH solution 0.1M and in a basic D-glucose solution with different glucose concentrations (10mM and 50mM). The effect of the potential applied, the glucose concentration and the reaction time on conversion, selectivity and faradic efficiency were also investigated. 3D Ni electrocatalyst showed promising activity in the conversion of glucose towards gluconic acid, the sample calcined at 500°C showing the best results.

Supported metal nanoparticles for sustainable green catalytic processes

Preformed Au nanoparticles supported on activated carbon and TiO2 were synthesised by sol-immobilisation. Polyethylene glycol, polyvinyl pyrrolidone and polyvinyl alcohol were used as stabilisers for the gold nanoparticles at different polymer/Au wt/wt ratios for each polymer. The effect of polymer/Au wt/wt ratios was investigated on (i) the average nanoparticle size, (ii) catalytic activity for two reactions, 4-nitrophenol reduction and glucose oxidation to glucaric acid. 4-nitrophenol reduction is recognised as a model reaction for nanomaterial catalytic activity tests; glucose oxidation to glucaric acid is a reaction that is traditionally carried out with concentrated nitric acid, for which alternative reaction pathways are looked for in an effort to reduce its environmental impact. The catalysts were characterised from the nanoparticle synthesis by colloidal method by means of UV-vis spectroscopy and DLS analysis, to the immobilisation step by XRD and TEM. The effect of the polymer:Au wt/wt ratio on nanoparticle size depends on the polymer nature, and point out the need to optimise supported nanoparticle synthesis protocols in the future depending on the type of stabiliser. The catalytic tests revealed that the polymers interact with Au nanoparticles through different active sites. Activated carbon (AC) and TiO2 were compared as supports for Au nanoparticles stabilised by PVA at PVA/Au 0,65 wt/wt. AC-supported Au NPs were the most active for glucose oxidation while TiO2-stabilised Au NPs were five times more active in 4-nitrophenol reduction that AC-supported NPs. Hence support and stabiliser are important parameters that should be optimised in order to achieve high catalytic activity for a given reaction.

Synthesis and surface characterization of metal (Mn, Ti) hexacyanoferrate electrodes

Due to the limited resources of lithium, new chemistries based on the abundant and cheap sodium and even zinc have been proposed for the battery market. Prussian Blue Analogues (PBAs) are a class of compounds which have been explored for many different applications because of their intriguing electrochemical and magnetic properties. Manganese and titanium hexacyanoferrate (MnHCF and TiHCF) belong to the class of PBAs. In this work, MnHCF and TiHCF electrodes were synthetized, cycled with cyclic voltammetry (CV) in different setups and subsequently, the surfaces were characterized with X-ray Photoelectron Spectroscopy (XPS). The setups chosen for CVs were coin cell with zinc aqueous solution for the MnHCF series, three-electrode cell and symmetric coin cell with sodium aqueous solution for the TiHCF series. The electrodes were treated with different number of cycles to evaluate the chemical changes and alterations in oxidation states during cycling.

Fabrication of 2D and 3D microelectrode arrays for amperometric dopamine sensing: towards a metal free approach to bioelectronics

Dopamine is a neurotransmitter which has a role in several psychiatric and neurological disorders. In-vivo detection of its concentration at the microscopic scale would benefit the study of these conditions and help in the development of therapies. The ideal sensor would be biocompatible, able to probe concentrations in microscopic volumes and sensitive to the small physiological concentrations of this molecule (10 nM - 1 μM). The ease of oxidation of dopamine makes it possible to detect it by electrochemical methods. An additional requirement in this kind of experiments when run in water, though, is to have a large potential window inside which no redox reactions with water take place. A promising class of materials which are being explored is the one of pyrolyzed photoresists. Photoresists can be lithographically patterned with micrometric resolution and after pyrolysis leave a glassy carbon material which is conductive, biocompatible and has a large electrochemical water window. In this work I developed a fabrication procedure for microelectrode arrays with three dimensional electrodes, making the whole device using just a negative photoresist called SU8. Making 3D electrodes could be a way to enhance the sensitivity of the electrodes without occupying a bigger footprint on the device. I characterized the electrical, morphological, and electrochemical properties of these electrodes, in particular their sensitivity to dopamine. I also fabricated and tested a two dimensional device for comparison. The three dimensional devices fabricated showed inferior properties to their two dimensional counter parts. I found a possible explanation and suggested some ways in which the fabrication could be improved.

Geochemistry Of Acid Mine Drainage From A Coal Mining Area And Processes Controlling Metal Attenuation In Stream Waters, Southern Brazil.

Acid drainage influence on the water and sediment quality was investigated in a coal mining area (southern Brazil). Mine drainage showed pH between 3.2 and 4.6 and elevated concentrations of sulfate, As and metals, of which, Fe, Mn and Zn exceeded the limits for the emission of effluents stated in the Brazilian legislation. Arsenic also exceeded the limit, but only slightly. Groundwater monitoring wells from active mines and tailings piles showed pH interval and chemical concentrations similar to those of mine drainage. However, the river and ground water samples of municipal public water supplies revealed a pH range from 7.2 to 7.5 and low chemical concentrations, although Cd concentration slightly exceeded the limit adopted by Brazilian legislation for groundwater. In general, surface waters showed large pH range (6 to 10.8), and changes caused by acid drainage in the chemical composition of these waters were not very significant. Locally, acid drainage seemed to have dissolved carbonate rocks present in the local stratigraphic sequence, attenuating the dispersion of metals and As. Stream sediments presented anomalies of these elements, which were strongly dependent on the proximity of tailings piles and abandoned mines. We found that precipitation processes in sediments and the dilution of dissolved phases were responsible for the attenuation of the concentrations of the metals and As in the acid drainage and river water mixing zone. In general, a larger influence of mining activities on the chemical composition of the surface waters and sediments was observed when enrichment factors in relation to regional background levels were used.

Bipolar Tribocharging Signal During Friction Force Fluctuations At Metal-insulator Interfaces.

Friction and triboelectrification of materials show a strong correlation during sliding contacts. Friction force fluctuations are always accompanied by two tribocharging events at metal-insulator [e.g., polytetrafluoroethylene (PTFE)] interfaces: injection of charged species from the metal into PTFE followed by the flow of charges from PTFE to the metal surface. Adhesion maps that were obtained by atomic force microscopy (AFM) show that the region of contact increases the pull-off force from 10 to 150 nN, reflecting on a resilient electrostatic adhesion between PTFE and the metallic surface. The reported results suggest that friction and triboelectrification have a common origin that must be associated with the occurrence of strong electrostatic interactions at the interface.

Electrochemical Oxidation Of Landfill Leachate In A Flow Reactor: Optimization Using Response Surface Methodology.

Response surface methodology based on Box-Behnken (BBD) design was successfully applied to the optimization in the operating conditions of the electrochemical oxidation of sanitary landfill leachate aimed for making this method feasible for scale up. Landfill leachate was treated in continuous batch-recirculation system, where a dimensional stable anode (DSA(©)) coated with Ti/TiO2 and RuO2 film oxide were used. The effects of three variables, current density (milliampere per square centimeter), time of treatment (minutes), and supporting electrolyte dosage (moles per liter) upon the total organic carbon removal were evaluated. Optimized conditions were obtained for the highest desirability at 244.11 mA/cm(2), 41.78 min, and 0.07 mol/L of NaCl and 242.84 mA/cm(2), 37.07 min, and 0.07 mol/L of Na2SO4. Under the optimal conditions, 54.99 % of chemical oxygen demand (COD) and 71.07 ammonia nitrogen (NH3-N) removal was achieved with NaCl and 45.50 of COD and 62.13 NH3-N with Na2SO4. A new kinetic model predicted obtained from the relation between BBD and the kinetic model was suggested.