Reversible Scavenging of Dioxygen from Air by a Copper Complex.

We report that exposing the dipyrrin complex (EMindL)Cu(N2) to air affords rapid, quantitative uptake of O2 in either solution or the solid-state to yield (EMindL)Cu(O2). The air and thermal stability of (EMindL)Cu(O2) is unparalleled in molecular copper-dioxygen coordination chemistry, attributable to the ligand flanking groups which preclude the [Cu(O2)]1+ core from degradation. Despite the apparent stability of (EMindL)Cu(O2), dioxygen binding is reversible over multiple cycles with competitive solvent exchange, thermal cycling, and redox manipulations. Additionally, rapid, catalytic oxidation of 1,2-diphenylhydrazine to azoarene with the generation of hydrogen peroxide is observed, through the intermittency of an observable (EMindL)Cu(H2O2) adduct. The design principles gleaned from this study can provide insight for the formation of new materials capable of reversible scavenging of O2 from air under ambient conditions with low-coordinate CuI sorbents.

Microbial fuel cell biosensor for the determination of biochemical oxygen demand of wastewater samples containing readily and slowly biodegradable organics.

OBJECTIVES: Single-chamber air cathode microbial fuel cells (MFCs) were applied as biosensors for biochemical oxygen demand (BOD) measurement of real wastewaters with considerable suspended and/or slowly biodegradable organic content. RESULTS: The measurement method consists of batch sample injection, continuous measurement of cell voltage and calculation of total charge (Q) gained during the biodegradation of organic content. Diverse samples were analyzed: acetate and peptone samples containing only soluble readily biodegradable substrates; corn starch and milk samples with suspended and colloidal organics; real domestic and brewery wastewaters. Linear regression fitted to the Q vs. BOD5 measurement points of the real wastewaters provided high (> 0.985) R2 values. Time requirement of the measurement varied from 1 to 4 days, depending on the composition of the sample. CONCLUSIONS: Relative error of BOD measured in the MFCs comparing with BOD5 was less than 10%, thus the method might be a good basis for the development of on-site automatic BOD sensors for real wastewater samples.

Hybrid Analytical Platform Based on Field-Asymmetric Ion Mobility Spectrometry, Infrared Sensing, and Luminescence-Based Oxygen Sensing for Exhaled Breath Analysis.

The reliable online analysis of volatile compounds in exhaled breath remains a challenge, as a plethora of molecules occur in different concentration ranges (i.e., ppt to %) and need to be detected against an extremely complex background matrix. Although this complexity is commonly addressed by hyphenating a specific analytical technique with appropriate preconcentration and/or preseparation strategies prior to detection, we herein propose the combination of three different detector types based on truly orthogonal measurement principles as an alternative solution: Field-asymmetric ion mobility spectrometry (FAIMS), Fourier-transform infrared (FTIR) spectroscopy-based sensors utilizing substrate-integrated hollow waveguides (iHWG), and luminescence sensing (LS). By carefully aligning the experimental needs and measurement protocols of all three methods, they were successfully integrated into a single compact analytical platform suitable for online measurements. The analytical performance of this prototype system was tested via artificial breath samples containing nitrogen (N2), oxygen (O2), carbon dioxide (CO2), and acetone as a model volatile organic compound (VOC) commonly present in breath. All three target analytes could be detected within their respectively breath-relevant concentration range, i.e., CO2 and O2 at 3-5 % and at ~19.6 %, respectively, while acetone could be detected with LOQs as low as 165-405 ppt. Orthogonality of the three methods operating in concert was clearly proven, which is essential to cover a possibly wide range of detectable analytes. Finally, the remaining challenges toward the implementation of the developed hybrid FAIMS-FTIR-LS system for exhaled breath analysis for metabolic studies in small animal intensive care units are discussed.

Oxygen transfer rates in shaken culture vessels from Fernbach flasks to microtiter plates.

By a sulfite oxidation method, oxygen transfer rates (OTRs) were determined in 11 types of culture vessels from 2.8-L Fernbach (FB) flasks to 96-, 48-, and 24-well square deepwell microtiter plates (MTPs). OTRs ranged from 140 mM/h in 250-mL Ultrayield™ flasks shaken at 300 rpm with a 50 mm diameter shaker throw to 5 mM/h in unbaffled FBs shaken at 200 rpm with a 25 mm throw. Baffles in FBs increased OTRs 6-12-fold under various shaking conditions, and up to five-fold in 250-mL flasks, depending on the type of baffles. Corner-baffling was superior to bottom-baffling in glass, 250-mL flasks. In MTPs, OTRs increased with increasing well size and decreasing fill volume. At 50 mm throw and 300 rpm, 24-well MTPs had OTRs comparable to corner-baffled, 250-mL flasks (∼100 mM/h). The OTRs in unbaffled flasks were relatively insensitive to shaking conditions, increasing less than two-fold between the most modest and the most vigorous conditions. There was no consistency across vessels as to whether the alternate incubation conditions of 70 mm throw and 250 rpm produced higher OTRs than the 50 mm throw and 300 rpm regimen. No increase in OTR was seen in any MTP when the cover hole diameter was increased beyond 4.5 mm. OTRs decreased as viscosity increased, falling smoothly in unbaffled flasks and 24-well MTPs, but 48-well and 96-well MTPs showed precipitous OTR drops as viscosity increased. Matching the OTRs of screening vessels to the oxygen uptake rates of microbial cultures can greatly reduce the number of false positive strains that are forwarded from microbial screens. Biotechnol. Bioeng. 2016;113: 1729-1735. © 2016 Wiley Periodicals, Inc.

Spatially Separated Photosystem II and a Silicon Photoelectrochemical Cell for Overall Water Splitting: A Natural-Artificial Photosynthetic Hybrid.

Integrating natural and artificial photosynthetic platforms is an important approach to developing solar-driven hybrid systems with exceptional function over the individual components. A natural-artificial photosynthetic hybrid platform is formed by wiring photosystem II (PSII) and a platinum-decorated silicon photoelectrochemical (PEC) cell in a tandem manner based on a photocatalytic-PEC Z-scheme design. Although the individual components cannot achieve overall water splitting, the hybrid platform demonstrated the capability of unassisted solar-driven overall water splitting. Moreover, H2 and O2 evolution can be separated in this system, which is ascribed to the functionality afforded by the unconventional Z-scheme design. Furthermore, the tandem configuration and the spatial separation between PSII and artificial components provide more opportunities to develop efficient natural-artificial hybrid photosynthesis systems.

Cryogenic separation of an oxygen-argon mixture in natural air samples for the determination of isotope and molecular ratios.

RATIONALE: The separation and purification of oxygen-argon mixtures are critical in the high-precision analysis of Δ(17) O and δ(O2 /Ar) for geochemical applications. At present, chromatographic methods are used for the separation and purification of oxygen-argon mixtures or pure oxygen, but these methods require the use of high-purity helium as a carrier gas. Considerable interest has been expressed in the development of a helium-free cryogenic separation of oxygen-argon mixtures in natural air samples. METHODS: The precise and simplified cryogenic separation of oxygen-argon mixtures from natural air samples presented here was made possible using a single 5A (30/60 mesh) molecular sieve column. The method involves the trapping of eluted gases using molecular sieves at liquid nitrogen temperature, which is associated with isotopic fractionation. We tested the proposed method for the determination of isotopic fractionations during the gas exchange between water and atmospheric air at equilibrium. The dependency of fractionation was studied at different water temperatures and for different methods of equilibration (bubbling and stirring). Isotopic and molecular fractionations during gas desorption from molecular sieves were studied for different amounts and types of molecular sieves. RESULTS: Repeated measurements of atmospheric air yielded a reproducibility (±SD) of 0.021 ‰, 0.044 ‰, 15 per meg and 1.9 ‰ for δ(17) O, δ(18) O, Δ(17) O and δ(O2 /Ar) values, respectively. We applied the method to determine equilibrium isotope fractionation during gas exchange between air and water. Consistent δ(18) O and Δ(17) O results were obtained with the latest two studies, whereas there was a significant difference in δ(18) O values between seawater and deionized water. CONCLUSIONS: We have revised a helium-free, cryogenic separation of oxygen-argon mixtures in natural air samples for isotopic and molecular ratio analysis. The use of a single 13X (1/8" pellet) molecular sieve yielded the smallest isotopic and molecular fractionations, and this fractionation by molecular sieves can be corrected by the amount of molecular sieve used in the experiment. The reproducibility of the method was tested by the measurement of the oxygen isotope ratios of dissolved oxygen at equilibrium with atmospheric air. We confirmed that the choice of methods for making air-equilibrated water was not related to the magnitude of isotope fractionation, whereas there was a difference between seawater and deionized water.

18O enrichment in phosphorus pools extracted from soybean leaves.

The objective of this study was to investigate the isotopic composition of oxygen bound to phosphate (δ(18)O-PO(4)) in different phosphorus (P) pools in plant leaves. As a model plant we used soybean (Glycine max cv Toliman) grown in the presence of ample P in hydroponic cultures. The leaf blades were extracted with 0.3 M trichloroacetic acid (TCA) and with 10 M nitric acid. These extractions allowed measurement of the TCA-soluble reactive P (TCA P) that is rapidly cycled within the cell and the total leaf P. The difference between total leaf P and TCA P yielded the structural P which includes organic P compounds not extractable by TCA. P uptake and its translocation and transformation within the soybean plants lead to an (18)O enrichment of TCA P (δ(18)O-PO(4) between 16.9 and 27.5‰) and structural P (δ(18)O-PO(4) between 42.6 and 68.0 ‰) compared with 12.4‰ in the phosphate in the nutrient solution. δ(18)O values of phosphate extracted from soybean leaves grown under optimal conditions are greater than the δ(18)O-PO(4) values of the provided P source. Furthermore, the δ(18)O-PO(4) of TCA P seems to be controlled by the δ(18)O of leaf water and the activity of inorganic pyrophosphatase or other pyrophosphatases.

Interferences from oxygen reduction reactions in bioelectroanalytical measurements: the case study of nitrate and nitrite biosensors.

Bioelectroanalytical procedures based on cathodic processes are often subject to interference from dissolved oxygen. At the potentials applied for analyte detection, oxygen reduction may occur directly at the electrode or may be catalyzed by the electron mediators or the sensing enzyme of the biosensor. These processes affect the background current and may thus result in erroneous analyte quantification. In this review, current strategies to circumvent these oxygen interferences are presented and critically assessed with respect to their compatibility for on-site monitoring with amperometric biosensing devices operating at low potential. The main strategies consist in (1) use of oxygen scavenging systems to remove dissolved oxygen from the sample, (2) design of bioelectroanalytical approaches to shift the applied potential for analyte detection to more positive values, and (3) development of electrode materials to increase the overpotential for the oxygen reduction reaction. The latest developments in these approaches have recently led to the first biosensing devices based on reductases fully compatible with on-site monitoring requirements and this opens up possibilities for their widespread application.

Enhanced water splitting by Fe2O3-TiO2-FTO photoanode with modified energy band structure.

The effect of TiO2 layer applied to the conventional Fe2O3/FTO photoanode to improve the photoelectrochemical performance was assessed from the viewpoint of the microstructure and energy band structure. Regardless of the location of the TiO2 layer in the photoanodes, that is, Fe2O3/TiO2/FTO or TiO2/Fe2O3/FTO, high performance was obtained when α-Fe2O3 and H-TiNT/anatase-TiO2 phases existed in the constituent Fe2O3 and TiO2 layers after optimized heat treatments. The presence of the Fe2O3 nanoparticles with high uniformity in the each layer of the Fe2O3/TiO2/FTO photoanode achieved by a simple dipping process seemed to positively affect the performance improvement by modifying the energy band structure to a more favorable one for efficient electrons transfer. Our current study suggests that the application of the TiO2 interlayer, together with α -Fe2O3 nanoparticles present in the each constituent layers, could significantly contribute to the performance improvement of the conventional Fe2O3 photoanode.

Plasmonic photoanodes for solar water splitting with visible light.

We report a plasmonic water splitting cell in which 95% of the effective charge carriers derive from surface plasmon decay to hot electrons, as evidenced by fuel production efficiencies up to 20-fold higher at visible, as compared to UV, wavelengths. The cell functions by illuminating a dense array of aligned gold nanorods capped with TiO(2), forming a Schottky metal/semiconductor interface which collects and conducts the hot electrons to an unilluminated platinum counter-electrode where hydrogen gas evolves. The resultant positive charges in the Au nanorods function as holes and are extracted by an oxidation catalyst which electrocatalytically oxidizes water to oxygen gas.

Removal of COD and colour in real pharmaceutical wastewater by photoelectrocatalytic oxidation method.

In this study, TiO2/Ni photo-anode and multi-walled carbon nano-tubes (MWCNTs) air cathode were prepared by the dip-coating method, and the photoelectrocatalytic degradation of real pharmaceutical wastewater was investigated in the self-made reactor. The combination of the TiO2/Ni electrode and MWCNTs air cathode was adopted to treat the pharmaceutical wastewater by the process of photoelectrocatalysis. Various operational parameters to achieve optimum efficiency of this photoelectrocatalytic degradation system are presented, such as applied bias voltage, NaCl concentration, pH and different degradation methods. Under the optimal conditions, the removal of chemical oxygen demand (COD) and colour are 93.5% and 78.5% respectively. The possible roles of the anode-cathode on the reactions and the probable mechanisms of effect were also discussed. The photoelectrocatalytic technology can be used for the long-term treatment of real pharmaceutical wastewater.

Application of advanced oxidation processes for cleaning of industrial water generated in wet dedusting of shaft furnace gases.

The paper presents results of studies into advanced oxidation processes in 03 and 03/UV systems. An advanced oxidation process (AOP) was conducted to reduce the load of impurities in circulating waters from wet de-dusting of shaft furnace gases. Besides inorganic impurities, i.e. mainly arsenic compounds (16 g As L(-1) on average), lead, zinc, chlorides and sulphates, the waters also contain some organic material. The organic material is composed of a complex mixture that contains, amongst others, aliphatic compounds, phenol and its derivatives, pyridine bases, including pyridine, and its derivatives. The test results show degradation of organic and inorganic compounds during ozonation and photo-oxidation processes. Analysis of the solutions from the processes demonstrated that the complex organic material in the industrial water was oxidized in ozonation and in photo-oxidation, which resulted in formation of aldehydes and carboxylic acids. Kinetic degradation of selected pollutants is presented. Obtained results indicated that the O3/UV process is more effective in degradation of organic matter than ozonation. Depending on the process type, precipitation of the solid phase was observed. The efficiency of solid-phase formation was higher in photo-oxidation with ozone. It was found that the precipitated solid phase is composed mainly of arsenic, iron and oxygen.

Enhanced photoelectrochemical water-splitting effect with a bent ZnO nanorod photo anode decorated with Ag nanoparticles.

Zinc oxide (ZnO) nanorods coated with silver (Ag) film on a polyethylene terephthalate (PET)flexible substrate were used as the photo anode for water splitting. The hybrid nanostructures were prepared via low-temperature hydrothermal growth and electron beam evaporation. The effects of plasmonic enhanced absorption, surface recombination inhibition and improved charge transport are investigated by varying the Ag thickness. Light trapping and absorption enhancement are further studied by optimizing the curvature of the PET substrates. The maximum short circuit current density (JSC, 0.616 mA cm -2) and the photoelectron conversion efficiency (PCE, 0.81%) are achieved with an optimized Ag film thickness of 10 nm and substrate bending radius of 6.0 mm. The maximum JSC and PCE are seven times and ten times, respectively, higher than those of the bare ZnO nanorods on flexible substrates without bending. The overall PEC performance improvement is attributed to the plasmonic effects induced by Ag film and improved charge transport due to inhibition of ZnO surface charge recombination. Enhanced light trapping (harvesting) induced by bending the PET substrates further improved the overall efficiency.

Effect of doping (C or N) and co-doping (C+N) on the photoactive properties of magnetron sputtered titania coatings for the application of solar water-splitting.

The photocatalytic splitting of water into hydrogen and oxygen using a photoelectrochemical (PEC) cell containing titanium dioxide (TiO2) photoanode is a potentially renewable source of chemical fuels. However, the size of the band gap (-3.2 eV) of the TiO2 photocatalyst leads to its relatively low photoactivity toward visible light in a PEC cell. The development of materials with smaller band gaps of approximately 2.4 eV is therefore necessary to operate PEC cells efficiently. This study investigates the effect of dopant (C or N) and co-dopant (C+N) on the physical, structural and photoactivity of TiO2 nano thick coating. TiO2 nano-thick coatings were deposited using a closed field DC reactive magnetron sputtering technique, from titanium target in argon plasma with trace addition of oxygen. In order to study the influence of doping such as C, N and C+N inclusions in the TiO2 coatings, trace levels of CO2 or N2 or CO2+N2 gas were introduced into the deposition chamber respectively. The properties of the deposited nano-coatings were determined using Spectroscopic Ellipsometry, SEM, AFM, Optical profilometry, XPS, Raman, X-ray diffraction UV-Vis spectroscopy and tri-electrode potentiostat measurements. Coating growth rate, structure, surface morphology and roughness were found to be significantly influenced by the types and amount of doping. Substitutional type of doping in all doped sample were confirmed by XPS. UV-vis measurement confirmed that doping (especially for C doped sample) facilitate photoactivity of sputtered deposited titania coating toward visible light by reducing bandgap. The photocurrent density (indirect indication of water splitting performance) of the C-doped photoanode was approximately 26% higher in comparison with un-doped photoanode. However, coating doped with nitrogen (N or N+C) does not exhibit good performance in the photoelectrochemical cell due to their higher charge recombination properties.

Extra-low-temperature oxygen storage capacity of CeO2 nanocrystals with cubic facets.

Herein we demonstrate the extra-low-temperature oxygen storage capacity (OSC) of cerium oxide nanocrystals with cubic (100) facets. A considerable OSC occurs at 150 °C without active species loading. This temperature is 250 °C lower than that of irregularly shaped cerium oxide. This result indicates that cubic (100) facets of cerium oxide have the characteristics to be a superior low-temperature catalyst.

Formation of C-C and C-O bonds and oxygen removal in reactions of alkanediols, alkanols, and alkanals on copper catalysts.

This study reports evidence for catalytic deoxygenation of alkanols, alkanals, and alkanediols on dispersed Cu clusters with minimal use of external H(2) and with the concurrent formation of new C-C and C-O bonds. These catalysts selectively remove O-atoms from these oxygenates as CO or CO(2) through decarbonylation or decarboxylation routes, respectively, that use C-atoms present within reactants or as H(2)O using H(2) added or formed in situ from CO/H(2)O mixtures via water-gas shift. Cu catalysts fully convert 1,3-propanediol to equilibrated propanol-propanal intermediates that subsequently form larger oxygenates via aldol-type condensation and esterification routes without detectable involvement of the oxide supports. Propanal-propanol-H(2) equilibration is mediated by their chemisorption and interconversion at surfaces via C-H and O-H activation and propoxide intermediates. The kinetic effects of H(2), propanal, and propanol pressures on turnover rates, taken together with measured selectivities and the established chemical events for base-catalyzed condensation and esterification reactions, indicate that both reactions involve kinetically relevant bimolecular steps in which propoxide species, acting as the base, abstract the α-hydrogen in adsorbed propanal (condensation) or attack the electrophilic C-atom at its carbonyl group (esterification). These weakly held basic alkoxides render Cu surfaces able to mediate C-C and C-O formation reactions typically catalyzed by basic sites inherent in the catalyst, instead of provided by coadsorbed organic moieties. Turnover rates for condensation and esterification reactions decrease with increasing Cu dispersion, because low-coordination corner and edge atoms prevalent on small clusters stabilize adsorbed intermediates and increase the activation barriers for the bimolecular kinetically relevant steps required for both reactions.

Kinetics investigation of oxygen storage capacity in La2O3-CeO2 solid solution.

La2O3-CeO2 nanopowders with different La2O3 (0-20 mol%) were prepared by the sol-gel method. The modification of the cubic structure of ceria by substituting La3+ for Ce4+ into the lattice of CeO2 has been investigated. The crystal structure of La2O3-CeO2 nanomaterials has been examined by X-ray powder diffraction and analyzed by the Rietveld refinement method. The introduction of La3+ enlarges the octahedral void of unit cell in the cubic CeO2, which favors the oxygen migration in the crystal lattice. Raman characterization results show that the wavenumber of the La2O3-CeO2 solid solution shifted to red and the oxygen vacancy increased with lanthana content in Ce(1-x)La(x)O(2-x/2). The oxygen vacancy, generated by La3+ substituting for Ce4+, could supply more channels for oxygen migration through the lattice. The changes of lattice structure and the oxygen vacancy with La2O3 are correspondence with the results of oxygen storage capacity (OSC) measurement, which indicate that the changes of macro-performance are connected with the microstructure deformation of La2O3-CeO2. The kinetics of Ce0.9La0.2O1.9 nanomaterials with the highest OSC value was studied and the apparent activation energy (E(a)) of reduction and oxidation process was calculated to be 5.6 and 6.0 kJ/mol, respectively. The low E(a) value might be one of the reasons for Ce0.8La0.2O1.9 nanomaterials with the high OSC value.

A built-in zero valent iron anaerobic reactor to enhance treatment of azo dye wastewater.

Waste scrap iron was packed into an upflow anaerobic sludge blanket (UASB) reactor to form a zero valent iron (ZVI) - UASB reactor system for treatment of azo dye wastewater. The ZVI acted as a reductant to decrease ORP in the reactor by more than 40 mv and functioned as an acid buffer to increase the pH in the reactor from 5.44 to 6.29, both of which improved the performance of the anaerobic reactor. As a result, the removal of color and COD in this reactor was 91.7% and 53%, respectively, which was significantly higher than that of a reference UASB reactor without ZVI. The UV-visible spectrum demonstrated that absorption bands of the azo dye from the ZVI-UASB reactor were substantially reduced. The ZVI promoted methanogenesis, which was confirmed by an increase in CH(4) content in the biogas from 47.9% to 64.8%. The ZVI bed was protected well from rusting, which allowed it to function stably. The effluent could be further purified only by pH adjustment because the Fe(2+) released from ZVI served as a flocculent.

Using a constructed wetland for non-point source pollution control and river water quality purification: a case study in Taiwan.

The Kaoping River Rail Bridge Constructed Wetland, which was commissioned in 2004, is one of the largest constructed wetlands in Taiwan. This multi-function wetland has been designed for the purposes of non-point source (NPS) pollutant removal, wastewater treatment, wildlife habitat, recreation, and education. The major influents of this wetland came from the local drainage trench containing domestic, agricultural, and industrial wastewaters, and effluents from the wastewater treatment plant of a paper mill. Based on the quarterly investigation results from 2007 to 2009, more than 96% of total coliforms (TC), 48% of biochemical oxygen demand (BOD), and 40% of nutrients (e.g. total nitrogen, total phosphorus) were removed via the constructed wetland system. Thus, the wetland system has a significant effect on water quality improvement and is capable of removing most of the pollutants from the local drainage system before they are discharged into the downgradient water body. Other accomplishments of this constructed wetland system include the following: providing more green areas along the riversides, offering more water assessable eco-ponds and eco-gardens for the public, and rehabilitating the natural ecosystem. The Kaoping River Rail Bridge Constructed Wetland has become one of the most successful multi-function constructed wetlands in Taiwan. The experience obtained from this study will be helpful in designing similar natural treatment systems for river water quality improvement and wastewater treatment.

Removal of COD and colour from young municipal landfill leachate by Fenton process.

Landfill is a common solution for the final disposal of municipal solid waste in Turkey. In recent years, studies of landfill leachate treatment by Fenton process have indicated that these methods can effectively reduce concentrations of organic contaminants and colour. The aim of this study is to investigate the removal efficiencies of colour and organic matter as COD from young municipal landfill leachate and the effect of operating conditions such as initial pH and Fenton's reagent dosage. Leachate was collected from municipal sanitary landfill located in city of Konya, Turkey. The main characteristics of the leachate were: pH = 7.25, colour = 3510 ptCo, COD = 38200 mgL(-1), BOD5 = 22000 mgL(-1), ratio of BOD5/COD was 0.58 and alkalinity as CaCO3 = 10250 mgL(-1). It is observed that presenting a high value of COD and BOD5 and the rate of BOD5/COD values indicate that the leachate can be defined as young. The treatment of the leachate by Fenton process was carried out in a batch reactor. Under the optimal operation conditions (initial pH = 3, 2000 mgL(-1) Fe2+ and 5000 mgL(-1) H2O2), 55.9% of the initial COD and 89.4% colour were removed.