The vertical distribution of prokaryotes in the surface sediment of Jiaolong cold seep at the northern South China Sea.

PubMed

Wu, Yuzhi; Qiu, Jian-Wen; Qian, Pei-Yuan; Wang, Yong

2018-05-01

In deep-sea cold seeps, microbial communities are shaped by geochemical components in seepage solutions. In the present study, we report the composition of microbial communities and potential metabolic activities in the surface sediment of Jiaolong cold seep at the northern South China Sea. Pyrosequencing of 16S rRNA gene amplicons revealed that a majority of the microbial inhabitants of the surface layers (0-6 cm) were sulfur oxidizer bacteria Sulfurimonas and archaeal methane consumer ANME-1, while sulfate reducer bacteria SEEP-SRB1, ANME-1 and ANME-2 dominated the bottom layers (8-14 cm). The potential ecological roles of the microorganisms were further supported by the presence of functional genes for methane oxidation, sulfur oxidation, sulfur reduction and nitrate reduction in the metagenomes. Metagenomic analysis revealed a significant correlation between coverage of 16S rRNA gene of sulfur oxidizer bacteria, functional genes involved in sulfur oxidation and nitrate reduction in different layers, indicating that sulfur oxidizing may be coupled to nitrate reducing at the surface layers of Jiaolong seeping site. This is probably related to the sulfur oxidizers of Sulfurimonas and Sulfurovum, which may be the capacity of nitrate reduction or associated with unidentified syntrophic nitrate-reducing microbes in the surface of the cold seep.

Analytical bond order potential for simulations of BeO 1D and 2D nanostructures and plasma-surface interactions

NASA Astrophysics Data System (ADS)

Byggmästar, J.; Hodille, E. A.; Ferro, Y.; Nordlund, K.

2018-04-01

An analytical interatomic bond order potential for the Be-O system is presented. The potential is fitted and compared to a large database of bulk BeO and point defect properties obtained using density functional theory. Its main applications include simulations of plasma-surface interactions involving oxygen or oxide layers on beryllium, as well as simulations of BeO nanotubes and nanosheets. We apply the potential in a study of oxygen irradiation of Be surfaces, and observe the early stages of an oxide layer forming on the Be surface. Predicted thermal and elastic properties of BeO nanotubes and nanosheets are simulated and compared with published ab initio data.

Ultrahigh vacuum and low-temperature cleaning of oxide surfaces using a low-concentration ozone beam

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pratt, A.; Department of Physics, University of York, Heslington, York YO10 5DD; Graziosi, P.

We present a novel method of delivering a low-concentration (<15%) ozone beam to an ultra-high vacuum environment for the purpose of cleaning and dosing experimental samples through oxidation processing. The system described is safe, low-cost, and practical and overcomes the limitations of ozone transport in the molecular flow environment of high or ultrahigh vacuum whilst circumventing the use of pure ozone gas which is potentially highly explosive. The effectiveness of this method in removing surface contamination is demonstrated through comparison of high-temperature annealing of a simple oxide (MgO) in ozone and oxygen environments as monitored using quadrupole mass spectroscopy andmore » Auger electron spectroscopy. Additionally, we demonstrate the potential of ozone for obtaining clean complex oxide surfaces without the need for high-temperature annealing which may significantly alter surface structure.« less

Influence of controlled surface oxidation on the magnetic anisotropy of Co ultrathin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Di, N.; Maroun, F., E-mail: fouad.maroun@polytechnique.fr; Allongue, P.

2015-03-23

We studied the influence of controlled surface-limited oxidation of electrodeposited epitaxial Co(0001)/Au(111) films on their magnetic anisotropy energy using real time in situ magneto optical Kerr effect and density functional theory (DFT) calculations. We investigated the Co first electrochemical oxidation step which we demonstrate to be completely reversible and determined the structure of this oxide layer. We show that the interface magnetic anisotropy of the Co film increases by 0.36 erg/cm{sup 2} upon Co surface oxidation. We performed DFT calculations to determine the different surface structures in a wide potential range as well as the charge transfer at the Co surface.more » Our results suggest that the magnetic anisotropy change is correlated with a positive charge increase of 0.54 e{sup −} for the Co surface atom upon oxidation.« less

Evaluation of current techniques for isolation of chars as natural adsorbents

USGS Publications Warehouse

Chun, Y.; Sheng, G.; Chiou, C.T.

2004-01-01

Chars in soils or sediments may potentially influence the soil/sediment sorption behavior. Current techniques for the isolation of black carbon including chars rely often on acid demineralization, base extraction, and chemical oxidation to remove salts and minerals, humic acid, and refractory kerogen, respectively. Little is known about the potential effects of these chemical processes on the char surface and adsorptive properties. This study examined the effects of acid demineralization, base extraction, and acidic Cr2O72- oxidation on the surface areas, surface acidity, and benzene adsorption characteristics of laboratory-produced pinewood and wheat-residue chars, pure or mixed with soils, and a commercial activated carbon. Demineralization resulted in a small reduction in the char surface area, whereas base extraction showed no obvious effect. Neither demineralization nor base extraction caused an appreciable variation in benzene adsorption and presumably the char surface properties. By contrast, the Cr2O 72- oxidation caused a >31% reduction in char surface area. The Boehm titration, supplemented by FTIR spectra, indicated that the surface acidity of oxidized chars increased by a factor between 2.3 and 12 compared to nonoxidized chars. Benzene adsorption with the oxidized chars was lower than that with the non-oxidized chars by a factor of >8.9; both the decrease in char surface area and the increase in char surface acidity contributed to the reduction in char adsorptive power. Although the Cr 2O72- oxidation effectively removes resistant kerogen, it is not well suited for the isolation of chars as contaminant adsorbents because of its destructive nature. Alternative nondestructive techniques that preserve the char surface properties and effectively remove kerogen must be sought.

Enhanced Lifetime of Polymer Solar Cells by Surface Passivation of Metal Oxide Buffer Layers.

PubMed

Venkatesan, Swaminathan; Ngo, Evan; Khatiwada, Devendra; Zhang, Cheng; Qiao, Qiquan

2015-07-29

The role of electron selective interfaces on the performance and lifetime of polymer solar cells were compared and analyzed. Bilayer interfaces consisting of metal oxide films with cationic polymer modification namely poly ethylenimine ethoxylated (PEIE) were found to enhance device lifetime compared to bare metal oxide films when used as an electron selective cathode interface. Devices utilizing surface-modified metal oxide layers showed enhanced lifetimes, retaining up to 85% of their original efficiency when stored in ambient atmosphere for 180 days without any encapsulation. The work function and surface potential of zinc oxide (ZnO) and ZnO/PEIE interlayers were evaluated using Kelvin probe and Kelvin probe force microscopy (KPFM) respectively. Kelvin probe measurements showed a smaller reduction in work function of ZnO/PEIE films compared to bare ZnO films when aged in atmospheric conditions. KPFM measurements showed that the surface potential of the ZnO surface drastically reduces when stored in ambient air for 7 days because of surface oxidation. Surface oxidation of the interface led to a substantial decrease in the performance in aged devices. The enhancement in the lifetime of devices with a bilayer interface was correlated to the suppressed surface oxidation of the metal oxide layers. The PEIE passivated surface retained a lower Fermi level when aged, which led to lower trap-assisted recombination at the polymer-cathode interface. Further photocharge extraction by linearly increasing voltage (Photo-CELIV) measurements were performed on fresh and aged samples to evaluate the field required to extract maximum charges. Fresh devices with a bare ZnO cathode interlayer required a lower field than devices with ZnO/PEIE cathode interface. However, aged devices with ZnO required a much higher field to extract charges while aged devices with ZnO/PEIE showed a minor increase compared to the fresh devices. Results indicate that surface modification can act as a suitable passivation layer to suppress oxidation in metal oxide thin films for enhanced lifetime in inverted organic solar cells.

First-Principles Mechanistic Analysis of Dimethyl Ether Electro-Oxidation on Monometallic Single-Crystal Surfaces

DOE PAGES

Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos

2014-08-27

Dimethyl ether is an attractive alternative to petroleum fuels due to its physical properties, comparable energy density to methanol and ethanol, and minimal deleterious environmental/toxicological effects. For direct fuel cells, it has a number of advantages over other prominent fuels, including easier storage with respect to hydrogen, lower toxicity and crossover when compared to methanol, and more facile complete oxidation as compared to ethanol (which includes a relatively difficult to break C–C bond). However, the dimethyl ether electro-oxidation reaction is poorly understood, hindering the development of improved electrocatalysts. Using periodic, self-consistent (PW91-GGA) density functional theory calculations, we evaluate the thermochemistrymore » of dimethyl ether (DME) electro-oxidation, at the elementary step level, on 12 model, closed-packed facets of pure transition metals: Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os, Ru, and Re. From the calculated thermochemistry, we determine the most probable reaction paths on each of these surfaces, focusing on Pt as a model system. Our results predict two key electro-oxidation peaks. At lower potentials, there is a peak corresponding to partial oxidation of DME to CO (and other surface poisoning species) or complete oxidation to CO 2 via formic acid as a key intermediate. A second, higher-potential peak is due to complete oxidation of adsorbed CO (and other surface poisoning species) to CO 2. Assuming the catalysts remain in their metallic state during the DME electro-oxidation process, our results suggest that the onset potential of the surfaces increases in the order Cu < Ni < Os < Rh < Ir < Co < Ru < Pt < Ag < Pd < Re < Au. Using our results, we construct a theoretical phase diagram showing predicted catalyst activity based on two key reactivity descriptors, the free energies of adsorbed CO and OH. Here, we compare all results to methanol electro-oxidation to understand key mechanistic differences and their impacts on optimal catalyst design for direct DME fuel cells.« less

Electrochemical oxidation of 243Am(III) in nitric acid by a terpyridyl-derivatized electrode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dares, C. J.; Lapides, A. M.; Mincher, B. J.

A high surface area, tin-doped indium oxide electrode surface-derivatized with a terpyridine ligand has been applied to the oxidation of trivalent americium to Am(V) and Am(VI) in nitric acid. Potentials as low as 1.8 V vs. the saturated calomel electrode are used, 0.7 V lower than the 2.6 V potential for one-electron oxidation of Am(III) to Am(IV) in 1 M acid. This simple electrochemical procedure provides, for the first time, a method for accessing the higher oxidation states of Am in non-complexing media for developing the coordination chemistries of Am(V) and Am(VI) and, more importantly, for separation of americium frommore » nuclear waste streams.« less

Dimethyl ether electro-oxidation on platinum surfaces

DOE PAGES

Roling, Luke T.; Herron, Jeffrey A.; Budiman, Winny; ...

2016-02-27

A first-principles density functional theory study was performed in this paper to elucidate the mechanism of dimethyl ether electro-oxidation on three low-index platinum surfaces (Pt(111), Pt(100), and Pt(211)). The goal of this study is to provide a fundamental explanation for the high activity observed experimentally on Pt(100) compared to Pt(111) and stepped surfaces. We determine that the enhanced activity of Pt(100) stems from more facile C–O bond breaking kinetics, as well as from easier removal of CO as a surface poison through activation of water. In general, the C–O bond (in CH xOCH y) becomes easier to break as dimethylmore » ether is dehydrogenated to a greater extent. In contrast, dehydrogenation becomes more difficult as more hydrogen atoms are removed. We perform two analyses of probable reaction pathways, which both identify CHOC and CO as the key reaction intermediates on these Pt surfaces. We show that the reaction mechanism on each surface is dependent on the cell operating potential, as increasing the potential facilitates C–H bond scission, in turn promoting the formation of intermediates for which C–O scission is more facile. We additionally demonstrate that CO oxidation determines the high overpotential required for electro-oxidation on Pt surfaces. Finally, at practical operating potentials (~0.60 V RHE), we determine that C–O bond breaking is most likely the most difficult step on all three Pt surfaces studied.« less

Vanadium As a Potential Membrane Material for Carbon Capture: Effects of Minor Flue Gas Species.

PubMed

Yuan, Mengyao; Liguori, Simona; Lee, Kyoungjin; Van Campen, Douglas G; Toney, Michael F; Wilcox, Jennifer

2017-10-03

Vanadium and its surface oxides were studied as a potential nitrogen-selective membrane material for indirect carbon capture from coal or natural gas power plants. The effects of minor flue gas components (SO 2 , NO, NO 2 , H 2 O, and O 2 ) on vanadium at 500-600 °C were investigated by thermochemical exposure in combination with X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and in situ X-ray diffraction (XRD). The results showed that SO 2 , NO, and NO 2 are unlikely to have adsorbed on the surface vanadium oxides at 600 °C after exposure for up to 10 h, although NO and NO 2 may have exhibited oxidizing effects (e.g., exposure to 250 ppmv NO/N 2 resulted in an 2.4 times increase in surface V 2 O 5 compared to exposure to just N 2 ). We hypothesize that decomposition of surface vanadium oxides and diffusion of surface oxygen into the metal bulk are both important mechanisms affecting the composition and morphology of the vanadium membrane. The results and hypothesis suggest that the carbon capture performance of the vanadium membrane can potentially be strengthened by material and process improvements such as alloying, operating temperature reduction, and flue gas treatment.

Theoretical investigation of the activity of cobalt oxides for the electrochemical oxidation of water.

PubMed

Bajdich, Michal; García-Mota, Mónica; Vojvodic, Aleksandra; Nørskov, Jens K; Bell, Alexis T

2013-09-11

The presence of layered cobalt oxides has been identified experimentally in Co-based anodes under oxygen-evolving conditions. In this work, we report the results of theoretical investigations of the relative stability of layered and spinel bulk phases of Co oxides, as well as the stability of selected surfaces as a function of applied potential and pH. We then study the oxygen evolution reaction (OER) on these surfaces and obtain activity trends at experimentally relevant electro-chemical conditions. Our calculated volume Pourbaix diagram shows that β-CoOOH is the active phase where the OER occurs in alkaline media. We calculate relative surface stabilities and adsorbate coverages of the most stable low-index surfaces of β-CoOOH: (0001), (0112), and (1014). We find that at low applied potentials, the (1014) surface is the most stable, while the (0112) surface is the more stable at higher potentials. Next, we compare the theoretical overpotentials for all three surfaces and find that the (1014) surface is the most active one as characterized by an overpotential of η = 0.48 V. The high activity of the (1014) surface can be attributed to the observation that the resting state of Co in the active site is Co(3+) during the OER, whereas Co is in the Co(4+) state in the less active surfaces. Lastly, we demonstrate that the overpotential of the (1014) surface can be lowered further by surface substitution of Co by Ni. This finding could explain the experimentally observed enhancement in the OER activity of Ni(y)Co(1-y)O(x) thin films with increasing Ni content. All energetics in this work were obtained from density functional theory using the Hubbard-U correction.

Effect of Strong Acid Functional Groups on Electrode Rise Potential in Capacitive Mixing by Double Layer Expansion

DOE PAGES

Hatzell, Marta C.; Raju, Muralikrishna; Watson, Valerie J.; ...

2014-11-03

We report that the amount of salinity-gradient energy that can be obtained through capacitive mixing based on double layer expansion depends on the extent the electric double layer (EDL) is altered in a low salt concentration (LC) electrolyte (e.g., river water). We show that the electrode-rise potential, which is a measure of the EDL perturbation process, was significantly (P = 10 –5) correlated to the concentration of strong acid surface functional groups using five types of activated carbon. Electrodes with the lowest concentration of strong acids (0.05 mmol g –1) had a positive rise potential of 59 ± 4 mVmore » in the LC solution, whereas the carbon with the highest concentration (0.36 mmol g –1) had a negative rise potential (₋31 ± 5 mV). Chemical oxidation of a carbon (YP50) using nitric acid decreased the electrode rise potential from 46 ± 2 mV (unaltered) to ₋6 ± 0.5 mV (oxidized), producing a whole cell potential (53 ± 1.7 mV) that was 4.4 times larger than that obtained with identical electrode materials (from 12 ± 1 mV). Changes in the EDL were linked to the behavior of specific ions in a LC solution using molecular dynamics and metadynamics simulations. The EDL expanded in the LC solution when a carbon surface (pristine graphene) lacked strong acid functional groups, producing a positive-rise potential at the electrode. In contrast, the EDL was compressed for an oxidized surface (graphene oxide), producing a negative-rise electrode potential. In conclusion, these results established the linkage between rise potentials and specific surface functional groups (strong acids) and demonstrated on a molecular scale changes in the EDL using oxidized or pristine carbons.« less

Relativistic potential energy surfaces of initial oxidations of Si(100) by atomic oxygen: The importance of surface dimer triplet state

NASA Astrophysics Data System (ADS)

Kim, Tae-Rae; Shin, Seokmin; Choi, Cheol Ho

2012-06-01

The non-relativistic and relativistic potential energy surfaces (PESs) of the symmetric and asymmetric reaction paths of Si(100)-2×1 oxidations by atomic oxygen were theoretically explored. Although only the singlet PES turned out to exist as a major channel leading to "on-dimer" product, both the singlet and triplet PESs leading to "on-top" products are attractive. The singlet PESs leading to the two surface products were found to be the singlet combinations (open-shell singlet) of the low-lying triplet state of surface silicon dimer and the ground 3P state of atomic oxygen. The triplet state of the "on-top" product can also be formed by the ground singlet state of the surface silicon dimer and the same 3P oxygen. The attractive singlet PESs leading to the "on-dimer" and "on-top" products made neither the intersystem crossings from triplet to singlet PES nor high energy 1D of atomic oxygen necessary. Rather, the low-lying triplet state of surface silicon dimer plays an important role in the initial oxidations of silicon surface.

Evolutionary Optimization of a Charge Transfer Ionic Potential Model for Ta/Ta-Oxide Heterointerfaces

DOE PAGES

Sasikumar, Kiran; Narayanan, Badri; Cherukara, Mathew; ...

2017-03-19

Heterostructures of tantalum and its oxide are of tremendous technological interest for a myriad of technological applications, including electronics, thermal management, catalysis and biochemistry. In particular, local oxygen stoichiometry variation in TaO x memristors comprising of thermodynamically stable metallic (Ta) and insulating oxide (Ta 2O 5) have been shown to result in fast switching on the subnanosecond timescale over a billion cycles. This rapid switching opens up the potential for advanced functional platforms such as stateful logic operations and neuromorphic computation. Despite its broad importance, an atomistic scale understanding of oxygen stoichiometry variation across Ta/TaO x heterointerfaces, such as duringmore » early stages of oxidation and oxide growth, is not well understood. This is mainly due to the lack of a unified interatomic potential model for tantalum oxides that can accurately describe metallic (Ta), ionic (TaO x) as well as mixed (Ta/TaO x interfaces) bonding environments simultaneously. To address this challenge, we introduce a Charge Transfer Ionic Potential (CTIP) model for Ta/Ta-oxide system by training against lattice parameters, cohesive energies, equations of state (EOS), elastic properties, and surface energies of the various experimentally observed Ta 2O 5 polymorphs (hexagonal, orthorhombic and monoclinic) obtained from density functional theory (DFT) calculations. The best CTIP parameters are determined by employing a global optimization scheme driven by genetic algorithms followed by local Simplex optimization. Our newly developed CTIP potential accurately predicts structure, thermodynamics, energetic ordering of polymorphs, as well as elastic and surface properties of both Ta and Ta 2O 5, in excellent agreement with DFT calculations and experiments. We employ our newly parameterized CTIP potential to investigate the early stages of oxidation and atomic scale mechanisms associated with oxide growth on Ta surface at various temperatures. Furthermore, the CTIP potential developed in this work is an invaluable tool to investigate atomic-scale mechanisms and transport phenomena underlying the response of Ta/TaO x interfaces to external stimuli (e.g, temperature, pressure, strain, electric field etc.), as well as other interesting dynamical phenomena including the physics of switching dynamics in TaO x based memristors and neuromorphic devices.« less

Interface bonding in silicon oxide nanocontacts: interaction potentials and force measurements.

PubMed

Wierez-Kien, M; Craciun, A D; Pinon, A V; Roux, S Le; Gallani, J L; Rastei, M V

2018-04-01

The interface bonding between two silicon-oxide nanoscale surfaces has been studied as a function of atomic nature and size of contacting asperities. The binding forces obtained using various interaction potentials are compared with experimental force curves measured in vacuum with an atomic force microscope. In the limit of small nanocontacts (typically <10 3 nm 2 ) measured with sensitive probes the bonding is found to be influenced by thermal-induced fluctuations. Using interface interactions described by Morse, embedded atom model, or Lennard-Jones potential within reaction rate theory, we investigate three bonding types of covalent and van der Waals nature. The comparison of numerical and experimental results reveals that a Lennard-Jones-like potential originating from van der Waals interactions captures the binding characteristics of dry silicon oxide nanocontacts, and likely of other nanoscale materials adsorbed on silicon oxide surfaces. The analyses reveal the importance of the dispersive surface energy and of the effective contact area which is altered by stretching speeds. The mean unbinding force is found to decrease as the contact spends time in the attractive regime. This contact weakening is featured by a negative aging coefficient which broadens and shifts the thermal-induced force distribution at low stretching speeds.

Interface bonding in silicon oxide nanocontacts: interaction potentials and force measurements

NASA Astrophysics Data System (ADS)

Wierez-Kien, M.; Craciun, A. D.; Pinon, A. V.; Le Roux, S.; Gallani, J. L.; Rastei, M. V.

2018-04-01

The interface bonding between two silicon-oxide nanoscale surfaces has been studied as a function of atomic nature and size of contacting asperities. The binding forces obtained using various interaction potentials are compared with experimental force curves measured in vacuum with an atomic force microscope. In the limit of small nanocontacts (typically <103 nm2) measured with sensitive probes the bonding is found to be influenced by thermal-induced fluctuations. Using interface interactions described by Morse, embedded atom model, or Lennard-Jones potential within reaction rate theory, we investigate three bonding types of covalent and van der Waals nature. The comparison of numerical and experimental results reveals that a Lennard-Jones-like potential originating from van der Waals interactions captures the binding characteristics of dry silicon oxide nanocontacts, and likely of other nanoscale materials adsorbed on silicon oxide surfaces. The analyses reveal the importance of the dispersive surface energy and of the effective contact area which is altered by stretching speeds. The mean unbinding force is found to decrease as the contact spends time in the attractive regime. This contact weakening is featured by a negative aging coefficient which broadens and shifts the thermal-induced force distribution at low stretching speeds.

Will ethylene oxide sterilization influence the application of novel Cu/LDPE nanocomposite intrauterine devices?

PubMed

Xia, Xianping; Wang, Yun; Cai, Shuizhou; Xie, Changsheng; Zhu, Changhong

2009-01-01

Copper/low-density polyethylene (Cu/LDPE) nanocomposite intrauterine device (IUD) is an implanted medicinal device that must be sterilized before use. Sterilization processes act either chemically or physically, leading to a lethal change in the structure or function of organic macromolecules in microorganisms. Given the nature of their action, sterilization might also attack the macromolecules of polymers by the same mechanisms, resulting in changes in surface functional groups and in the internal structure of the polymer. If sterilization leads to changes in surface functional groups and in the internal structure of the LDPE matrix, which will influence the mechanical property and cupric ions release rate of novel Cu/LDPE nanocomposite IUDs, potential clinical application will be limited. Therefore, it is necessary to study the influence of ethylene oxide sterilization on the potential clinical application of novel Cu/LDPE nanocomposite IUDs. The influence of ethylene oxide sterilization on the internal structure, surface functional groups, mechanical property and cupric ions release rate of novel Cu/LDPE nanocomposite IUDs was studied using differential scanning calorimetry, attenuated total reflection Fourier transform infrared spectroscopy, tensile testing and absorbance measurement. Ethylene oxide sterilization did not have any influence on the internal structure, surface functional groups, mechanical property and cupric ions release rate of novel Cu/LDPE nanocomposite intrauterine devices. Ethylene oxide sterilization will not affect the potential application of novel Cu/LDPE nanocomposite IUDs.

Surface functionalization of dopamine coated iron oxide nanoparticles for various surface functionalities

NASA Astrophysics Data System (ADS)

Sherwood, Jennifer; Xu, Yaolin; Lovas, Kira; Qin, Ying; Bao, Yuping

2017-04-01

We present effective conjugation of four small molecules (glutathione, cysteine, lysine, and Tris(hydroxymethyl)aminomethane) onto dopamine-coated iron oxide nanoparticles. Conjugation of these molecules could improve the surface functionality of nanoparticles for more neutral surface charge at physiological pH and potentially reduce non-specific adsorption of proteins to nanoparticles surfaces. The success of conjugation was evaluated with dynamic light scattering by measuring the surface charge changes and Fourier transform infrared spectroscopy for surface chemistry analysis. The stability of dopamine-coated nanoparticles and the ability of conjugated nanoparticles to reduce the formation of protein corona were evaluated by measuring the size and charge of the nanoparticles in biological medium. This facile conjugation method opens up possibilities for attaching various surface functionalities onto iron oxide nanoparticle surfaces for biomedical applications.

Influence of surface oxidation on ion dynamics and capacitance in porous and nonporous carbon electrodes

DOE PAGES

Dyatkin, Boris; Zhang, Yu; Mamontov, Eugene; ...

2016-04-07

Here, we investigate the influence of surface chemistry and ion confinement on capacitance and electrosorption dynamics of room-temperature ionic liquids (RTILs) in supercapacitors. Using air oxidation and vacuum annealing, we produced defunctionalized and oxygen-rich surfaces of carbide-derived carbons (CDCs) and graphene nanoplatelets (GNPs). While oxidized surfaces of porous CDCs improve capacitance and rate handling abilities of ions, defunctionalized nonporous GNPs improve charge storage densities on planar electrodes. Quasi-elastic neutron scattering (QENS) and inelastic neutron scattering (INS) probed the structure, dynamics, and orientation of RTIL ions confined in divergently functionalized pores. Oxidized, ionophilic surfaces draw ions closer to pore surfaces andmore » enhance potential-driven ion transport during electrosorption. Molecular dynamics (MD) simulations corroborated experimental data and demonstrated the significance of surface functional groups on ion orientations, accumulation densities, and capacitance.« less

Sorption of lead ions on diatomite and manganese oxides modified diatomite.

PubMed

Al-Degs, Y; Khraisheh, M A; Tutunji, M F

2001-10-01

Naturally occurring diatomaceous earth (diatomite) has been tested as a potential sorbent for Pb(II) ions. The intrinsic exchange properties were further improved by modification with manganese oxides. Modified adsorbent (referred to as Mn-diatomite) showed a higher tendency for adsorbing lead ions from solution at pH 4. The high performance exhibited by Mn-diatomite was attributed to increased surface area and higher negative surface charge after modification. Scanning electron microscope pictures revealed a birnessite structure of manganese oxides, which was featured by a plate-like-crystal structure. Diatomite filtration quality was improved after modification by manganese oxides. Good filtration qualities combined with high exchange capacity emphasised the potential use of Mn-diatomite in filtration systems.

Heterogeneous water oxidation: surface activity versus amorphization activation in cobalt phosphate catalysts.

PubMed

González-Flores, Diego; Sánchez, Irene; Zaharieva, Ivelina; Klingan, Katharina; Heidkamp, Jonathan; Chernev, Petko; Menezes, Prashanth W; Driess, Matthias; Dau, Holger; Montero, Mavis L

2015-02-16

Is water oxidation catalyzed at the surface or within the bulk volume of solid oxide materials? This question is addressed for cobalt phosphate catalysts deposited on inert electrodes, namely crystallites of pakhomovskyite (Co3(PO4)2⋅8 H2O, Pak) and phosphate-containing Co oxide (CoCat). X-ray spectroscopy reveals that oxidizing potentials transform the crystalline Pak slowly (5-8 h) but completely into the amorphous CoCat. Electrochemical analysis supports high-TOF surface activity in Pak, whereas its amorphization results in dominating volume activity of the thereby formed CoCat material. In the directly electrodeposited CoCat, volume catalysis prevails, but not at very low levels of the amorphous material, implying high-TOF catalysis at surface sites. A complete picture of heterogeneous water oxidation requires insight in catalysis at the electrolyte-exposed "outer surface", within a hydrated, amorphous volume phase, and modes and kinetics of restructuring upon operation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficacy of simple short-term in vitro assays for predicting the potential of metal oxide nanoparticles to cause pulmonary inflammation.

PubMed

Lu, Senlin; Duffin, Rodger; Poland, Craig; Daly, Paul; Murphy, Fiona; Drost, Ellen; Macnee, William; Stone, Vicki; Donaldson, Ken

2009-02-01

There has been concern regarding risks from inhalation exposure to nanoparticles (NPs). The large number of particles requiring testing means that alternative approaches to animal testing are needed. We set out to determine whether short-term in vitro assays that assess intrinsic oxidative stress potential and membrane-damaging potency of a panel of metal oxide NPs can be used to predict their inflammogenic potency. For a panel of metal oxide NPs, we investigated intrinsic free radical generation, oxidative activity in an extracellular environment, cytotoxicity to lung epithelial cells, hemolysis, and inflammation potency in rat lungs. All exposures were carried out at equal surface area doses. Only nickel oxide (NiO) and alumina 2 caused significant lung inflammation when instilled into rat lungs at equal surface area, suggesting that these two had extra surface reactivity. We observed significant free radical generation with 4 of 13 metal oxides, only one of which was inflammogenic. Only 3 of 13 were significantly hemolytic, two of which were inflammogenic. Potency in generating free radicals in vitro did not predict inflammation, whereas alumina 2 had no free radical activity but was inflammogenic. The hemolysis assay was correct in predicting the proinflammatory potential of 12 of 13 of the particles examined. Using a battery of simple in vitro tests, it is possible to predict the inflammogenicity of metal oxide NPs, although some false-positive results are likely. More research using a larger panel is needed to confirm the efficacy and generality of this approach for metal oxide NPs.

Effect of anodic treatment on the electrocatalytic activity of superficial Raney nickel catalyst in cathodic hydrogen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Korovin, N.V.; Kozlova, N.I.; Kumenko, M.V.

This work is concerned with the effect of oxidation on the activity of Raney nickel catalyst in cathodic hydrogen evolution. The superficial Raney nickel catalyst (nickel SRC) was prepared by a previously described procedure. The surface of the nickel SRC was oxidized by applying an anodic sweep over the potential range from 0.25 to 1.00 V with a potential sweep rate of 1 mV/sec. The rate of cathodic hydrogen evolution increases after pretreatment of the surface of nickel SRC by application of an anodic pulse. A significant increase in the reaction rate most probably is due to oxygen adsorption onmore » the nickel SRC surface. The largest increase in the amount of weakly bound hydrogen corresponds to the most active electrode. Oxidation of the nickel surface by an anodic pulse causes both an acceleration and a retardation of the cathodic hydrogen evolution reaction.« less

Chlorine activation indoors and outdoors via surface-mediated reactions of nitrogen oxides with hydrogen chloride

PubMed Central

Raff, Jonathan D.; Njegic, Bosiljka; Chang, Wayne L.; Gordon, Mark S.; Dabdub, Donald; Gerber, R. Benny; Finlayson-Pitts, Barbara J.

2009-01-01

Gaseous HCl generated from a variety of sources is ubiquitous in both outdoor and indoor air. Oxides of nitrogen (NOy) are also globally distributed, because NO formed in combustion processes is oxidized to NO2, HNO3, N2O5 and a variety of other nitrogen oxides during transport. Deposition of HCl and NOy onto surfaces is commonly regarded as providing permanent removal mechanisms. However, we show here a new surface-mediated coupling of nitrogen oxide and halogen activation cycles in which uptake of gaseous NO2 or N2O5 on solid substrates generates adsorbed intermediates that react with HCl to generate gaseous nitrosyl chloride (ClNO) and nitryl chloride (ClNO2), respectively. These are potentially harmful gases that photolyze to form highly reactive chlorine atoms. The reactions are shown both experimentally and theoretically to be enhanced by water, a surprising result given the availability of competing hydrolysis reaction pathways. Airshed modeling incorporating HCl generated from sea salt shows that in coastal urban regions, this heterogeneous chemistry increases surface-level ozone, a criteria air pollutant, greenhouse gas and source of atmospheric oxidants. In addition, it may contribute to recently measured high levels of ClNO2 in the polluted coastal marine boundary layer. This work also suggests the potential for chlorine atom chemistry to occur indoors where significant concentrations of oxides of nitrogen and HCl coexist. PMID:19620710

Electrochemical oxidation of hydrazine and its derivatives on the surface of metal electrodes in alkaline media

NASA Astrophysics Data System (ADS)

Asazawa, Koichiro; Yamada, Koji; Tanaka, Hirohisa; Taniguchi, Masatoshi; Oguro, Keisuke

Electrochemical oxidation of hydrazine and its derivatives on the surface of various metal electrodes in alkaline media was investigated. A comparison of various polycrystalline metal electrodes (Ni, Co, Fe, Cu, Ag, Au, and Pt) showed that Co and Ni electrodes have a lower onset potential for hydrazine oxidation than the Pt electrode. The onset oxidation potential of APA (aminopolyacrylamide), a hydrazine derivative (-0.127 V vs. reversible hydrogen electrode, RHE), was similar to that of hydrazine hydrate (-0.178 V vs. RHE) in the case of the Co electrode. APA oxidation was possible because of hydrazine desorption that was caused by APA hydrolysis. The hydrolysis reaction was brought about by a heat treatment. This result suggests that the hydrazine hydrolysis reaction of hydrazine derivatives makes it possible to store hydrazine hydrate safely.

Chalcopyrite dissolution: Scanning photoelectron microscopy examination of the evolution of sulfur species with and without added iron or pyrite

NASA Astrophysics Data System (ADS)

Li, Yubiao; Qian, Gujie; Brown, Paul L.; Gerson, Andrea R.

2017-09-01

Dissolution and oxidation of sulfide minerals play key roles in both acid and metalliferous rock drainage and supergene enrichment. Surface speciation heterogeneity, critical to understanding mechanisms of mineral sulfide dissolution, has to date largely not been considered. To this end synchrotron scanning photoelectron microscopy (SPEM) was employed to examine freshly fractured and partially dissolved chalcopyrite (CuFeS2) surfaces (pH 1.0 HClO4 solution, redox potential 650 mV relative to a standard hydrogen electrode, 75 °C). S2- (bulk), S22- and Sn2- were found to be present on all samples at varying concentrations. Oxidation was observed to take place heterogeneously at the sub-micron scale. As compared to chalcopyrite partially dissolved for 5 days, extended dissolution to 10 days did not show appreciably enhanced oxidation of surface species; however surface roughness increased markedly due to the growth/overlap of oxidised sulfur species. On addition of 4 mM iron both S0 and SO42- were observed but not SO32-, indicating that the greater Fe3+ activity/concentration promotes heterogeneous sulfur oxidation. On contact of pyrite (FeS2) with chalcopyrite, significantly greater chalcopyrite surface oxidation was observed than for the other systems examined, with S0, SO32- and SO42- being identified heterogeneously across the surface. It is proposed that chalcopyrite oxidative dissolution is enhanced by increasing its cathodic area, e.g. contacting with pyrite, while increased Fe3+ activity/concentration also contributes to increased dissolution rates. The high degree of surface heterogeneity of these surface products indicates that these surfaces are not passivated by their formation. These results suggest that chalcopyrite dissolution will be accelerated when in contact with pyrite at solution redox potential intermediate between the rest potentials of chalcopyrite and pyrite (560 mV and 660 mV, respectively) and/or iron rich acidic waters with resulting enhanced formation of secondary sulfur containing species and release of copper and iron. This in turn suggests accelerated supergene formation and enhanced metalliferous drainage under these conditions.

The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis

NASA Astrophysics Data System (ADS)

Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S.

2017-10-01

Nanosized Ir-black (3 nm) and Ir-oxide (5 nm) oxygen evolution electrocatalysts showing high performance in polymer electrolyte membrane (PEM) water electrolysis based on Aquivion® short-side chain ionomer membrane are investigated to understand the role of the Ir oxidation state on the electrocatalytic activity and stability. Despite the smaller mean crystallite size, the Ir-black electrocatalyst shows significantly lower initial performance than the Ir-oxide. During operation at high current density, the Ir-black shows a decrease of cell potential with time whereas the Ir-oxide catalyst shows increasing cell potential resulting in a degradation rate of about 10 μV/h, approaching 1000 h. The unusual behaviour of the Ir-black results from the oxidation of metallic Ir to IrOx. The Ir-oxide catalyst shows instead a hydrated structure on the surface and a negative shift of about 0.5 eV for the Ir 4f binding energy after 1000 h electrolysis operation. This corresponds to the formation of a sub-stoichiometric Ir-oxide on the surface. These results indicate that a hydrated IrO2 with high oxidation state on the surface is favourable in decreasing the oxygen evolution overpotential. Modifications of the Ir chemical oxidation state during operation can affect significantly the catalytic activity and durability of the electrolysis system.

Next Steps Forward in Understanding Martian Surface and Subsurface Chemistry

NASA Astrophysics Data System (ADS)

Carrier, Brandi L.

2017-09-01

The presence of oxidants such as hydrogen peroxide (H2O2) and perchlorate (ClO4-), which have been detected on Mars, has significant implications for chemistry and astrobiology. These oxidants can increase the reactivity of the Martian soil, accelerate the decomposition of organic molecules, and depress the freezing point of water. The study by Crandall et al. "Can Perchlorates be Transformed to Hydrogen Peroxide Products by Cosmic Rays on the Martian Surface" reveals a new formation mechanism by which hydrogen peroxide and other potential oxidants can be generated via irradiation of perchlorate by cosmic rays. This study represents an important next step in developing a full understanding of Martian surface and subsurface chemistry, particularly with respect to degradation of organic molecules and potential biosignatures.

Jumps in electric potential and in temperature at the electrode surfaces of the solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Kjelstrup, S.; Bedeaux, D.

1997-02-01

The electric potential profile and the temperature profile across a formation cell have been derived for the first time, using irreversible thermodynamics for bulk and surface systems. The method was demonstrated with the solid oxide fuel cell. The expression for the cell potential reduces to the classical formula when we assume equilibrium for polarized oxygen atoms across the electrolyte. Using data from the literature, we show for some likely assumptions, how the cell potential is generated at the anode, and how the energy is dissipated throughout the cell. The thermal gradient amounts to 5 × 10 8 Km -1 when the current density is 10 4 Am -2 and the thermal resistance of the surface scales like the electrical resistance.

Effect of Surface Preparation on the 815°C Oxidation of Single-Crystal Nickel-Based Superalloys

NASA Astrophysics Data System (ADS)

Sudbrack, Chantal K.; Beckett, Devon L.; MacKay, Rebecca A.

2015-11-01

A primary application for single-crystal superalloys has been jet engine turbine blades, where operation temperatures reach well above 1000°C. The NASA Glenn Research Center is considering use of single-crystal alloys for future, lower temperature application in the rims of jet engine turbine disks. Mechanical and environmental properties required for potential disk rim operation at 815°C are being examined, including the oxidation and corrosion behavior, where there is little documentation at intermediate temperatures. In this study, single-crystal superalloys, LDS-1101+Hf and CMSX-4+Y, were prepared with different surface finishes and compared after isothermal and cyclic oxidation exposures. Surface finish has a clear effect on oxide formation at 815°C. Machined low-stress ground surfaces after exposure for 440 h produce thin Al2O3 external scales, which is consistent with higher temperature oxidation, whereas polished surfaces with a mirror finish yield much thicker NiO external scales with subscale of Cr2O3-spinel-Al2O3, which may offer less reliable oxidation resistance. Additional experiments separate the roles of cold-work, localized deformation, and the extent of polishing and surface roughness on oxide formation.

Structural Evolution of a Ni Alloy Surface During High-Temperature Oxidation

DOE PAGES

Oleksak, Richard P.; Carney, Casey S.; Holcomb, Gordon R.; ...

2017-11-20

We show that considerable structural transformations occur at a Ni alloy surface during the transient stages of high-temperature oxidation. This was demonstrated by exposing the alloy to high-temperature CO 2 for short times at both atmospheric and supercritical pressures. A protective Cr-rich oxide layer formed after only 5 min at 700 °C and persisted for longer exposures up to 500 h. Voids formed and grew over time by the condensation of metal vacancies generated during oxidation, while the alloy surface recrystallized after sufficient oxidation had occurred. The oxygen potential established at the oxide/alloy interface led to oxidation along the newlymore » formed grain boundaries as well as adjacent to and inside of the voids. Al, the most stable oxide-former and present at low concentration in the alloy, was preferentially oxidized in these regions. Furthermore, the results provide an improved understanding of the internal oxidation of Al and its role in enhancing scale adhesion for this class of Ni alloys.« less

Surface-Potential-Based Metal-Oxide-Silicon-Varactor Model for RF Applications

NASA Astrophysics Data System (ADS)

Miyake, Masataka; Sadachika, Norio; Navarro, Dondee; Mizukane, Yoshio; Matsumoto, Kenji; Ezaki, Tatsuya; Miura-Mattausch, Mitiko; Mattausch, Hans Juergen; Ohguro, Tatsuya; Iizuka, Takahiro; Taguchi, Masahiko; Kumashiro, Shigetaka; Miyamoto, Shunsuke

2007-04-01

We have developed a surface-potential-based metal-oxide-silicon (MOS)-varactor model valid for RF applications up to 200 GHz. The model enables the calculation of the MOS-varactor capacitance seamlessly from the depletion region to the accumulation region and explicitly considers the carrier-response delay causing a non-quasi-static (NQS) effect. It has been observed that capacitance reduction due to this non-quasi-static effect limits the MOS-varactor application to an RF regime.

The Nature of Surface Oxides on Corrosion-Resistant Nickel Alloy Covered by Alkaline Water

PubMed Central

2010-01-01

A nickel alloy with high chrome and molybdenum content was found to form a highly resistive and passive oxide layer. The donor density and mobility of ions in the oxide layer has been determined as a function of the electrical potential when alkaline water layers are on the alloy surface in order to account for the relative inertness of the nickel alloy in corrosive environments. PMID:20672134

Exploring routes to tailor the physical and chemical properties of oxides via doping: an STM study

NASA Astrophysics Data System (ADS)

Nilius, Niklas

2015-08-01

Doping opens fascinating possibilities for tailoring the electronic, optical, magnetic, and chemical properties of oxides. The dopants perturb the intrinsic behavior of the material by generating charge centers for electron transfer into adsorbates, by inducing new energy levels for electronic and optical excitations, and by altering the surface morphology and hence the adsorption and reactivity pattern. Despite a vivid scientific interest, knowledge on doped oxides is limited when compared to semiconductors, which reflects the higher complexity and the insulating nature of many oxides. In fact, atomic-scale studies, aiming at a mechanistic understanding of dopant-related processes, are still scarce. In this article, we review our scanning tunneling microscopy (STM) experiments on thin, crystalline oxide films with a defined doping level. We demonstrate how the impurities alter the surface morphology and produce cationic/anionic vacancies in order to keep the system charge neutral. We discuss how individual dopants can be visualized in the lattice, even if they reside in subsurface layers. By means of STM-conductance and x-ray photoelectron spectroscopy, we determine the electronic impact of dopants, including the energies of their eigen states and local band-bending effects in the host oxide. Electronic transitions between dopant-induced gap states give rise to new optical modes, as detected with STM luminescence spectroscopy. From a chemical perspective, dopants are introduced to improve the redox potential of oxide materials. Electron transfer from Mo-donors, for example, alters the growth behavior of gold and activates O2 molecules on a wide-gap CaO surface. Such results demonstrate the enormous potential of doped oxides in heterogeneous catalysis. Our experiments address the issue of doping from a fundamental viewpoint, posing questions on the lattice position, charge state, and electron-transfer potential of the impurity ions. Whether doped oxides are suitable to catalyze surface reactions needs to be explored in more applied studies in the future.

MnO2/CNT supported Pt and PtRu nanocatalysts for direct methanol fuel cells.

PubMed

Zhou, Chunmei; Wang, Hongjuan; Peng, Feng; Liang, Jiahua; Yu, Hao; Yang, Jian

2009-07-07

Pt/MnO2/carbon nanotube (CNT) and PtRu/MnO2/CNT nanocomposites were synthesized by successively loading hydrous MnO2 and Pt (or PtRu alloy) nanoparticles on CNTs and were used as anodic catalysts for direct methanol fuel cells (DMFCs). The existence of MnO2 on the surface of CNTs effectively increases the proton conductivity of the catalyst, which then could remarkably improve the performance of the catalyst in methanol electro-oxidation. As a result, Pt/MnO2/CNTs show higher electrochemical active surface area and better methanol electro-oxidation activity, compared with Pt/CNTs. As PtRu alloy nanoparticles were deposited on the surface of MnO2/CNTs instead of Pt, the PtRu/MnO2/CNT catalyst shows not only excellent electro-oxidation activity to methanol with forward anodic peak current density of 901 A/gPt but also good CO oxidation ability with lower preadsorbed CO oxidation onset potential (0.33 V vs Ag/AgCl) and peak potential (0.49 V vs Ag/AgCl) at room temperature.

Oxidants at the Surface of Mars: A Review in Light of Recent Exploration Results.

PubMed

Lasne, J; Noblet, A; Szopa, C; Navarro-González, R; Cabane, M; Poch, O; Stalport, F; François, P; Atreya, S K; Coll, P

2016-12-01

In 1976, the Viking landers carried out the most comprehensive search for organics and microbial life in the martian regolith. Their results indicate that Mars' surface is lifeless and, surprisingly, depleted in organics at part-per-billion levels. Several biology experiments on the Viking landers gave controversial results that have since been explained by the presence of oxidizing agents on the surface of Mars. These oxidants may degrade abiotic or biological organics, resulting in their nondetection in the regolith. As several exploration missions currently focus on the detection of organics on Mars (or will do so in the near future), knowledge of the oxidative state of the surface is fundamental. It will allow for determination of the capability of organics to survive on a geological timescale, the most favorable places to seek them, and the best methods to process the samples collected at the surface. With this aim, we review the main oxidants assumed to be present on Mars, their possible formation pathways, and those laboratory studies in which their reactivity with organics under Mars-like conditions has been evaluated. Among the oxidants assumed to be present on Mars, only four have been detected so far: perchlorate ions (ClO 4 - ) in salts, hydrogen peroxide (H 2 O 2 ) in the atmosphere, and clays and metal oxides composing surface minerals. Clays have been suggested as catalysts for the oxidation of organics but are treated as oxidants in the following to keep the structure of this article straightforward. This work provides an insight into the oxidizing potential of the surface of Mars and an estimate of the stability of organic matter in an oxidizing environment. Key Words: Mars surface-Astrobiology-Oxidant-Chemical reactions. Astrobiology 16, 977-996.

Effects of oxygen chemical potential on the anisotropy of the adsorption properties of Zr surfaces.

PubMed

Zhang, Hai-Hui; Xie, Yao-Ping; Yao, Mei-Yi; Xu, Jing-Xiang; Zhang, Jin-Long; Hu, Li-Juan

2018-05-30

The anisotropy of metal oxidation is a fundamental issue, and the oxidation of Zr surfaces also attracts much attention due to the application of Zr alloys as cladding materials for nuclear fuels in nuclear power plants. In this study, we systematically investigate the diagram of O adsorption on low Miller index Zr surfaces by using first-principles calculations based on density functional theory calculations. We find that O adsorption on the basal surface, Zr(0001), is more favourable than that on the prism surfaces, Zr(112[combining macron]0) and Zr(101[combining macron]0), under strong O-reducing conditions, while O adsorption on the prism surface is more favourable than that of the basal surface under weak O-reducing conditions and the O-rich conditions. Our findings reveal that the anisotropy of adsorption properties of O on the Zr surfaces is dependent on the O chemical potential in the environment. Furthermore, the ability of the prism for O adsorption is stronger than that of the basal surface under the O-rich condition, which is consistent with the experimental observation that the oxidation of the prism Zr surface is easier than that of the basal surface. Systematic surveys show the adsorption ability of the surface under strong O-reducing conditions is determined by the low coordination numbers of surface atoms and surface geometrical structures, while the adsorption ability of the surface under weak O-reducing conditions and O-rich conditions is only determined by the low coordination number of surface atoms. These results can provide an atomic scale understanding of the initial oxidation of Zr surfaces, which inevitably affects the growth of protective passivation layers that play critical roles in the corrosion resistance of Zr cladding materials.

Streaming potential method for characterizing interaction of electrical double layers between rice roots and Fe/Al oxide-coated quartz in situ.

PubMed

Liu, Zhao-Dong; Wang, Hai-Cui; Li, Jiu-Yu; Xu, Ren-Kou

2017-10-01

The interaction between rice roots and Fe/Al oxide-coated quartz was investigated through zeta potential measurements and column leaching experiments in present study. The zeta potentials of rice roots, Fe/Al oxide-coated quartz, and the binary systems containing rice roots and Fe/Al oxide-coated quartz were measured by a specially constructed streaming potential apparatus. The interactions between rice roots and Fe/Al oxide-coated quartz particles were evaluated/deduced based on the differences of zeta potentials between the binary systems and the single system of rice roots. The zeta potentials of the binary systems moved in positive directions compared with that of rice roots, suggesting that there were overlapping of diffuse layers of electric double layers on positively charged Fe/Al oxide-coated quartz and negatively charged rice roots and neutralization of positive charge on Fe/Al oxide-coated quartz with negative charge on rice roots. The greater amount of positive charges on Al oxide led to the stronger interaction of Al oxide-coated quartz with rice roots and the more shift of zeta potential compared with Fe oxide. The overlapping of diffuse layers on Fe/Al oxide-coated quartz and rice roots was confirmed by column leaching experiments. The greater overlapping of diffuse layers on Al oxide and rice roots led to more simultaneous adsorptions of K + and NO 3 - and greater reduction in leachate electric conductivity when the column containing Al oxide-coated quartz and rice roots was leached with KNO 3 solution, compared with the columns containing rice roots and Fe oxide-coated quartz or quartz. When the KNO 3 solution was replaced with deionized water to flush the columns, more K + and NO 3 - were desorbed from the binary system containing Al oxide-coated quartz and rice roots than from other two binary systems, suggesting that the stronger electrostatic interaction between Al oxide and rice roots promoted the desorption of K + and NO 3 - from the binary system and enhanced overlapping of diffuse layers on these oppositely charged surfaces compared with other two binary systems. In conclusion, the overlapping of diffuse layers occurred between positively charged Fe/Al oxides and rice roots, which led to neutralization of opposite charge and affected adsorption and desorption of ions onto and from the charged surfaces of Fe/Al oxides and rice roots.

Potentiometric and electrokinetic signatures of iron(II) interactions with (α,γ)-Fe2O3.

PubMed

Toczydłowska, Diana; Kędra-Królik, Karolina; Nejbert, Krzysztof; Preočanin, Tajana; Rosso, Kevin M; Zarzycki, Piotr

2015-10-21

The electrochemical signatures of Fe(II) interactions with iron(III) oxides are poorly understood, despite their importance in controlling the amount of mobilized iron. Here, we report the potentiometric titration of α,γ-Fe2O3 oxides exposed to Fe(II) ions. We monitored in situ surface and ζ potentials, the ratio of mobilized ferric to ferrous, and the periodically analyzed nanoparticle crystal structure using X-ray diffraction. Electrokinetic potential reveals weak but still noticeable specific sorption of Fe(II) to the oxide surface under acidic conditions, and pronounced adsorption under alkaline conditions that results in a surface potential reversal. By monitoring the aqueous iron(II/III) fraction, we found that the addition of Fe(II) ions produces platinum electrode response consistent with the iron solubility-activity curve. Although, XRD analysis showed no evidence of γ-Fe2O3 transformations along the titration pathway despite iron cycling between aqueous and solid reservoirs, the magnetite formation cannot be ruled out.

Surface oxidation: an effective way to induce piezoelectricity in 2D black phosphorus

NASA Astrophysics Data System (ADS)

Li, Jiabin; Zhao, Ting; He, Chaoyu; Zhang, Kaiwang

2018-03-01

In this letter, first-principles methods are employed to investigate the elastic stiffness and piezoelectric tensors of surface-oxidized black phosphorene. Our results show that the piezoelectric coefficients d 11 and d 12 for surface-oxidized black phosphorene are 88.54 pm V-1 and  -1.94 pm V-1, respectively, which are comparable to those of group-IV monochalcogenides and more remarkable than those of the experimentally viable h-BN and MoS2. These results indicate that surface-oxidization is an effective way to make black phosphorene into an excellent piezoelectric material for potential applications in sensors, actuators, electric field generators and any other applications requiring electrical and mechanical energy conversion. We expect further experimental exploration on this interesting result to confirm our predictions.

Ethanol oxidation on Pt single-crystal electrodes: surface-structure effects in alkaline medium.

PubMed

Busó-Rogero, Carlos; Herrero, Enrique; Feliu, Juan M

2014-07-21

Ethanol oxidation in 0.1 M NaOH on single-crystal electrodes has been studied using electrochemical and FTIR techniques. The results show that the activity order is the opposite of that found in acidic solutions. The Pt(111) electrode displays the highest currents and also the highest onset potential of all the electrodes. The onset potential for the oxidation of ethanol is linked to the adsorption of OH on the electrode surface. However, small (or even negligible) amounts of CO(ads) and carbonate are detected by FTIR, which implies that cleavage of the C-C bond is not favored in this medium. The activity of the electrodes diminishes quickly upon cycling. The diminution of the activity is proportional to the measured currents and is linked to the formation and polymerization of acetaldehyde, which adsorbs onto the electrode surface and prevents further oxidation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methane Oxidation on Pd-Ceria. A DFT Study of the Combustion Mechanism over Pd, PdO and Pd-ceria Sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mayernick, Adam D.; Janik, Michael J.

2010-12-24

Palladium/ceria exhibits unique catalytic activity for hydrocarbon oxidation; however, the chemical and structural properties of active sites on the palladium–ceria surface are difficult to characterize. Strong interactions between palladium and the ceria support stabilize oxidized Pd δ+ species, which may contribute to the significant activity of Pd/ceria for methane oxidation. We present a density functional theory (DFT + U) investigation into methane oxidation over Pd/ceria and quantify the activity of the Pd xCe 1-xO 2(1 1 1) mixed oxide surface in comparison with the PdO(1 0 0) and Pd(1 1 1) surfaces. The methane activation barrier is lowest over themore » Pd xCe 1-xO 2(1 1 1) surface, even lower than over the Pd(1 1 1) surface or low coordinated stepped or kinked Pd sites. Subsequent reaction steps in complete oxidation, including product desorption and vacancy refilling, are considered to substantiate that methane activation remains the rate-limiting step despite the low barrier over Pd xCe 1-xO 2(1 1 1). The low barrier over the Pd xCe 1-xO 2(1 1 1) surface demonstrates that mixed ceria-noble metal oxides offer the potential for improved hydrocarbon oxidation performance with respect to dispersed noble metal particles on ceria.« less

Methane oxidation on Pd–Ceria: A DFT study of the mechanism over PdxCe1-xO2, Pd, and PdO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mayernick, Adam D.; Janik, Michael J.

2011-02-14

Palladium/ceria exhibits unique catalytic activity for hydrocarbon oxidation; however, the chemical and structural properties of active sites on the palladium–ceria surface are difficult to characterize. Strong interactions between palladium and the ceria support stabilize oxidized Pdδ+ species, which may contribute to the significant activity of Pd/ceria for methane oxidation. We present a density functional theory (DFT + U) investigation into methane oxidation over Pd/ceria and quantify the activity of the Pd xCe 1-xO 2(1 1 1) mixed oxide surface in comparison with the PdO(1 0 0) and Pd(1 1 1) surfaces. The methane activation barrier is lowest over the Pdmore » xCe 1-xO 2(1 1 1) surface, even lower than over the Pd(1 1 1) surface or low coordinated stepped or kinked Pd sites. Subsequent reaction steps in complete oxidation, including product desorption and vacancy refilling, are considered to substantiate that methane activation remains the rate-limiting step despite the low barrier over Pd xCe 1-xO 2(1 1 1). The low barrier over the Pd xCe 1-xO 2(1 1 1) surface demonstrates that mixed ceria-noble metal oxides offer the potential for improved hydrocarbon oxidation performance with respect to dispersed noble metal particles on ceria.« less

Cryptic oxygen oases: Hypolithic photosynthesis in hydrothermal areas and implications for Archean surface oxidation

NASA Astrophysics Data System (ADS)

Havig, J. R.; Hamilton, T. L.

2017-12-01

Mounting geochemical evidence suggests microorganisms capable of oxygenic photosynthesis (e.g., Cyanobacteria) colonized Archean continental surfaces, driving oxidative weathering of detrital pyrites prior to the 2.5 Ga great oxidation event. Modern terrestrial environments dominated by single-celled phototrophs include hydrothermal systems (e.g., Yellowstone National Park) and hypolithic communities found in arid to hyper-arid deserts (e.g., McMurdo Dry Valleys of Antarctica, Atacama Desert of Chile). Recent work indicates terrestrial hydrothermal systems date back at least as far as 3.5 Ga. Here, we explore phototrophic communities in both hypolithic (sub-sinter) and hydrothermal (subaqueous and subaerial) environments in Yellowstone National Park as potential analogs to Archean continental surfaces. Hydrothermal sub-sinter environments provide ideal conditions for phototrophic microbial communities, including blocking of harmful UV radiation, trapping and retention of moisture, and protection from erosion by rain and surface runoff. Hypolithic communities in geothermal settings were similar in both composition and carbon uptake rates to nearby hot spring communities. We hypothesize that hydrothermal area hypolithic communities represent modern analogs of phototrophic microbial communities that colonized Archean continental surfaces, producing oxygen locally and facilitating microbially-mediated pyrite oxidation prior to the presence of free oxygen in the global atmosphere. These results have implications for oxidation of the early Earth surface, the search for biosignatures in the rock record, as well as for potential harbors of past life on Mars and the search for life on Exoplanets.

Modeling Insight into Battery Electrolyte Electrochemical Stability and Interfacial Structure.

PubMed

Borodin, Oleg; Ren, Xiaoming; Vatamanu, Jenel; von Wald Cresce, Arthur; Knap, Jaroslaw; Xu, Kang

2017-12-19

Electroactive interfaces distinguish electrochemistry from chemistry and enable electrochemical energy devices like batteries, fuel cells, and electric double layer capacitors. In batteries, electrolytes should be either thermodynamically stable at the electrode interfaces or kinetically stable by forming an electronically insulating but ionically conducting interphase. In addition to a traditional optimization of electrolytes by adding cosolvents and sacrificial additives to preferentially reduce or oxidize at the electrode surfaces, knowledge of the local electrolyte composition and structure within the double layer as a function of voltage constitutes the basis of manipulating an interphase and expanding the operating windows of electrochemical devices. In this work, we focus on how the molecular-scale insight into the solvent and ion partitioning in the electrolyte double layer as a function of applied potential could predict changes in electrolyte stability and its initial oxidation and reduction reactions. In molecular dynamics (MD) simulations, highly concentrated lithium aqueous and nonaqueous electrolytes were found to exclude the solvent molecules from directly interacting with the positive electrode surface, which provides an additional mechanism for extending the electrolyte oxidation stability in addition to the well-established simple elimination of "free" solvent at high salt concentrations. We demonstrate that depending on their chemical structures, the anions could be designed to preferentially adsorb or desorb from the positive electrode with increasing electrode potential. This provides additional leverage to dictate the order of anion oxidation and to effectively select a sacrificial anion for decomposition. The opposite electrosorption behaviors of bis(trifluoromethane)sulfonimide (TFSI) and trifluoromethanesulfonate (OTF) as predicted by MD simulation in highly concentrated aqueous electrolytes were confirmed by surface enhanced infrared spectroscopy. The proton transfer (H-transfer) reactions between solvent molecules on the cathode surface coupled with solvent oxidation were found to be ubiquitous for common Li-ion electrolyte components and dependent on the local molecular environment. Quantum chemistry (QC) calculations on the representative clusters showed that the majority of solvents such as carbonates, phosphates, sulfones, and ethers have significantly lower oxidation potential when oxidation is coupled with H-transfer, while without H-transfer their oxidation potentials reside well beyond battery operating potentials. Thus, screening of the solvent oxidation limits without considering H-transfer reactions is unlikely to be relevant, except for solvents containing unsaturated functionalities (such as C═C) that oxidize without H-transfer. On the anode, the F-transfer reaction and LiF formation during anion and fluorinated solvent reduction could be enhanced or diminished depending on salt and solvent partitioning in the double layer, again giving an additional tool to manipulate the order of reductive decompositions and interphase chemistry. Combined with experimental efforts, modeling results highlight the promise of interphasial compositional control by either bringing the desired components closer to the electrode surface to facilitate redox reaction or expelling them so that they are kinetically shielded from the potential of the electrode.

Effect of surface chemistries and characteristics of Ti6Al4V on the Ca and P adsorption and ion dissolution in Hank's ethylene diamine tetra-acetic acid solution.

PubMed

Chang, E; Lee, T M

2002-07-01

This study examined the influence of chemistries and surface characteristics of Ti6Al4V on the adsorption of Ca and P species and ion dissolution behavior of the material exposed in Hank's solution with 8.0 mM ethylene diamine tetra-acetic acid at 37 degrees C. The variation of chemistries of the alloy and nano-surface characteristics (chemistries of nano-surface oxides, amphoteric OH group adsorbed on oxides, and oxide thickness) was effected by surface modification and three passivation methods (34% nitric acid passivation. 400 degrees C heated in air, and aged in 100 degrees C water). X-ray photoelectron spectroscopy and Auger electron spectroscopy were used for surface analyses. The chemistries of nano-surface oxides in a range studied should not change the capability of Ca and P adsorption. Nor is the capability affected significantly by amphoteric OH group and oxide thickness. However, passivations influence the surface oxide thickness and the early stage ion dissolution rate of the alloy. The rate-limiting step of the rate can be best explained by metal-ion transport through the oxide film, rather than hydrolysis of the film. Variation of the chemistries of titanium alloy alters the electromotive force potential of the metal, thereby affecting the corrosion and ion dissolution rate.

Effects of surface chemistry and microstructure of electrolyte on oxygen reduction kinetics of solid oxide fuel cells

DOE PAGES

Park, Joong Sun; An, Jihwan; Lee, Min Hwan; ...

2015-11-01

In this study, we report systematic investigation of the surface properties of yttria-stabilized zirconia (YSZ) electrolytes with the control of the grain boundary (GB) density at the surface, and its effects on electrochemical activities. The GB density of thin surface layers deposited on single crystal YSZ substrates is controlled by changing the annealing temperature (750-1450 °C). Higher oxygen reduction reactions (ORR) kinetics is observed in samples annealed at lower temperatures. The higher ORR activity is ascribed to the higher GB density at the YSZ surface where 'mobile' oxide ion vacancies are more populated. Meanwhile, oxide ion vacancies concurrently created withmore » yttrium segregation at the surface at the higher annealing temperature are considered inactive to oxygen incorporation reactions. Our results provide additional insight into the interplay between the surface chemistry, microstructures, and electrochemical activity. They potentially provide important guidelines for engineering the electrolyte electrode interfaces of solid oxide fuel cells for higher electrochemical performance.« less

Niche differentiation of ammonia oxidizers and nitrite oxidizers in rice paddy soil.

PubMed

Ke, Xiubin; Angel, Roey; Lu, Yahai; Conrad, Ralf

2013-08-01

The dynamics of populations and activities of ammonia-oxidizing and nitrite-oxidizing microorganisms were investigated in rice microcosms treated with two levels of nitrogen. Different soil compartments (surface, bulk, rhizospheric soil) and roots (young and old roots) were collected at three time points (the panicle initiation, heading and maturity periods) of the season. The population dynamics of bacterial (AOB) and archaeal (AOA) ammonia oxidizers was assayed by determining the abundance (using qPCR) and composition (using T-RFLP and cloning/sequencing) of their amoA genes (coding for a subunit of ammonia monooxygenase), that of nitrite oxidizers (NOB) by quantifying the nxrA gene (coding for a subunit of nitrite oxidase of Nitrobacter spp.) and the 16S rRNA gene of Nitrospira spp. The activity of the nitrifiers was determined by measuring the rates of potential ammonia oxidation and nitrite oxidation and by quantifying the copy numbers of amoA and nxrA transcripts. Potential nitrite oxidation activity was much higher than potential ammonia oxidation activity and was not directly affected by nitrogen amendment demonstrating the importance of ammonia oxidizers as pace makers for nitrite oxidizer populations. Marked differences in the distribution of bacterial and archaeal ammonia oxidizers, and of Nitrobacter-like and Nitrospira-like nitrite oxidizers were found in the different compartments of planted paddy soil indicating niche differentiation. In bulk soil, ammonia-oxidizing bacteria (Nitrosospira and Nitrosomonas) were at low abundance and displayed no activity, but in surface soil their activity and abundance was high. Nitrite oxidation in surface soil was dominated by Nitrospira spp. By contrast, ammonia-oxidizing Thaumarchaeota and Nitrobacter spp. seemed to dominate nitrification in rhizospheric soil and on rice roots. In contrast to soil compartment, the level of N fertilization and the time point of sampling had only little effect on the abundance, composition and activity of the nitrifying communities. The results of our study show that in rice fields population dynamics and activity of nitrifiers is mainly differentiated by the soil compartments rather than by nitrogen amendment or season. © 2013 John Wiley & Sons Ltd and Society for Applied Microbiology.

Abstracts on the International Conference on Noise in Physical Systems (7th) and the International Conference on 1/f Noise (3rd) Held at Montpellier, France on 17-20 May 1983.

DTIC Science & Technology

1983-05-20

an impurity-mobility reduction factor of about 100. We finally note that there is no indication of an emitter-base noise source due to oxide surface...in N2 + 1% 02, at 11000C, for 3 hrs. Different phosphorus surface concentrations have been realized using different in situ oxidation times (prior to...depletion change per unit area at the surface potential Ts = 1.5 OF , Cox and C are the oxide and the depletion capacitances per unit area

Surface study of films formed on copper and brass at open circuit potential

NASA Astrophysics Data System (ADS)

Procaccini, R.; Schreiner, W. H.; Vázquez, M.; Ceré, S.

2013-03-01

The corrosion resistance of Cu-Zn alloys strongly depends on the quality of the protective passive film. This study focuses on the influence of Zn on the composition of oxide films on copper and brass (Cu77Zn21Al2) in borax 0.1 mol L-1 (pH 9.2) solution, where the solubility of copper oxides is minimal. The effect of the presence of chloride ions at low concentration (0.01 mol L-1) in the electrolyte was also evaluated. Both conditions were studied using a set of different electrochemical, optical and surface techniques such as cyclic voltammetry, differential reflectance, X-ray photoelectron spectroscopy and Raman spectroscopy. A duplex Cu2O/CuO layer forms on copper at potentials positive to the open circuit potential (OCP), while in the case of brass, zinc compounds are also incorporated to the surface film. It also became evident that a surface film can be formed on these materials even at potentials negative to the OCP. Zn(II) species are the main constituents of the films growing on brass, while copper oxides are incorporated to the surface film when approaching the OCP. The presence of chloride ions at low concentrations contributes to the dissolution of the oxo-hydroxides formed during the early stages of the aging process at open circuit potential. Also, copper chloro-compounds are formed, as shown by Raman spectroscopy for both copper and brass electrodes.

Platinum redispersion on metal oxides in low temperature fuel cells.

PubMed

Tripković, Vladimir; Cerri, Isotta; Nagami, Tetsuo; Bligaard, Thomas; Rossmeisl, Jan

2013-03-07

We have analyzed the aptitude of several metal oxide supports (TiO(2), SnO(2), NbO(2), ZrO(2), SiO(2), Ta(2)O(5) and Nb(2)O(5)) to redisperse platinum under electrochemical conditions pertinent to the Proton Exchange Membrane Fuel Cell (PEMFC) cathode. The redispersion on oxide supports in air has been studied in detail; however, due to different operating conditions it is not straightforward to link the chemical and the electrochemical environment. The largest differences reflect in (1) the oxidation state of the surface (the oxygen species coverage), (2) temperature and (3) the possibility of platinum dissolution at high potentials and the interference of redispersion with normal working potential of the PEMFC cathode. We have calculated the PtO(x) (x = 0, 1, 2) adsorption energies on different metal oxides' surface terminations as well as inside the metal oxides' bulk, and we have concluded that NbO(2) might be a good support for platinum redispersion at PEMFC cathodes.

Influence of Nitinol wire surface treatment on oxide thickness and composition and its subsequent effect on corrosion resistance and nickel ion release.

PubMed

Clarke, B; Carroll, W; Rochev, Y; Hynes, M; Bradley, D; Plumley, D

2006-10-01

Medical implants and devices are now used successfully in surgical procedures on a daily basis. Alloys of nickel and titanium, and in particular Nitinol are of special interest in the medical device industry, because of their shape memory and superelastic properties. The corrosion behavior of nitinol in the body is also of critical importance because of the known toxicological effects of nickel. The stability of a NiTi alloy in the physiological environment is dependant primarily on the properties of the mostly TiO(2) oxide layer that is present on the surface. For the present study, a range of nitinol wires have been prepared using different drawing processes and a range of surface preparation procedures. It is clear from the results obtained that the wire samples with very thick oxides also contain a high nickel content in the oxide layer. The untreated samples with the thicker oxides show the lowest pitting potential values and greater nickel release in both long and short-term experiments. It was also found that after long-term immersion tests breakdown potentials increased for samples that exhibited lower values initially. From these results it would appear that surface treatment is essential for the optimum bioperformance of nitinol. (c) 2006 Wiley Periodicals, Inc

Peroxides and the survivability of microorganisms on the surface of Mars.

PubMed

Mancinelli, R L

1989-01-01

Results of the Viking mission seem to indicate that there is a ubiquitous layer of highly oxidizing aeolian material covering the Martian surface. This layer is thought to oxidize organic material that may settle on it, and is therefore responsible for the lack of detection of organic matter on the planet's surface by Viking. The mechanism that creates the oxidizing condition is not well understood, nor is the extent of the oxidation potential of this material. It has been suggested that the oxidizing nature of the soil is due to photochemical reactions which create hydrogen peroxide and superoxides in the surface soil. One question of importance to planetary protection regarding this material is, what is its potential for destroying terrestrial microorganisms, thus making the surface of Mars "self-sterilizing"? Using data obtained by the gas exchange experiment on Viking, and for simplicity assuming that all of the O2 released came from H2O2, the concentration range for H2O2 on the surface of Mars can be calculated to be 25-250 ppm. The microbial disinfection rate by H2O2 is concentration dependent, and is highly variable within the microbial community. Data from our laboratory indicate that certain soil bacteria survive and grow to stationary phase in 30,000 ppm H2O2. However, the total number of organisms decreases in the presence of H2O2. These results indicate that it is doubtful that the presence of H2O2 alone on Mars would make the surface "self-sterilizing".

A Closer Look at Solar Wind Sputtering of Lunar Surface Materials

NASA Technical Reports Server (NTRS)

Barghouty, A. F.; Adams, J. H., Jr.; Meyer, F.; Mansur, L.; Reinhold, C.

2008-01-01

Solar-wind induced potential sputtering of the lunar surface may be a more efficient erosive mechanism than the "standard" kinetic (or physical) sputtering. This is partly based on new but limited laboratory measurements which show marked enhancements in the sputter yields of slow-moving, highly-charged ions impacting oxides. The enhancements seen in the laboratory can be orders of magnitude for some surfaces and highly charged incident ions, but seem to depend very sensitively on the properties of the impacted surface in addition to the fluence, energy and charge of the impacting ion. For oxides, potential sputtering yields are markedly enhanced and sputtered species, especially hydrogen and light ions, show marked dependence on both charge and dose.

Studying Reaction Intermediates Formed at Graphenic Surfaces

NASA Astrophysics Data System (ADS)

Sarkar, Depanjan; Sen Gupta, Soujit; Narayanan, Rahul; Pradeep, Thalappil

2014-03-01

We report in-situ production and detection of intermediates at graphenic surfaces, especially during alcohol oxidation. Alcohol oxidation to acid occurs on graphene oxide-coated paper surface, driven by an electrical potential, in a paper spray mass spectrometry experiment. As paper spray ionization is a fast process and the time scale matches with the reaction time scale, we were able to detect the intermediate, acetal. This is the first observation of acetal formed in surface oxidation. The process is not limited to alcohols and the reaction has been extended to aldehydes, amines, phosphenes, sugars, etc., where reaction products were detected instantaneously. By combining surface reactions with ambient ionization and mass spectrometry, we show that new insights into chemical reactions become feasible. We suggest that several other chemical transformations may be studied this way. This work opens up a new pathway for different industrially and energetically important reactions using different metal catalysts and modified substrate.

[Corrosion resistant properties of different anodized microtopographies on titanium surfaces].

PubMed

Fangjun, Huo; Li, Xie; Xingye, Tong; Yueting, Wang; Weihua, Guo; Weidong, Tian

2015-12-01

To investigate the corrosion resistant properties of titanium samples prepared by anodic oxidation with different surface morphologies. Pure titanium substrates were treated by anodic oxidation to obtain porous titanium films in micron, submicron, and micron-submicron scales. The surface morphologies, coating cross-sectional morphologies, crystalline structures, and surface roughness of these samples were characterized. Electrochemical technique was used to measure the corrosion potential (Ecorr), current density of corrosion (Icorr), and polarization resistance (Rp) of these samples in a simulated body fluid. Pure titanium could be modified to exhibit different surface morphologies by the anodic oxidation technique. The Tafel curve results showed that the technique can improve the corrosion resistance of pure titanium. Furthermore, the corrosion resistance varied with different surface morphologies. The submicron porous surface sample demonstrated the best corrosion resistance, with maximal Ecorr and Rp and minimal Icorr. Anodic oxidation technology can improve the corrosion resistance of pure titanium in a simulated body fluid. The submicron porous surface sample exhibited the best corrosion resistance because of its small surface area and thick barrier layer.

X-ray reflectivity study of formation of multilayer porous anodic oxides of silicon.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chu, Y.; Fenollosa, R.; Parkhutik, V.

1999-07-21

The paper reports data on the kinetics of anodic oxide films growth on silicon in aqueous solutions of phosphoric acids as well as a study of the morphology of the oxides grown in a special regime of the oscillating anodic potential. X-ray reflectivity measurements were performed on the samples of anodic oxides using an intense synchrotron radiation source. They have a multilayer structure as revealed by theoretical fitting of the reflectivity data. The oscillations of the anodic potential are explained in terms of synchronized oxidation/dissolution reactions at the silicon surface and accumulation of mechanic stress in the oxide film.

Corrosion resistance of titanium ion implanted AZ91 magnesium alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu Chenglong; Xin Yunchang; Tian Xiubo

2007-03-15

Degradable metal alloys constitute a new class of materials for load-bearing biomedical implants. Owing to their good mechanical properties and biocompatibility, magnesium alloys are promising in degradable prosthetic implants. The objective of this study is to improve the corrosion behavior of surgical AZ91 magnesium alloy by titanium ion implantation. The surface characteristics of the ion implanted layer in the magnesium alloys are examined. The authors' results disclose that an intermixed layer is produced and the surface oxidized films are mainly composed of titanium oxide with a lesser amount of magnesium oxide. X-ray photoelectron spectroscopy reveals that the oxide has threemore » layers. The outer layer which is 10 nm thick is mainly composed of MgO and TiO{sub 2} with some Mg(OH){sub 2}. The middle layer that is 50 nm thick comprises predominantly TiO{sub 2} and MgO with minor contributions from MgAl{sub 2}O{sub 4} and TiO. The third layer from the surface is rich in metallic Mg, Ti, Al, and Ti{sub 3}Al. The effects of Ti ion implantation on the corrosion resistance and electrochemical behavior of the magnesium alloys are investigated in simulated body fluids at 37{+-}1 deg. C using electrochemical impedance spectroscopy and open circuit potential techniques. Compared to the unimplanted AZ91 alloy, titanium ion implantation significantly shifts the open circuit potential (OCP) to a more positive potential and improves the corrosion resistance at OCP. This phenomenon can be ascribed to the more compact surface oxide film, enhanced reoxidation on the implanted surface, as well as the increased {beta}-Mg{sub 12}Al{sub 17} phase.« less

Influence of Surface Properties of Filtration-Layer Metal Oxide on Ceramic Membrane Fouling during Ultrafiltration of Oil/Water Emulsion.

PubMed

Lu, Dongwei; Zhang, Tao; Gutierrez, Leo; Ma, Jun; Croué, Jean-Philippe

2016-05-03

In this work, ceramic ultrafiltration membranes deposited with different metal oxides (i.e., TiO2, Fe2O3, MnO2, CuO, and CeO2) of around 10 nm in thickness and similar roughness were tested for O/W emulsion treatment. A distinct membrane fouling tendency was observed, which closely correlated to the properties of the filtration-layer metal oxides (i.e., surface hydroxyl groups, hydrophilicity, surface charge, and adhesion energy for oil droplets). Consistent with the distinct bond strength of the surface hydroxyl groups, hydrophilicity of these common metal oxides is quite different. The differences in hydrophilicity consequently lead to different adhesion of these metal oxides toward oil droplets, consistent with the irreversible membrane fouling tendency. In addition, the surface charge of the metal oxide opposite to that of emulsion can help to alleviate irreversible membrane fouling in ultrafiltration. Highly hydrophilic Fe2O3 with the lowest fouling tendency could be a potential filtration-layer material for the fabrication/modification of ceramic membranes for O/W emulsion treatment. To the best of our knowledge, this is the first study clearly showing the correlations between surface properties of filtration-layer metal oxides and ceramic membrane fouling tendency by O/W emulsion.

Probing the Surface of Platinum during the Hydrogen Evolution Reaction in Alkaline Electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoerzinger, Kelsey A.; Favaro, Marco; Ross, Philip N.

Understanding the surface chemistry of electrocatalysts in operando can bring insight into the reaction mechanism, and ultimately the design of more efficient materials for sustainable energy storage and conversion. Recent progress in synchrotron based X-ray spectroscopies for in operando characterization allows us to probe the solid/liquid interface directly while applying an external potential, applied here to the model system of Pt in alkaline electrolyte for the hydrogen evolution reaction (HER). We employ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to identify the oxidation and reduction of Pt-oxides and hydroxides on the surface as a function of applied potential, and further assessmore » the potential for hydrogen adsorption and absorption (hydride formation) during and after the HER. This new window into the surface chemistry of Pt in alkaline brings insight into the nature of the rate limiting step, the extent of H ad/absorption and it’s persistence at more anodic potentials.« less

Corrosion of NiTi Wires with Cracked Oxide Layer

NASA Astrophysics Data System (ADS)

Racek, Jan; Šittner, Petr; Heller, Luděk; Pilch, Jan; Petrenec, Martin; Sedlák, Petr

2014-07-01

Corrosion behavior of superelastic NiTi shape memory alloy wires with cracked TiO2 surface oxide layers was investigated by electrochemical corrosion tests (Electrochemical Impedance Spectroscopy, Open Circuit Potential, and Potentiodynamic Polarization) on wires bent into U-shapes of various bending radii. Cracks within the oxide on the surface of the bent wires were observed by FIB-SEM and TEM methods. The density and width of the surface oxide cracks dramatically increase with decreasing bending radius. The results of electrochemical experiments consistently show that corrosion properties of NiTi wires with cracked oxide layers (static load keeps the cracks opened) are inferior compared to the corrosion properties of the straight NiTi wires covered by virgin uncracked oxides. Out of the three methods employed, the Electrochemical Impedance Spectroscopy seems to be the most appropriate test for the electrochemical characterization of the cracked oxide layers, since the impedance curves (Nyquist plot) of differently bent NiTi wires can be associated with increasing state of the surface cracking and since the NiTi wires are exposed to similar conditions as the surfaces of NiTi implants in human body. On the other hand, the potentiodynamic polarization test accelerates the corrosion processes and provides clear evidence that the corrosion resistance of bent superelastic NiTi wires degrades with oxide cracking.

Effects of pretreatment processes for Zr electrorefining of oxidized Zircaloy-4 cladding tubes

NASA Astrophysics Data System (ADS)

Hwa Lee, Chang; Lee, Yoo Lee; Jeon, Min Ku; Choi, Yong Taek; Kang, Kweon Ho; Park, Geun Il

2014-06-01

The effect of pretreatment processes for the Zr electrorefining of oxidized Zircaloy-4 cladding tubes is examined in LiCl-KCl-ZrCl4 molten salts at 500 °C. The cyclic voltammetries reveal that the Zr dissolution kinetics is highly dependent on the thickness of a Zr oxide layer formed at 500 °C under air atmosphere. For the Zircaloy-4 tube covered with a 1 μm thick oxide layer, the Zr dissolution process is initiated from a non-stoichiometric Zr oxide surface through salt treatment at an open circuit potential in the molten salt electrolyte. The Zr dissolution of the samples in the middle range of oxide layer thickness appears to be more effectively derived by the salt treatment coupled with an anodic potential application at an oxidation potential of Zr. A modification of the process scheme offers an applicability of Zr electrorefining for the treatment of oxidized cladding hull wastes.

Tuning graphitic oxide for initiator- and metal-free aerobic epoxidation of linear alkenes

NASA Astrophysics Data System (ADS)

Pattisson, Samuel; Nowicka, Ewa; Gupta, Upendra N.; Shaw, Greg; Jenkins, Robert L.; Morgan, David J.; Knight, David W.; Hutchings, Graham J.

2016-09-01

Graphitic oxide has potential as a carbocatalyst for a wide range of reactions. Interest in this material has risen enormously due to it being a precursor to graphene via the chemical oxidation of graphite. Despite some studies suggesting that the chosen method of graphite oxidation can influence the physical properties of the graphitic oxide, the preparation method and extent of oxidation remain unresolved for catalytic applications. Here we show that tuning the graphitic oxide surface can be achieved by varying the amount and type of oxidant. The resulting materials differ in level of oxidation, surface oxygen content and functionality. Most importantly, we show that these graphitic oxide materials are active as unique carbocatalysts for low-temperature aerobic epoxidation of linear alkenes in the absence of initiator or metal. An optimum level of oxidation is necessary and materials produced via conventional permanganate-based methods are far from optimal.

In situ Visualization of Electrocatalytic Reaction Activity at Quantum Dots for Water Oxidation.

PubMed

Chen, Ying; Fu, Jiaju; Cui, Chen; Jiang, Dechen; Chen, Zixuan; Chen, Hong-Yuan; Zhu, Jun-Jie

2018-06-11

Exploring electrocatalytic reactions on nanomaterial surface can give crucial information for the development of robust catalysts. Here, electrocatalytic reaction activity at single quantum dots (QDs) loaded silica micro-particles involved in water oxidation is visualized using electrochemiluminescence (ECL) microscopy. Under positive potential, the active redox centers at QDs induce the generation of hydroperoxide surface intermediates as coreactant to remarkably enhance ECL emission from luminol derivative for imaging. For the first time, in situ visualization of catalytic activity in water oxidation at QDs catalyst was achieved, supported by a linear relation between ECL intensity and turn over frequency. A very slight diffusion trend attributed to only luminol species proved in situ capture of hydroperoxide surface intermediates at catalytic active sites of QDs. This work provides tremendous potential in on-line imaging of electrocatalytic reaction and visual evaluation of catalyst performance.

Fabrication of photocatalytically active vanadium oxide nanostructures via plasma route

NASA Astrophysics Data System (ADS)

Kajita, Shin; Yoshida, Tomoko; Ohno, Noriyasu; Ichino, Yusuke; Yoshida, Naoaki

2018-05-01

Plasma irradiation was used to create nanostructured vanadium oxide with potential commercial and industrial applications. Morphology changes were induced at the nano- and micro-meter scale, accompanied by the growth of helium nanobubbles. Micrometer-sized pillars, cube-shaped nanostructures, and fuzzy fiberform nanostructures were grown on the surface; the necessary conditions in terms of the incident ion energy and the surface temperature for those morphology changes were revealed. Hydrogen production experiments using a photocatalytic reaction with aqueous methanol solution were conducted on the fabricated samples. Enhanced H2 production was confirmed with the plasma irradiated nanostructured sample that had been oxidized in air atmosphere. Photocatalytically inactive vanadium oxide exhibited a high photocatalytic activity after nanostructurization of the surface by helium plasma irradiation.

Oxidized zirconium on ceramic; Catastrophic coupling.

PubMed

Ozden, V E; Saglam, N; Dikmen, G; Tozun, I R

2017-02-01

Oxidized zirconium (Oxinium™; Smith & Nephew, Memphis, TN, USA) articulated with polyethylene in total hip arthroplasty (THA) appeared to have the potential to reduce wear dramatically. The thermally oxidized metal zirconium surface is transformed into ceramic-like hard surface that is resistant to abrasion. The exposure of soft zirconium metal under hard coverage surface after the damage of oxidized zirconium femoral head has been described. It occurred following joint dislocation or in situ succeeding disengagement of polyethylene liner. We reported three cases of misuse of Oxinium™ (Smith & Nephew, Memphis, TN, USA) heads. These three cases resulted in catastrophic in situ wear and inevitable failure although there was no advice, indication or recommendation for this use from the manufacturer. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Oxidants at the Surface of Mars: A Review in Light of Recent Exploration Results

NASA Astrophysics Data System (ADS)

Lasne, J.; Noblet, A.; Szopa, C.; Navarro-González, R.; Cabane, M.; Poch, O.; Stalport, F.; François, P.; Atreya, S. K.; Coll, P.

2016-12-01

In 1976, the Viking landers carried out the most comprehensive search for organics and microbial life in the martian regolith. Their results indicate that Mars' surface is lifeless and, surprisingly, depleted in organics at part-per-billion levels. Several biology experiments on the Viking landers gave controversial results that have since been explained by the presence of oxidizing agents on the surface of Mars. These oxidants may degrade abiotic or biological organics, resulting in their nondetection in the regolith. As several exploration missions currently focus on the detection of organics on Mars (or will do so in the near future), knowledge of the oxidative state of the surface is fundamental. It will allow for determination of the capability of organics to survive on a geological timescale, the most favorable places to seek them, and the best methods to process the samples collected at the surface. With this aim, we review the main oxidants assumed to be present on Mars, their possible formation pathways, and those laboratory studies in which their reactivity with organics under Mars-like conditions has been evaluated. Among the oxidants assumed to be present on Mars, only four have been detected so far: perchlorate ions (ClO4-) in salts, hydrogen peroxide (H2O2) in the atmosphere, and clays and metal oxides composing surface minerals. Clays have been suggested as catalysts for the oxidation of organics but are treated as oxidants in the following to keep the structure of this article straightforward. This work provides an insight into the oxidizing potential of the surface of Mars and an estimate of the stability of organic matter in an oxidizing environment.

Synchrotron-Based In Situ Characterization of Carbon-Supported Platinum and Platinum Monolayer Electrocatalysts

DOE PAGES

Sasaki, Kotaro; Marinkovic, Nebojsa; Isaacs, Hugh S.; ...

2015-11-17

Understanding oxidation/dissolution mechanisms of Pt is critical in designing durable catalysts for the oxygen reduction reaction (ORR), but exact mechanisms remain unclear. Our present work explores the oxidation/dissolution of Pt and Pt monolayer (ML) electrocatalysts over a wide range of applied potentials using cells that facilitate in situ measurements by combining X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) measurements. Furthermore, the X-ray absorption near edge structure (XANES) measurement demonstrated that Pt nanoparticle surfaces were oxidized from metallic Pt to α-PtO 2-type oxide during the potential sweep from 0.41 to 1.5 V, and the transition state of O or OHmore » adsorption on Pt and the onset of the place exchange process were revealed by the delta mu (Δμ) method. Only the top layers of Pt nanoparticles were oxidized, while the inner Pt atoms remained intact. At a higher potential over 1.9 V, α-PtO 2-type surface oxides dissolve due to local acidification caused by the oxygen evolution reaction and carbon corrosion. Pt oxidation of Pt ML on the Pd nanoparticle electrocatalyst is considerably hampered compared with the Pt/C catalyst, presumably because preferential Pd oxidation proceeds at the defects in Pt MLs up to 0.91 V and through O penetrated through the Pt MLs by the place exchange process above 1.11 V.« less

In vitro cytotoxicity of iron oxide nanoparticles: effects of chitosan and polyvinyl alcohol as stabilizing agents

NASA Astrophysics Data System (ADS)

Tran, Phong A.; Nguyen, Hiep T.; Fox, Kate; Tran, Nhiem

2018-03-01

Iron oxide magnetic nanoparticles have significant potential in biomedical applications such as in diagnosis, imaging and therapeutic agent delivery. The choice of stabilizers and surface functionalization is important as it is known to strongly influence the cytotoxicity of the nanoparticles. The present study aimed at investigating the effects of surface charges on the cytotoxicity of iron oxide nanoparticles. We used a co-precipitation method to synthesize iron oxide nanoparticles which were then stabilized with either chitosan (CS) or polyvinyl alcohol (PVA) which have net positive charge and zero charge at physiological pH, respectively. The nanoparticles were characterized in terms of size, charges and chemical oxidation state. Cytotoxicity of the nanoparticles was assessed using mouse fibroblast cells and was correlated with surface charges of the nanoparticles and their aggregation.

Fabrication and characterization of iron oxide dextran composite layers

NASA Astrophysics Data System (ADS)

Iconaru, S. L.; Predoi, S. A.; Beuran, M.; Ciobanu, C. S.; Trusca, R.; Ghita, R.; Negoi, I.; Teleanu, G.; Turculet, S. C.; Matei, M.; Badea, Monica; Prodan, A. M.

2018-02-01

Super paramagnetic iron oxide nanoparticles such as maghemite have been shown to exhibit antimicrobial properties [1-5]. Moreover, the iron oxide nanoparticles have been proposed as a potential magnetically controllable antimicrobial agent which could be directed to a specific infection [3-5]. The present research has focused on studies of the surface and structure of iron oxide dextran (D-IO) composite layers surface and structure. These composite layers were deposited on Si substrates. The structure of iron oxide dextran composite layers was investigated by X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) while the surface morphology was evaluated by Scanning Electron Microscopy (SEM). The structural characterizations of the iron oxide dextran composite layers revealed the basic constituents of both iron and dextran structure. Furthermore, the in vitro evaluation of the antifungal effect of the complex layers, which have been shown revealed to be active against C. albicans cells at distinct intervals of time, is exhibited. Our research came to confirm the fungicidal effect of iron oxide dextran composite layers. Also, our results suggest that iron oxide dextran surface may be used for medical treatment of biofilm associated Candida infections.

Nickel-based anodic electrocatalysts for fuel cells and water splitting

NASA Astrophysics Data System (ADS)

Chen, Dayi

Our world is facing an energy crisis, so people are trying to harvest and utilize energy more efficiently. One of the promising ways to harvest energy is via solar water splitting to convert solar energy to chemical energy stored in hydrogen. Another of the options to utilize energy more efficiently is to use fuel cells as power sources instead of combustion engines. Catalysts are needed to reduce the energy barriers of the reactions happening at the electrode surfaces of the water-splitting cells and fuel cells. Nickel-based catalysts happen to be important nonprecious electrocatalysts for both of the anodic reactions in alkaline media. In alcohol fuel cells, nickel-based catalysts catalyze alcohol oxidation. In water splitting cells, they catalyze water oxidation, i.e., oxygen evolution. The two reactions occur in a similar potential range when catalyzed by nickel-based catalysts. Higher output current density, lower oxidation potential, and complete substrate oxidation are preferred for the anode in the applications. In this dissertation, the catalytic properties of nickel-based electrocatalysts in alkaline medium for fuel oxidation and oxygen evolution are explored. By changing the nickel precursor solubility, nickel complex nanoparticles with tunable sizes on electrode surfaces were synthesized. Higher methanol oxidation current density is achieved with smaller nickel complex nanoparticles. DNA aggregates were used as a polymer scaffold to load nickel ion centers and thus can oxidize methanol completely at a potential about 0.1 V lower than simple nickel electrodes, and the methanol oxidation pathway is changed. Nickel-based catalysts also have electrocatalytic activity towards a wide range of substrates. Experiments show that methanol, ethanol, glycerol and glucose can be deeply oxidized and carbon-carbon bonds can be broken during the oxidation. However, when comparing methanol oxidation reaction to oxygen evolution reaction catalyzed by current nickel-based catalysts, methanol oxidation suffers from high overpotential and catalyst poisoning by high concentration of substrates, so current nickel-based catalysts are more suitable to be used as oxygen evolution catalysts. A photoanode design that applies nickel oxides to a semiconductor that is incorporated with surface-plasmonic metal electrodes to do solar water oxidation with visible light is proposed.

Observing the Electrochemical Oxidation of Co Metal at the Solid/Liquid Interface Using Ambient Pressure X-ray Photoelectron Spectroscopy

DOE PAGES

Han, Yong; Axnanda, Stephanus; Crumlin, Ethan J.; ...

2017-08-28

Some rcent advances of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) have enabled the chemical composition and the electrical potential profile at a liquid/electrode interface under electrochemical reaction conditions to be directly probed. In this work, we apply this operando technique to study the surface chemical composition evolution on a Co metal electrode in 0.1 M KOH aqueous solution under various electrical biases. It is found that an ~12.2 nm-thick layer of Co(OH) 2 forms at a potential of about -0.4 V Ag/AgCl, and upon increasing the anodic potential to about +0.4 V Ag/AgCl, this layer is partially oxidized into cobaltmore » oxyhydroxide (CoOOH). A CoOOH/Co(OH) 2 mixture layer is formed on the top of the electrode surface. Finally, the oxidized surface layer can be reduced to Co0 at a cathodic potential of -1.35 VAg/Cl. Our observations indicate that the ultrathin layer containing cobalt oxyhydroxide is the active phase for oxygen evolution reaction (OER) on a Co electrode in an alkaline electrolyte, consistent with previous studies.« less

THE EFFECTS OF POLARIZATION UPON THE STEEL WIRE-NITRIC ACID MODEL OF NERVE ACTIVITY.

PubMed

Bishop, G H

1927-11-20

The active process in a short length of steel wire passivated by 65 per cent nitric acid has been observed under the influence of a polarizing current, and the form of the potential recorded by the cathode ray oscillograph. In the passive wire, 80 per cent of the total potential drop takes place at the anode, 20 per cent at the cathode. The change from active to passive states, as measured by the potential change, is very abrupt compared to the duration of activity and the potential curve at a point on the wire is probably almost rectangular. The duration of the refractory state is decreased at the anode and increased at the cathode, as in nerve. This fact is against the idea that reactivity after passivation results from a partial reduction of an oxide layer. Soft iron wire passivated by anodal polarization repassivates after activation in acid of a dilution that fails to passivate it initially. It soon becomes rhythmic with a very short refractory phase, and then reacts continuously. Such a wire exhibits a very sharp alternation between a dark brown oxide coat during activity, and a bright clean surface during passivation. A passive steel wire in nitric acid shows many of the characteristics of an inert electrode such as platinum, and it may be inferred that, superposed upon the primary passivation potential, there exists an electrode or oxidation-reduction potential equilibrium between the effects of the various constituents of the solution. It is suggested that the phenomena of nerve-like reactivity in this system may involve an alternation between two protective coatings of the steel wire. During activity, the surface becomes mechanically coated with a brown oxide. If this coating does not adhere, due to gas convection or to rapid solution of the oxide, passivation does not result. Under sufficiently intense oxidizing conditions, a second oxide coat may form in the interstices of the first, and cover the surface as the first coating dissolves off. This furnishes the electrochemical protection of passivation, which is followed by the gradual attainment of electrode equilibrium with the solution.

THE EFFECTS OF POLARIZATION UPON THE STEEL WIRE-NITRIC ACID MODEL OF NERVE ACTIVITY

PubMed Central

Bishop, George H.

1927-01-01

The active process in a short length of steel wire passivated by 65 per cent nitric acid has been observed under the influence of a polarizing current, and the form of the potential recorded by the cathode ray oscillograph. In the passive wire, 80 per cent of the total potential drop takes place at the anode, 20 per cent at the cathode. The change from active to passive states, as measured by the potential change, is very abrupt compared to the duration of activity and the potential curve at a point on the wire is probably almost rectangular. The duration of the refractory state is decreased at the anode and increased at the cathode, as in nerve. This fact is against the idea that reactivity after passivation results from a partial reduction of an oxide layer. Soft iron wire passivated by anodal polarization repassivates after activation in acid of a dilution that fails to passivate it initially. It soon becomes rhythmic with a very short refractory phase, and then reacts continuously. Such a wire exhibits a very sharp alternation between a dark brown oxide coat during activity, and a bright clean surface during passivation. A passive steel wire in nitric acid shows many of the characteristics of an inert electrode such as platinum, and it may be inferred that, superposed upon the primary passivation potential, there exists an electrode or oxidation-reduction potential equilibrium between the effects of the various constituents of the solution. It is suggested that the phenomena of nerve-like reactivity in this system may involve an alternation between two protective coatings of the steel wire. During activity, the surface becomes mechanically coated with a brown oxide. If this coating does not adhere, due to gas convection or to rapid solution of the oxide, passivation does not result. Under sufficiently intense oxidizing conditions, a second oxide coat may form in the interstices of the first, and cover the surface as the first coating dissolves off. This furnishes the electrochemical protection of passivation, which is followed by the gradual attainment of electrode equilibrium with the solution. PMID:19872388

Effect of chemical etching and aging in boiling water on the corrosion resistance of Nitinol wires with black oxide resulting from manufacturing process.

PubMed

Shabalovskaya, S; Rondelli, G; Anderegg, J; Simpson, B; Budko, S

2003-07-15

The effect of chemical etching in a HF/HNO(3) acid solution and aging in boiling water on the corrosion resistance of Nitinol wires with black oxide has been evaluated with the use of potentiodynamic, modified potentiostatic ASTM F746, and scratch tests. Scanning-electron microscopy, elemental XPS, and Auger analysis were employed to characterize surface alterations induced by surface treatment and corrosion testing. The effect of aging in boiling water on the temperatures of martensitic transformations and shape recovery was evaluated by means of measuring the wire electroresistance. After corrosion tests, as-received wires revealed uniformly cracked surfaces reminiscent of the stress-corrosion-cracking phenomenon. These wires exhibited negative breakdown potentials in potentiostatic tests and variable breakdown potentials in potentiodynamic tests (- 100 mV to + 400 mV versus SCE). Wires with treated surfaces did not reveal cracking or other traces of corrosion attacks in potentiodynamic tests up to + 900-1400-mV potentials and no pitting after stimulation at + 800 mV in potentiostatic tests. They exhibited corrosion behavior satisfactory for medical applications. Significant improvement of corrosion parameters was observed on the reverse scans in potentiodynamic tests after exposure of treated wires to potentials > 1000 mV. In scratch tests, the prepared surfaces repassivated only at low potentials, comparable to that of stainless steel. Tremendous improvement of the corrosion behavior of treated Nitinol wires is associated with the removal of defect surface material and the growth of stable TiO(2) oxide. The role of precipitates in the corrosion resistance of Nitinol-scratch repassivation capacity in particular-is emphasized in the discussion. Copyright 2003 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 66B: 331-340, 2003

Carbon aerogel-based supercapacitors modified by hummers oxidation method.

PubMed

Xu, Yuelong; Ren, Bin; Wang, Shasha; Zhang, Lihui; Liu, Zhenfa

2018-05-14

Carbon aerogels of an inter-connected three-dimensional (3D) structure are a potential carbon material for supercapacitors. We report a new oxidation modification method to prepare a series of modified carbon aerogels (OM-CA) by Hummers oxidation method. Oxidation-modified carbon aerogels (OM-CA) are obtained from carbon aerogel powders oxidized by Hummers method. Sulfuric acid stoichiometry is studied in order to investigate the effect of the surface oxygen group on surface area and electrochemical performance. Additionally, heteroatoms are doped into carbon aerogels in the oxidation process. The effect of heteroatom doping on electrochemical performance as a supercapacitor electrode material is investigated. When the amount of sulfuric acid is 40 wt%, the dopping manganese content is 0.9 mol%, the specific surface area of OM-CA is 450 m 2 /g, and its specific capacitance is 151 F g -1 at 0.5 A g -1 , which is achieved by heteroatom doping and texture properties. In addition, OM-CA composite supercapacitors exhibit a stable cycle life at a current density of 0.5 A g -1 and retain 98.0% of initial capacitance over 500 cycles, and OM-CA-40% still presents a higher capacity, up to 148 F g -1 at 0.5 A g -1 . The high specific surface area and specific capacitance suggest the porous carbon material has potential applications in supercapacitors. Copyright © 2018 Elsevier Inc. All rights reserved.

Oxidative nanopatterning of titanium generates mesoporous surfaces with antimicrobial properties

PubMed Central

Variola, Fabio; Zalzal, Sylvia Francis; Leduc, Annie; Barbeau, Jean; Nanci, Antonio

2014-01-01

Mesoporous surfaces generated by oxidative nanopatterning have the capacity to selectively regulate cell behavior, but their impact on microorganisms has not yet been explored. The main objective of this study was to test the effects of such surfaces on the adherence of two common bacteria and one yeast strain that are responsible for nosocomial infections in clinical settings and biomedical applications. In addition, because surface characteristics are known to affect bacterial adhesion, we further characterized the physicochemical properties of the mesoporous surfaces. Focused ion beam (FIB) was used to generate ultrathin sections for elemental analysis by energy-dispersive X-ray spectroscopy (EDS), nanobeam electron diffraction (NBED), and high-angle annular dark field (HAADF) scanning transmission electron microscopy (STEM) imaging. The adherence of Staphylococcus aureus, Escherichia coli and Candida albicans onto titanium disks with mesoporous and polished surfaces was compared. Disks with the two surfaces side-by-side were also used for direct visual comparison. Qualitative and quantitative results from this study indicate that bacterial adhesion is significantly hindered by the mesoporous surface. In addition, we provide evidence that it alters structural parameters of C. albicans that determine its invasiveness potential, suggesting that microorganisms can sense and respond to the mesoporous surface. Our findings demonstrate the efficiency of a simple chemical oxidative treatment in generating nanotextured surfaces with antimicrobial capacity with potential applications in the implant manufacturing industry and hospital setting. PMID:24872694

Thin film lubrication of hexadecane confined by iron and iron oxide surfaces: A crucial role of surface structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ta, D. T.; Tieu, A. K.; Zhu, H. T., E-mail: hongtao@uow.edu.au

2015-10-28

A comparative analysis of thin film lubrication of hexadecane between different iron and its oxide surfaces has been carried out using classical molecular dynamic simulation. An ab initio force-field, COMPASS, was applied for n-hexadecane using explicit atom model. An effective potential derived from density functional theory calculation was utilized for the interfacial interaction between hexadecane and the tribo-surfaces. A quantitative surface parameterization was introduced to investigate the influence of surface properties on the structure, rheological properties, and tribological performance of the lubricant. The results show that although the wall-fluid attraction of hexadecane on pure iron surfaces is significantly stronger thanmore » its oxides, there is a considerable reduction of shear stress of confined n-hexadecane film between Fe(100) and Fe(110) surfaces compared with FeO(110), FeO(111), Fe{sub 2}O{sub 3}(001), and Fe{sub 2}O{sub 3}(012). It was found that, in thin film lubrication of hexadecane between smooth iron and iron oxide surfaces, the surface corrugation plays a role more important than the wall-fluid adhesion strength.« less

High concentration effects of neutral-potential-well interface traps on recombination dc current-voltage lineshape in metal-oxide-silicon transistors

NASA Astrophysics Data System (ADS)

Chen, Zuhui; Jie, Bin B.; Sah, Chih-Tang

2008-11-01

Steady-state Shockley-Read-Hall kinetics is employed to explore the high concentration effect of neutral-potential-well interface traps on the electron-hole recombination direct-current current-voltage (R-DCIV) properties in metal-oxide-silicon field-effect transistors. Extensive calculations include device parameter variations in neutral-trapping-potential-well electron interface-trap density NET (charge states 0 and -1), dopant impurity concentration PIM, oxide thickness Xox, forward source/drain junction bias VPN, and transistor temperature T. It shows significant distortion of the R-DCIV lineshape by the high concentrations of the interface traps. The result suggests that the lineshape distortion observed in past experiments, previously attributed to spatial variation in surface impurity concentration and energy distribution of interface traps in the silicon energy gap, can also arise from interface-trap concentration along surface channel region.

Ordered Fe(II)Ti(IV)O3 Mixed Monolayer Oxide on Rutile TiO2(011).

PubMed

Halpegamage, Sandamali; Ding, Pan; Gong, Xue-Qing; Batzill, Matthias

2015-08-25

Oxide monolayers supported or intermixed with an oxide support are potential nanocatalysts whose properties are determined by the interplay with the support. For fundamental studies of monolayer oxides on metal oxide supports, well-defined systems are needed, but so far, the synthesis of monolayer oxides with long-range order on single-crystal oxide surfaces is rare. Here, we show by a combination of scanning tunneling microscopy, photoemission spectroscopy, and density functional theory (DFT)-based computational analysis that the rutile TiO2(011) surface supports the formation of an ordered mixed FeTiO3 monolayer. Deposition of iron in a slightly oxidizing atmosphere (10(-8) Torr O2) and annealing to 300 °C results in a well-ordered surface structure with Fe in a 2+ charge state and Ti in a 4+ charge states. Low-energy ion scattering suggests that the cation surface composition is close to half Fe and half Ti. This surface is stable in ultrahigh vacuum to annealing temperatures of 300 °C before the iron is reduced. DFT simulations confirm that a surface structure with coverage of 50% FeO units is stable and forms an ordered structure. Although distinct from known bulk phases of the iron-titanium oxide systems, the FeTiO3 monolayer exhibits some resemblance to the ilmenite structure, which may suggest that a variety of different mixed oxide phases (of systems that exist in a bulk ilmenite phase) may be synthesized in this way on the rutile TiO2(011) substrate.

Nonfouling Characteristics of Dextran-Containing Surfaces

PubMed Central

Martwiset, Surangkhana; Koh, Anna E.; Chen, Wei

2008-01-01

Hydroxyl groups in dextrans have been selectively oxidized to aldehyde groups by sodium periodate in a controlled fashion with percentage of conversion ranging from 6% to 100%. Dextrans (10 k, 70 k, 148 k, 500 k, and 2 000 kDa) and oxidized 10 k dextrans have been successfully grafted to functionalized silicon surfaces. The effect of molecular weight on protein adsorption is not nearly as striking as that of the extent of oxidation. When ∼ 25% of the hydroxyl groups have been converted to aldehyde groups, there is negligible protein adsorption on surfaces containing the oxidized polysaccharides. Conformations of grafted polymers depend strongly on their chemical structures, i.e. the relative amounts of –OH and –CHO groups. That the dependence of the chain conformation as well as the protein resistance on the balance of the hydrogen bond donors (-OH) and the acceptors (-OH and –CHO) implies the importance of chemical structure of surface molecules, specifically the interactions between surface and surrounding water molecules on protein adsorption. Oxidized dextrans are potential poly(ethylene glycol)-alternatives for nonfouling applications. PMID:16952261

Measurement of UO2 surface oxidation using grazing-incidence x-ray diffraction: Implications for nuclear forensics

NASA Astrophysics Data System (ADS)

Tracy, Cameron L.; Chen, Chien-Hung; Park, Sulgiye; Davisson, M. Lee; Ewing, Rodney C.

2018-04-01

Nuclear forensics involves determination of the origin and history of interdicted nuclear materials based on the detection of signatures associated with their production and trafficking. The surface oxidation undergone by UO2 when exposed to air is a potential signature of its atmospheric exposure during handling and transport. To assess the sensitivity of this oxidation to atmospheric parameters, surface sensitive grazing-incidence x-ray diffraction (GIXRD) measurements were performed on UO2 samples exposed to air of varying relative humidity (34%, 56%, and 95% RH) and temperature (room temperature, 50 °C, and 100 °C). Near-surface unit cell contraction was observed following exposure, indicating oxidation of the surface and accompanying reduction of the uranium cation ionic radii. The extent of unit cell contraction provides a measure of the extent of oxidation, allowing for comparison of the effects of various exposure conditions. No clear influence of relative humidity on the extent of oxidation was observed, with samples exhibiting similar degrees of unit cell contraction at all relative humidities investigated. In contrast, the thickness of the oxidized layers increased substantially with increasing temperature, such that differences on the order of 10 °C yielded readily observable crystallographic signatures of the exposure conditions.

Solar-Wind Protons and Heavy Ions Sputtering of Lunar Surface Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barghouty, N.; Meyer, Fred W; Harris, Peter R

2011-01-01

Lunar surface materials are exposed to {approx}1 keV/amu solar-wind protons and heavy ions on almost continuous basis. As the lunar surface consists of mostly oxides, these materials suffer, in principle, both kinetic and potential sputtering due to the actions of the solar-wind ions. Sputtering is an important mechanism affecting the composition of both the lunar surface and its tenuous exosphere. While the contribution of kinetic sputtering to the changes in the composition of the surface layer of these oxides is well understood and modeled, the role and implications of potential sputtering remain unclear. As new potential-sputtering data from multi-charged ionsmore » impacting lunar regolith simulants are becoming available from Oak Ridge National Laboratory's MIRF, we examine the role and possible implications of potential sputtering of Lunar KREEP soil. Using a non-equilibrium model we demonstrate that solar-wind heavy ions induced sputtering is critical in establishing the timescale of the overall solar-wind sputtering process of the lunar surface. We also show that potential sputtering leads to a more pronounced and significant differentiation between depleted and enriched surface elements. We briefly discuss the impacts of enhanced sputtering on the composition of the regolith and the exosphere, as well as of solar-wind sputtering as a source of hydrogen and water on the moon.« less

Evidence for decoupled electron and proton transfer in the electrochemical oxidation of ammonia on Pt(100)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katsounaros, Ioannis; Chen, Ting; Gewirth, Andrew A.

The two traditional mechanisms of the electrochemical ammonia oxidation consider only concerted proton-electron transfer elementary steps and thus they predict that the rate–potential relationship is independent of the pH on the pH-corrected RHE potential scale. In this letter we show that this is not the case: the increase of the solution pH shifts the onset of the NH 3-to-N 2 oxidation on Pt(100) to lower potentials and also leads to higher surface concentration of formed N Oad before the latter is oxidized to nitrite. Therefore, we present a new mechanism for the ammonia oxidation which incorporates a deprotonation step occurringmore » prior to the electron transfer. The deprotonation step yields a negatively charged surface-adsorbed species which is discharged in a subsequent electron transfer step before the N–N bond formation. The negatively charged species is thus a precursor for the formation of N 2 and NO. The new mechanism should be a future guide for computational studies aiming at the identification of intermediates and corresponding activation barriers for the elementary steps. As a result, ammonia oxidation is a new example of a bond-forming reaction on (100) terraces which involves decoupled proton-electron transfer.« less

Evidence for decoupled electron and proton transfer in the electrochemical oxidation of ammonia on Pt(100)

DOE PAGES

Katsounaros, Ioannis; Chen, Ting; Gewirth, Andrew A.; ...

2016-01-12

The two traditional mechanisms of the electrochemical ammonia oxidation consider only concerted proton-electron transfer elementary steps and thus they predict that the rate–potential relationship is independent of the pH on the pH-corrected RHE potential scale. In this letter we show that this is not the case: the increase of the solution pH shifts the onset of the NH 3-to-N 2 oxidation on Pt(100) to lower potentials and also leads to higher surface concentration of formed N Oad before the latter is oxidized to nitrite. Therefore, we present a new mechanism for the ammonia oxidation which incorporates a deprotonation step occurringmore » prior to the electron transfer. The deprotonation step yields a negatively charged surface-adsorbed species which is discharged in a subsequent electron transfer step before the N–N bond formation. The negatively charged species is thus a precursor for the formation of N 2 and NO. The new mechanism should be a future guide for computational studies aiming at the identification of intermediates and corresponding activation barriers for the elementary steps. As a result, ammonia oxidation is a new example of a bond-forming reaction on (100) terraces which involves decoupled proton-electron transfer.« less

Antimicrobial properties and mechanism of magnesium oxide nanoparticles on Campylobacter, E. coli O157:H7, and Salmonella

USDA-ARS?s Scientific Manuscript database

Background: Metal oxide nanoparticles have considerable potential as antimicrobial agents in food safety applications due to their structure, surface properties, and stability. In this study, the antibacterial effects and mechanisms of Magnesium Oxide Nanoparticles (MgO NPs, with an average size o...

Microbes, Minerals and Electrodes at the Sanford Underground Research Facility (SURF): Electrochemistry 4100 ft below the surface.

NASA Astrophysics Data System (ADS)

Rowe, A. R.; Abuyen, K.; Casar, C. P.; Osburn, M. R.; Kruger, B.; El-Naggar, M.; Amend, J.

2017-12-01

Little is known about the importance of mineral oxidation processes in subsurface environments. This stems, in part from our limited insight into the biochemistry of many of these metabolisms, especially where redox interactions with solid surfaces is concerned. To this aim, we have been developing electrochemical cultivation techniques, to target enrichment and isolation of microbes capable of oxidative extracellular electron transfer (oxEET)—transfer of electrons from the exterior of the cell to the interior. Our previous worked focused on marine sediments; using an electrode poised at a given redox potential to isolate mineral-oxidizing microbes. Electrode oxidizing microbes isolated from these enrichments belong to the genera Thioclava, Marinobacter, Halomonas, Idiomarina, Thalassospira, and Pseudamonas; organisms commonly detected in marine and deep sea sediments but not generally associated with mineral, sulfur and/or iron oxidation. At the Sanford Underground Research Facility (SURF) in Leed, South Dakota, we have been utilizing similar electrocultivation techniques to understand: 1) the potential for mineral oxidation by subsurface microbes, 2) their selective colonization on mineral vs. electrode surfaces, as well as 3) the community composition of microbes capable of these metabolic interactions. An electrochemical and mineral enrichment scheme was designed and installed into a sulfidic groundwater flow, located at the 4100 ft level of the former gold mine. The communities enriched on electrodes (graphite and indium tin oxide coated glass) and minerals (sulfur, pyrite, and schists from the location) were compared to the long-term ground water microbial community observed. Ultimately, these observations will help inform the potential activity of a lithotrophic microbes in situ and will in turn guide our culturing efforts.

Iron-oxide colloidal nanoclusters: from fundamental physical properties to diagnosis and therapy

NASA Astrophysics Data System (ADS)

Kostopoulou, Athanasia; Brintakis, Konstantinos; Lascialfari, Alessandro; Angelakeris, Mavroeidis; Vasilakaki, Marianna; Trohidou, Kalliopi; Douvalis, Alexios P.; Psycharakis, Stylianos; Ranella, Anthi; Manna, Liberato; Lappas, Alexandros

2014-03-01

Research on magnetic nanocrystals attracts wide-spread interest because of their challenging fundamental properties, but it is also driven by problems of practical importance to the society, ranging from electronics (e.g. magnetic recording) to biomedicine. In that respect, iron oxides are model functional materials as they adopt a variety of oxidation states and coordinations that facilitate their use. We show that a promising way to engineer further their technological potential in diagnosis and therapy is the assembly of primary nanocrystals into larger colloidal entities, possibly with increased structural complexity. In this context, elevated-temperature nanochemistry (c.f. based on a polyol approach) permitted us to develop size-tunable, low-cytotoxicity iron-oxide nanoclusters, entailing iso-oriented nanocrystals, with enhanced magnetization. Experimental (magnetometry, electron microscopy, Mössbauer and NMR spectroscopies) results supported by Monte Carlo simulations are reviewed to show that such assemblies of surface-functionalized iron oxide nanocrystals have a strong potential for innovation. The clusters' optimized magnetic anisotropy (including microscopic surface spin disorder) and weak ferrimagnetism at room temperature, while they do not undermine colloidal stability, endow them a profound advantage as efficient MRI contrast agents and hyperthermic mediators with important biomedical potential.

Potential toxicity of nonregulated asbestiform minerals: balangeroite from the western Alps. Part 2: Oxidant activity of the fibers.

PubMed

Turci, Francesco; Tomatis, Maura; Gazzano, Elena; Riganti, Chiara; Martra, Gianmario; Bosia, Amalia; Ghigo, Dario; Fubini, Bice

2005-01-08

The asbestiform mineral balangeroite [(Mg,Fe2+,Fe3+,Mn2+)42Si16O54(OH)36], whose toxic potential is unknown, is associated with chrysotile asbestos in the western Alps (Balangero mine, Piedmont, Italy). In order to examine whether such fibers may contribute to the oxidative damage produced by local asbestos dusts when inhaled, balangeroite was studied by means of both cell-free and cellular tests, comparing the results with those concerning the most pathogenic asbestos form, crocidolite. Similarly to the crocidolite surface, iron was mobilized from balangeroite by chelators, to a different extent: deferoxamine > ascorbic acid > ferrozine. Poorly coordinated surface ions, as evaluated from the adsorption of NO as a probe molecule (by both calorimetry and infrared spectroscopy), are even more abundant on balangeroite than on crocidolite. The spin trapping technique shows that surface iron-derived Fenton activity (HO* from H2O2) is similar for the two fiber types, while a pretreatment in ascorbic acid, by reducing previously oxidized surface iron, activates the potential to cleave a C-H bond (yielding *CO2- from formate anion). Balangeroite, like crocidolite, produces nitrite accumulation, lipid peroxidation, and NO synthase activation in a human lung epithelial cell line (A549). All these findings, regarded as features related to the toxic potential of asbestos, suggest that balangeroite may be a potentially hazardous fiber per se and could be partly responsible for lung diseases reported in epidemiological studies in exposed miners.

Passivating Window/First Layer AR Coating for Space Solar Cells

NASA Technical Reports Server (NTRS)

Faur, Mircea; Faur, Maria; Bailey, S. G.; Flood, D. J.; Brinker, D. J.; Alterovitz, S. A.; Wheeler, D. R.; Matesscu, G.; Goradia, C.; Goradia, M.

2004-01-01

Chemically grown oxides, if well designed, offer excellent surface passivation of the emitter surface of space solar cells and can be used as effective passivating window/first layer AR coating. In this paper, we demonstrate the effectiveness of using a simple room temperature wet chemical technique to grow cost effective passivating layers on solar cell front surfaces after the front grid metallization step. These passivating layers can be grown both on planar and porous surfaces. Our results show that these oxide layers: (i) can effectively passivate the from the surface, (ii) can serve as an effective optical window/first layer AR coating, (iii) are chemically, thermally and UV stable, and (iv) have the potential of improving the BOL and especially the EOL efficiency of space solar cells. The potential of using this concept to simplify the III-V based space cell heterostructures while increasing their BOL and EOL efficiency is also discussed.

Fabrication of ultra thin anodic aluminium oxide membranes by low anodization voltages

NASA Astrophysics Data System (ADS)

Pastore, I.; Poplausks, R.; Apsite, I.; Pastare, I.; Lombardi, F.; Erts, D.

2011-06-01

Formation of ultrathin anodised aluminium oxide (AAO) membranes with high aspect ratio by Al anodization in sulphuric and oxalic acids at low potentials was investigated. Low anodization potentials ensure slow electrochemical reaction speeds and formation of AAO membranes with pore diameter and thickness below 20 nm and 70 nm respectively. Minimum time necessary for formation of continuous AAO membranes was determined. AAO membrane pore surface was covered with polymer Paraloid B72TM to transport it to the selected substrate. The fabricated ultra thin AAO membranes could be used to fabricate nanodot arrays on different surfaces.

Accelerated and enhanced bone formation on novel simvastatin-loaded porous titanium oxide surfaces.

PubMed

Nyan, Myat; Hao, Jia; Miyahara, Takayuki; Noritake, Kanako; Rodriguez, Reena; Kasugai, Shohei

2014-10-01

With increasing application of dental implants in poor-quality bones, the need for implant surfaces ensuring accelerated osseointegration and enhanced peri-implant bone regeneration is increased. A study was performed to evaluate the osseointegration and bone formation on novel simvastatin-loaded porous titanium oxide surface. Titanium screws were treated by micro-arc oxidation to form porous oxide surface and 25 or 50 μg of simvastatin was loaded. The nontreated control, micro-arc oxidized, and simvastatin-loaded titanium screws were surgically implanted into the proximal tibia of 16-week-old male Wistar rats (n = 36). Peri-implant bone volume, bone-implant contact, and mineral apposition rates were measured at 2 and 4 weeks. Data were analyzed by one-way analysis of variance followed by Tukey's post hoc test. New bone was formed directly on the implant surface in the bone marrow cavity in simvastatin-loaded groups since 2 weeks. Bone-implant contact values were significantly higher in simvastatin-loaded groups than control and micro-arc oxidized groups at both time points (p < .05). Peri-implant bone volume and mineral apposition rate of simvastatin-loaded groups were significantly higher than control and micro-arc oxidized groups at 2 weeks (p < .05). These data suggested that simvastatin-loaded porous titanium oxide surface provides faster osseointegration and peri-implant bone formation and it would be potentially applicable in poor-quality bones. © 2013 Wiley Periodicals, Inc.

Antimicrobial Activity of Nitric Oxide-Releasing Ti-6Al-4V Metal Oxide

PubMed Central

Reger, Nina A.; Meng, Wilson S.; Gawalt, Ellen S.

2017-01-01

Titanium and titanium alloy materials are commonly used in joint replacements, due to the high strength of the materials. Pathogenic microorganisms can easily adhere to the surface of the metal implant, leading to an increased potential for implant failure. The surface of a titanium-aluminum-vanadium (Ti-6Al-4V) metal oxide implant material was functionalized to deliver an small antibacterial molecule, nitric oxide. S-nitroso-penicillamine, a S-nitrosothiol nitric oxide donor, was covalently immobilized on the metal oxide surface using self-assembled monolayers. Infrared spectroscopy was used to confirm the attachment of the S-nitrosothiol donor to the Ti-Al-4V surface. Attachment of S-nitroso-penicillamine resulted in a nitric oxide (NO) release of 89.6 ± 4.8 nmol/cm2 under physiological conditions. This low concentration of nitric oxide reduced Escherichia coli and Staphylococcus epidermidis growth by 41.5 ± 1.2% and 25.3 ± 0.6%, respectively. Combining the S-nitrosothiol releasing Ti-6Al-4V with tetracycline, a commonly-prescribed antibiotic, increased the effectiveness of the antibiotic by 35.4 ± 1.3%, which allows for lower doses of antibiotics to be used. A synergistic effect of ampicillin with S-nitroso-penicillamine-modified Ti-6Al-4V against S. epidermidis was not observed. The functionalized Ti-6Al-4V surface was not cytotoxic to mouse fibroblasts. PMID:28635681

Iron cycling at corroding carbon steel surfaces.

PubMed

Lee, Jason S; McBeth, Joyce M; Ray, Richard I; Little, Brenda J; Emerson, David

2013-01-01

Surfaces of carbon steel (CS) exposed to mixed cultures of iron-oxidizing bacteria (FeOB) and dissimilatory iron-reducing bacteria (FeRB) in seawater media under aerobic conditions were rougher than surfaces of CS exposed to pure cultures of either type of microorganism. The roughened surface, demonstrated by profilometry, is an indication of loss of metal from the surface. In the presence of CS, aerobically grown FeOB produced tight, twisted helical stalks encrusted with iron oxides. When CS was exposed anaerobically in the presence of FeRB, some surface oxides were removed. However, when the same FeOB and FeRB were grown together in an aerobic medium, FeOB stalks were less encrusted with iron oxides and appeared less tightly coiled. These observations suggest that iron oxides on the stalks were reduced and solubilized by the FeRB. Roughened surfaces of CS and denuded stalks were replicated with culture combinations of different species of FeOB and FeRB under three experimental conditions. Measurements of electrochemical polarization resistance established different rates of corrosion of CS in aerobic and anaerobic media, but could not differentiate rate differences between sterile controls and inoculated exposures for a given bulk concentration of dissolved oxygen. Similarly, total iron in the electrolyte could not be used to differentiate treatments. The experiments demonstrate the potential for iron cycling (oxidation and reduction) on corroding CS in aerobic seawater media.

Iron cycling at corroding carbon steel surfaces

PubMed Central

Lee, Jason S.; McBeth, Joyce M.; Ray, Richard I.; Little, Brenda J.; Emerson, David

2013-01-01

Surfaces of carbon steel (CS) exposed to mixed cultures of iron-oxidizing bacteria (FeOB) and dissimilatory iron-reducing bacteria (FeRB) in seawater media under aerobic conditions were rougher than surfaces of CS exposed to pure cultures of either type of microorganism. The roughened surface, demonstrated by profilometry, is an indication of loss of metal from the surface. In the presence of CS, aerobically grown FeOB produced tight, twisted helical stalks encrusted with iron oxides. When CS was exposed anaerobically in the presence of FeRB, some surface oxides were removed. However, when the same FeOB and FeRB were grown together in an aerobic medium, FeOB stalks were less encrusted with iron oxides and appeared less tightly coiled. These observations suggest that iron oxides on the stalks were reduced and solubilized by the FeRB. Roughened surfaces of CS and denuded stalks were replicated with three culture combinations of different species of FeOB and FeRB under three experimental conditions. Measurements of electrochemical polarization resistance established different rates of corrosion of CS in aerobic and anaerobic media, but could not differentiate rate differences between sterile controls and inoculated exposures for a given bulk concentration of dissolved oxygen. Similarly, total iron in the electrolyte could not be used to differentiate treatments. The experiments demonstrate the potential for iron cycling (oxidation and reduction) on corroding CS in aerobic seawater media. PMID:24093730

Manganese Oxide Nanoarray-Based Monolithic Catalysts: Tunable Morphology and High Efficiency for CO Oxidation

DOE PAGES

Chen, Sheng-Yu; Song, Wenqiao; Lin, Hui-Jan; ...

2016-03-08

In this work, a generic one-pot hydrothermal synthesis route has been successfully designed and utilized to in situ grow uniform manganese oxide nanorods and nanowires onto the cordierite honeycomb monolithic substrates, forming a series of nanoarray-based monolithic catalysts. During the synthesis process, three types of potassium salt oxidants have been used with different reduction potentials, i.e., K 2Cr 2O 7, KClO 3, and K 2S 2O 8, denoted as HM-DCM, HM-PCR, and HM-PSF, respectively. The different reduction potentials of the manganese source (Mn 2+) and oxidants induced the formation of manganese oxide nanoarrays with different morphology, surface area, and reactivitymore » of carbon monoxide (CO) oxidation. K 2Cr 2O 7 and KClO 3 can induce sharp and long nanowires with slow growth rates due to their low reduction potentials. In comparison, the nanoarrays of HM-PSF presented shorter nanorods but displayed an efficient 90% CO oxidation conversion at 200 °C (T90) without noble-metal loading. Reducibility tests for the three monolithic catalysts by hydrogen temperature-programmed reduction revealed an activation energy order of HM-PSF > HM-DCM > HM-PCR for CO oxidation. The characterizations of oxygen temperature-programmed desorption and X-ray photoelectron spectroscopy indicated the abundant surface-adsorbed oxygen and lattice oxygen contributing to the superior reactivity of HM-PSF. Finally, the straightforward synthetic process showed a scalable, low-cost, and template-free method to fabricate manganese oxide nanoarray monolithic catalysts for exhaust treatment.« less

Surface Interrogation Scanning Electrochemical Microscopy for a Photoelectrochemical Reaction: Water Oxidation on a Hematite Surface.

PubMed

Kim, Jae Young; Ahn, Hyun S; Bard, Allen J

2018-03-06

To understand the pathway of a photoelectrochemical (PEC) reaction, quantitative knowledge of reaction intermediates is important. We describe here surface interrogation scanning electrochemical microscopy for this purpose (PEC SI-SECM), where a light pulse to a photoactive semiconductor film at a given potential generates intermediates that are then analyzed by a tip generated titrant at known times after the light pulse. The improvements were demonstrated for photoelectrochemical water oxidation (oxygen evolution) reaction on a hematite surface. The density of photoactive sites, proposed to be Fe 4+ species, on a hematite surface was successfully quantified, and the photoelectrochemical water oxidation reaction dynamics were elucidated by time-dependent redox titration experiments. The new configuration of PEC SI-SECM should find expanded usage to understand and investigate more complicated PEC reactions with other materials.

Controlling lipid oxidation via a biomimetic iron chelating active packaging material.

PubMed

Tian, Fang; Decker, Eric A; Goddard, Julie M

2013-12-18

Previously, a siderophore-mimetic metal chelating active packaging film was developed by grafting poly(hydroxamic acid) (PHA) from the surface of polypropylene (PP) films. The objective of the current work was to demonstrate the potential applicability of this PP-g-PHA film to control iron-promoted lipid oxidation in food emulsions. The iron chelating activity of this film was investigated, and the surface chemistry and color intensity of films were also analyzed after iron chelation. In comparison to the iron chelating activity in the free Fe(3+) solution, the PP-g-PHA film retained approximately 50 and 30% of its activity in nitrilotriacetic acid (NTA)/Fe(3+) and citric acid/Fe(3+) solutions, respectively (pH 5.0), indicating a strong chelating strength for iron. The ability of PP-g-PHA films to control lipid oxidation was demonstrated in a model emulsion system (pH 3.0). PP-g-PHA films performed even better than ethylenediaminetetraacetic acid (EDTA) in preventing the formation of volatile oxidation products. The particle size and ζ potential results of emulsions indicated that PP-g-PHA films had no adverse effects on the stability of the emulsion system. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) analysis suggested a non-migratory nature of the PP-g-PHA film surface. These results suggest that such biomimetic, non-migratory metal chelating active packaging films have commercial potential in protecting foods against iron-promoted lipid oxidation.

A surface-charge study on cellular-uptake behavior of F3-peptide-conjugated iron oxide nanoparticles.

PubMed

Zhang, Yu; Yang, Mo; Park, Ji-Ho; Singelyn, Jennifer; Ma, Huiqing; Sailor, Michael J; Ruoslahti, Erkki; Ozkan, Mihrimah; Ozkan, Cengiz

2009-09-01

Surface-charge measurements of mammalian cells in terms of Zeta potential are demonstrated as a useful biological characteristic in identifying cellular interactions with specific nanomaterials. A theoretical model of the changes in Zeta potential of cells after incubation with nanoparticles is established to predict the possible patterns of Zeta-potential change to reveal the binding and internalization effects. The experimental results show a distinct pattern of Zeta-potential change that allows the discrimination of human normal breast epithelial cells (MCF-10A) from human cancer breast epithelial cells (MCF-7) when the cells are incubated with dextran coated iron oxide nanoparticles that contain tumor-homing F3 peptides, where the tumor-homing F3 peptide specifically bound to nucleolin receptors that are overexpressed in cancer breast cells.

Measurement of the surface charge accumulation using anodic aluminum oxide(AAO) structure in an inductively coupled plasma

NASA Astrophysics Data System (ADS)

Park, Ji-Hwan; Oh, Seung-Ju; Lee, Hyo-Chang; Kim, Yu-Sin; Kim, Young-Cheol; Kim, June Young; Ha, Chang-Seoung; Kwon, Soon-Ho; Lee, Jung-Joong; Chung, Chin-Wook

2014-10-01

As the critical dimension of the nano-device shrinks, an undesired etch profile occurs during plasma etch process. One of the reasons is the local electric field due to the surface charge accumulation. To demonstrate the surface charge accumulation, an anodic aluminum oxide (AAO) membrane which has high aspect ratio is used. The potential difference between top electrode and bottom electrode in an anodic aluminum oxide contact structure is measured during inductively coupled plasma exposure. The voltage difference is changed with external discharge conditions, such as gas pressure, input power, and gas species and the result is analyzed with the measured plasma parameters.

Thermally oxidized titania nanotubes enhance the corrosion resistance of Ti6Al4V.

PubMed

Grotberg, John; Hamlekhan, Azhang; Butt, Arman; Patel, Sweetu; Royhman, Dmitry; Shokuhfar, Tolou; Sukotjo, Cortino; Takoudis, Christos; Mathew, Mathew T

2016-02-01

The negative impact of in vivo corrosion of metallic biomedical implants remains a complex problem in the medical field. We aimed to determine the effects of electrochemical anodization (60V, 2h) and thermal oxidation (600°C) on the corrosive behavior of Ti-6Al-4V, with serum proteins, at physiological temperature. Anodization produced a mixture of anatase and amorphous TiO2 nanopores and nanotubes, while the annealing process yielded an anatase/rutile mixture of TiO2 nanopores and nanotubes. The surface area was analyzed by the Brunauer-Emmett-Teller method and was estimated to be 3 orders of magnitude higher than that of polished control samples. Corrosion resistance was evaluated on the parameters of open circuit potential, corrosion potential, corrosion current density, passivation current density, polarization resistance and equivalent circuit modeling. Samples both anodized and thermally oxidized exhibited shifts of open circuit potential and corrosion potential in the noble direction, indicating a more stable nanoporous/nanotube layer, as well as lower corrosion current densities and passivation current densities than the smooth control. They also showed increased polarization resistance and diffusion limited charge transfer within the bulk oxide layer. The treatment groups studied can be ordered from greatest corrosion resistance to least as Anodized+Thermally Oxidized > Anodized > Smooth > Thermally Oxidized for the conditions investigated. This study concludes that anodized surface has a potential to prevent long term implant failure due to corrosion in a complex in-vivo environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Positron annihilation induced Auger electron spectroscopic studies of oxide surfaces

NASA Astrophysics Data System (ADS)

Nadesalingam, Manori

2005-03-01

Defects on oxide surfaces are well known to play a key role in catalysis. TiO2, MgO, SiO2 surfaces were investigated using Time-Of-Flight Positron induced Auger Electron Spectroscopy (TOF-PAES). Previous work in bulk materials has demonstrated that positrons are particularly sensitive to charged defects. In PAES energetic electron emission results from Auger transitions initiated by annihilation of core electrons with positrons trapped in an image-potential well at the surface. Annealed samples in O2 environment show a strong Auger peak of Oxygen. The implication of these results will be discussed

A bioactive coating with submicron-sized titania crystallites fabricated by induction heating of titanium after tensile deformations.

PubMed

Li, Ning-Bo; Xu, Wen-Hua; Xiao, Gui-Yong; Zhao, Jun-Han; Lu, Yu-Peng

2017-11-01

Thermal oxidation technology was widely investigated as one of effective surface modification method for improving the bioactivity and biocompatibility of titanium and its alloys. In this work, the induction heat oxidization method, a fast, efficient, economical and environmental protective technology, was applied to prepare the submicron-morphological oxide coating with variable rutile TiO 2 equiaxed crystallites on the surface of pure Ti substrates after cold-drawing with 10-20% deformations. The results showed the plastic-deformed Ti cylinders recrystallized during induction heating treatment (IHT) for 10-20s which resulted in evolution of microstructures as well as slight improvement of microhardness. The surface characteristics of TiO 2 crystallites in oxidation layers were determined by the microstructural evolutions of Ti substrate in terms of the nucleation and growth of TiO 2 crystallites. Specially, the oxidized surface with 50-75nm roughness and more uniform and finer equiaxed oxide grains remarkablely improved the apatite deposition after bioactive evaluation in 1.5 × SBF for 7 days. This work provided a potential method to create controlled bioactive oxide coatings with submicro-/nano-scaled TiO 2 crystallites on titanium substrate in terms of the role of metallographic microstructure in the formation process of titanium oxides. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of modification of oxide layer on NiTi stent corrosion resistance.

PubMed

Trépanier, C; Tabrizian, M; Yahia, L H; Bilodeau, L; Piron, D L

1998-01-01

Because of its good radiopacity, superelasticity, and shape memory properties, nickel-titanium (NiTi) is a potential material for fabrication of stents because these properties can facilitate their implantation and precise positioning. However, in vitro studies of NiTi alloys report the dependence of alloy biocompatibility and corrosion behavior on surface conditions. Surface oxidation seems to be very promising for improving the corrosion resistance and biocompatibility of NiTi. In this work, we studied the effect on corrosion resistance and surface characteristics of electropolishing, heat treatment, and nitric acid passivation of NiTi stents. Characterization techniques such as potentiodynamic polarization tests, scanning electron microscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy were used to relate corrosion behavior to surface characteristics and surface treatments. Results show that all of these surface treatments improve the corrosion resistance of the alloy. This improvement is attributed to the plastically deformed native oxide layer removal and replacement by a newly grown, more uniform one. The uniformity of the oxide layer, rather than its thickness and composition, seems to be the predominant factor to explain the corrosion resistance improvement.

Electrofluidic gating of a chemically reactive surface.

PubMed

Jiang, Zhijun; Stein, Derek

2010-06-01

We consider the influence of an electric field applied normal to the electric double layer at a chemically reactive surface. Our goal is to elucidate how surface chemistry affects the potential for field-effect control over micro- and nanofluidic systems, which we call electrofluidic gating. The charging of a metal-oxide-electrolyte (MOE) capacitor is first modeled analytically. We apply the Poisson-Boltzmann description of the double layer and impose chemical equilibrium between the ionizable surface groups and the solution at the solid-liquid interface. The chemically reactive surface is predicted to behave as a buffer, regulating the charge in the double layer by either protonating or deprotonating in response to the applied field. We present the dependence of the charge density and the electrochemical potential of the double layer on the applied field, the density, and the dissociation constants of ionizable surface groups and the ionic strength and the pH of the electrolyte. We simulate the responses of SiO(2) and Al(2)O(3), two widely used oxide insulators with different surface chemistries. We also consider the limits to electrofluidic gating imposed by the nonlinear behavior of the double layer and the dielectric strength of oxide materials, which were measured for SiO(2) and Al(2)O(3) films in MOE configurations. Our results clarify the response of chemically reactive surfaces to applied fields, which is crucial to understanding electrofluidic effects in real devices.

Graphitic and oxidised high pressure high temperature (HPHT) nanodiamonds induce differential biological responses in breast cancer cell lines.

PubMed

Woodhams, Benjamin; Ansel-Bollepalli, Laura; Surmacki, Jakub; Knowles, Helena; Maggini, Laura; de Volder, Michael; Atatüre, Mete; Bohndiek, Sarah

2018-06-19

Nanodiamonds have demonstrated potential as powerful sensors in biomedicine, however, their translation into routine use requires a comprehensive understanding of their effect on the biological system being interrogated. Under normal fabrication processes, nanodiamonds are produced with a graphitic carbon shell, but are often oxidized in order to modify their surface chemistry for targeting to specific cellular compartments. Here, we assessed the biological impact of this purification process, considering cellular proliferation, uptake, and oxidative stress for graphitic and oxidized nanodiamond surfaces. We show for the first time that oxidized nanodiamonds possess improved biocompatibility compared to graphitic nanodiamonds in breast cancer cell lines, with graphitic nanodiamonds inducing higher levels of oxidative stress despite lower uptake.

Conducting oxide formation and mechanical endurance of potential solid-oxide fuel cell interconnects in coal syngas environment

NASA Astrophysics Data System (ADS)

Liu, Kejia; Luo, Junhang; Johnson, Chris; Liu, Xingbo; Yang, J.; Mao, Scott X.

The oxidation properties of potential SOFCs materials Crofer 22 APU, Ebrite and Haynes 230 exposed in coal syngas at 800 °C for 100 h were studied. The phases and surface morphology of the oxide scales were characterized by X-ray diffraction, scanning electron microscopy and energy-dispersive X-ray analysis (EDX). The mechanical endurance and electrical resistance of the conducting oxides were characterized by indentation and electrical impedance, respectively. It was found that the syngas exposure caused the alloys to form porous oxide scales, which increased the electrical resistant and decreased the mechanical stability. As for short-term exposure in syngas, neither carbide nor metal dusting was found in the scales of all samples.

Physical characterization of a new composition of oxidized zirconium-2.5 wt% niobium produced using a two step process for biomedical applications

NASA Astrophysics Data System (ADS)

Pawar, V.; Weaver, C.; Jani, S.

2011-05-01

Zirconium and particularly Zr-2.5 wt%Nb (Zr2.5Nb) alloy are useful for engineering bearing applications because they can be oxidized in air to form a hard surface ceramic. Oxidized zirconium (OxZr) due to its abrasion resistant ceramic surface and biocompatible substrate alloy has been used as a bearing surface in total joint arthroplasty for several years. OxZr is characterized by hard zirconium oxide (oxide) formed on Zr2.5Nb using one step thermal oxidation carried out in air. Because the oxide is only at the surface, the bulk material behaves like a metal, with high toughness. The oxide, furthermore, exhibits high adhesion to the substrate because of an oxygen-rich diffusion hardened zone (DHZ) interposing between the oxide and the substrate. In this study, we demonstrate a two step process that forms a thicker DHZ and thus increased depth of hardening than that can be obtained using a one step oxidation process. The first step is thermal oxidation in air and the second step is a heat treatment in vacuum. The second step drives oxygen from the oxide formed in the first step deeper into the substrate to form a thicker DHZ. During the process only a portion of the oxide is dissolved. This new composition (DHOxZr) has approximately 4-6 μm oxide similar to that of OxZr. The nano-hardness of the oxide is similar but the DHZ is approximately 10 times thicker. The stoichiometry of the oxide is similar and a secondary phase rich in oxygen is present through the entire thickness. Due to the increased depth of hardening, the critical load required for the onset of oxide cracking is approximately 1.6 times more than that of the oxide of OxZr. This new composition has a potential to be used as a bearing surface in applications where greater depth of hardening is required.

Platinum recycling going green via induced surface potential alteration enabling fast and efficient dissolution

PubMed Central

Hodnik, Nejc; Baldizzone, Claudio; Polymeros, George; Geiger, Simon; Grote, Jan-Philipp; Cherevko, Serhiy; Mingers, Andrea; Zeradjanin, Aleksandar; Mayrhofer, Karl J. J.

2016-01-01

The recycling of precious metals, for example, platinum, is an essential aspect of sustainability for the modern industry and energy sectors. However, due to its resistance to corrosion, platinum-leaching techniques rely on high reagent consumption and hazardous processes, for example, boiling aqua regia; a mixture of concentrated nitric and hydrochloric acid. Here we demonstrate that complete dissolution of metallic platinum can be achieved by induced surface potential alteration, an ‘electrode-less' process utilizing alternatively oxidative and reductive gases. This concept for platinum recycling exploits the so-called transient dissolution mechanism, triggered by a repetitive change in platinum surface oxidation state, without using any external electric current or electrodes. The effective performance in non-toxic low-concentrated acid and at room temperature is a strong benefit of this approach, potentially rendering recycling of industrial catalysts, including but not limited to platinum-based systems, more sustainable. PMID:27767178

Probing size-dependent electrokinetics of hematite aggregates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kedra-Królik, Karolina; Rosso, Kevin M.; Zarzycki, Piotr

Aqueous particle suspensions of many kinds are stabilized by the electrostatic potential developed at their surfaces from reaction with water and ions. An important and less well understood aspect of this stabilization is the dependence of the electrostatic surface potential on particle size. Surface electrostatics are typically probed by measuring particle electrophoretic mobilities and quantified in the electrokinetic potential (f), using commercially available Zeta Potential Analyzers (ZPA). Even though ZPAs provide frequency-spectra (histograms) of electrophoretic mobility and hydrodynamic diameter, typically only the maximal-intensity values are reported, despite the information in the remainder of the spectra. Here we propose a mappingmore » procedure that inter-correlates these histograms to extract additional insight, in this case to probe particle size-dependent electrokinetics. Our method is illustrated for a suspension of prototypical iron (III) oxide (hematite, a-Fe2O3). We found that the electrophoretic mobility and f-potential are a linear function of the aggregate size. By analyzing the distribution of surface site types as a function of aggregate size we show that site coordination increases with increasing aggregate diameter. This observation explains why the acidity of the iron oxide particles decreases with increasing particle size.« less

Facile synthesis of birnessite-type manganese oxide nanoparticles as supercapacitor electrode materials.

PubMed

Liu, Lihu; Luo, Yao; Tan, Wenfeng; Zhang, Yashan; Liu, Fan; Qiu, Guohong

2016-11-15

Manganese oxides are environmentally benign supercapacitor electrode materials and, in particular, birnessite-type structure shows very promising electrochemical performance. In this work, nanostructured birnessite was facilely prepared by adding dropwise NH2OH·HCl to KMnO4 solution under ambient temperature and pressure. In order to fully exploit the potential of birnessite-type manganese oxide electrode materials, the effects of specific surface area, pore size, content of K(+), and manganese average oxidation state (Mn AOS) on their electrochemical performance were studied. The results showed that with the increase of NH2OH·HCl, the Mn AOS decreased and the corresponding pore sizes and specific surface area of birnessite increased. The synthesized nanostructured birnessite showed the highest specific capacitance of 245Fg(-1) at a current density of 0.1Ag(-1) within a potential range of 0-0.9V, and excellent cycle stability with a capacitance retention rate of 92% after 3000 cycles at a current density of 1.0Ag(-1). The present work implies that specific capacitance is mainly affected by specific surface area and pore volume, and provides a new method for the facile preparation of birnessite-type manganese oxide with excellent capacitive performance. Copyright © 2016 Elsevier Inc. All rights reserved.

Redox switching and oxygen evolution at oxidized metal and metal oxide electrodes: iron in base.

PubMed

Lyons, Michael E G; Doyle, Richard L; Brandon, Michael P

2011-12-28

Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified via analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of ca. 60 mV dec(-1) and ca. 120 mV dec(-1) are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from ca. 3/2 to ca. 1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates.

Influence of the surface speciation on biofilm attachment to chalcopyrite by Acidithiobacillus thiooxidans.

PubMed

Lara, René H; García-Meza, J Viridiana; González, Ignacio; Cruz, Roel

2013-03-01

Surfaces of massive chalcopyrite (CuFeS2) electrodes were modified by applying variable oxidation potential pulses under growth media in order to induce the formation of different secondary phases (e.g., copper-rich polysulfides, S n(2-); elemental sulfur, S(0); and covellite, CuS). The evolution of reactivity (oxidation capacity) of the resulting chalcopyrite surfaces considers a transition from passive or inactive (containing CuS and S n(2-)) to active (containing increasing amounts of S(0)) phases. Modified surfaces were incubated with cells of sulfur-oxidizing bacteria (Acidithiobacillus thiooxidans) for 24 h in a specific culture medium (pH 2). Abiotic control experiments were also performed to compare chemical and biological oxidation. After incubation, the density of cells attached to chalcopyrite surfaces, the structure of the formed biofilm, and their exopolysaccharides and nucleic acids were analyzed by confocal laser scanning microscopy (CLSM) and scanning electron microscopy coupled to dispersive X-ray analysis (SEM-EDS). Additionally, CuS and S n(2-)/S(0) speciation, as well as secondary phase evolution, was carried out on biooxidized and abiotic chalcopyrite surfaces using Raman spectroscopy and SEM-EDS. Our results indicate that oxidized chalcopyrite surfaces initially containing inactive S n(2-) and S n(2-)/CuS phases were less colonized by A. thiooxidans as compared with surfaces containing active phases (mainly S(0)). Furthermore, it was observed that cells were partially covered by CuS and S(0) phases during biooxidation, especially at highly oxidized chalcopyrite surfaces, suggesting the innocuous effect of CuS phases during A. thiooxidans performance. These results may contribute to understanding the effect of the concomitant formation of refractory secondary phases (as CuS and inactive S n(2-)) during the biooxidation of chalcopyrite by sulfur-oxidizing microorganisms in bioleaching systems.

Surface characteristics of sterilized electropolished NiTi shape memory alloy as biomaterials

NASA Astrophysics Data System (ADS)

Tabrizian, Maryam; Thierry, Benjamin; Savadogo, Omarou; Yahia, L'Hocine

1999-05-01

As a potential biomaterial for many medical applications, NiTi alloy derives its good biocompatibility and corrosion resistance from a homogeneous and protective oxide layer, mainly composed of TiO2, with little concentration of nickel. However, during corrosion testing at high potential, NiTi is susceptible to pitting corrosion, which may affect the amount of ions (nickel and titanium) released by the alloy and thus, may affect its biocompatibility. As a passivating treatment, electropolishing (EP) was demonstrated to decrease the amount of nickel on the surface and to remarkably improve the corrosion behavior of the alloy. After sterilization by ethylene oxide (EO), no modification of the promising corrosion behavior of electropolished NiTi were observed, although some surface modifications were reported. The corrosion resistance of ethylene oxide sterilized and electropolished samples ranked between that of the commonly used Ti6A14V and 316L (0.4 less than 1 less than 1.4 mV/SCE) implant alloys.

Electrochemical annealing of nanoporous gold by application of cyclic potential sweeps

PubMed Central

Sharma, Abeera; Bhattarai, Jay K.; Alla, Allan J.; Demchenko, Alexei V.; Stine, Keith J.

2015-01-01

An electrochemical method for annealing the pore sizes of nanoporous gold is reported. The pore sizes of nanoporous gold can be increased by electrochemical cycling with the upper potential limit being just at the onset of gold oxide formation. This study has been performed in electrolyte solutions including potassium chloride, sodium nitrate and sodium perchlorate. Scanning electron microscopy images have been used for ligament and pore size analysis. We examine the modifications of nanoporous gold due to annealing using electrochemical impedance spectroscopy, and cyclic voltammetry and offer a comparison of the surface coverage using the gold oxide stripping method as well as the method in which electrochemically accessible surface area is determined by using a diffusing redox probe. The effect of additives adsorbed on the nanoporous gold surface when subjected to annealing in different electrolytes as well as the subsequent structural changes in nanoporous gold are also reported. The effect of the annealing process on the application of nanoporous gold as a substrate for glucose electro-oxidation is briefly examined. PMID:25649027

Surface potential measurement of n-type organic semiconductor thin films by mist deposition via Kelvin probe microscopy

NASA Astrophysics Data System (ADS)

Odaka, Akihiro; Satoh, Nobuo; Katori, Shigetaka

2017-08-01

We partially deposited fullerene (C60) and phenyl-C61-butyric acid methyl ester thin films that are typical n-type semiconductor materials on indium-tin oxide by mist deposition at various substrate temperatures. The topographic and surface potential images were observed via dynamic force microscopy/Kelvin probe force microscopy with the frequency modulation detection method. We proved that the area where a thin film is deposited depends on the substrate temperature during deposition from the topographic images. It was also found that the surface potential depends on the substrate temperature from the surface potential images.

Surface modification of TiO2 with metal oxide nanoclusters: a route to composite photocatalytic materials.

PubMed

Nolan, Michael

2011-08-14

Density functional theory simulations show that modifying rutile TiO(2) with metal oxide nanoclusters produces composite materials with potential visible light photocatalytic activity. This journal is © The Royal Society of Chemistry 2011

Nitrous oxide and ammonia emissions from injected and broadcast applied dairy slurry

USDA-ARS?s Scientific Manuscript database

Trade-offs associated with surface application or injection of manure pose important environmental and agronomic concerns. Manure injection can conserve nitrogen (N) by decreasing ammonia volatilization. However, the injection band also creates conditions, which potentially favor nitrous oxide produ...

Island morphology statistics and growth mechanism for oxidation of the Al(111) surface with thermal O2 and NO

NASA Astrophysics Data System (ADS)

Sexton, J. Z.; Kummel, A. C.

2004-10-01

Scanning tunneling microscopy (STM) was employed to study the mechanism for the oxidation of Al(111) with thermal O2 and NO in the 20%-40% monolayer coverage regime. Experiments show that the islands formed upon exposure to thermal O2 and NO have dramatically different shapes, which are ultimately dictated by the dynamics of the gas surface interaction. The circumference-to-area ratio and other island morphology statistics are used to quantify the average difference in the two island types. Ultrahigh-vacuum STM was employed to make the following observations: (1) Oxygen islands on the Al(111) surface, formed upon exposure to thermal oxygen, are elongated and noncompact. (2) Mixed O/N islands on the Al(111) surface, formed upon exposure to thermal nitric oxide (NO), are round and compact. (3) STM movies acquired during thermal O2 exposure indicate that a complex mechanism involving chemisorption initiated rearrangement of preexisting oxygen islands leads to the asymmetric and elongated island shapes. The overall mechanism for the oxidation of the Al(111) surface can be summarized in three regimes. Low coverage is dominated by widely isolated small oxygen features (<3 O atoms) where normal dissociative chemisorption and oxygen abstraction mechanisms are present. At 20%-40% monolayer coverage, additional oxygen chemisorption induces rearrangement of preexisting islands to form free-energy minimum island shapes. At greater than ˜40% monolayer coverage, the apparent surface oxygen coverage asymptotes corresponding to the conversion of the 2D islands to 3D Al2O3 surface crystallites. The rearrangement of oxygen islands on the surface to form the observed islands indicates that there is a short-range oxygen-oxygen attractive potential and a long-range oxygen-oxygen repulsive potential.

Thermal shock induced oxidation of beryllium

NASA Astrophysics Data System (ADS)

Spilker, B.; Linke, J.; Pintsuk, G.; Wirtz, M.

2017-12-01

Beryllium has been chosen as a plasma facing material for the first wall of the experimental fusion reactor ITER, mainly because of its low atomic number and oxygen getter capabilities, which are favorable for a high plasma performance. While the steady state operational temperature of 250 °C has no deteriorating effect on the beryllium surface, transient plasma events can deposit power densities of up to 1 GW m-2 on the beryllium armor tiles. Previous research has shown that the oxidation of beryllium can occur under these thermal shock events. In the present study, S-65 grade beryllium specimens were exposed to 100 thermal shocks with an absorbed power density of 0.6 GW m-2 and a pulse duration of 1 ms, leading to a peak surface temperature of ˜800 °C. The induced surface morphology changes were compared to a steady state heated specimen at the same surface temperature with a holding time of 150 s. As a result, a pitting structure with an average pit diameter of ˜0.45 μm was observed on the thermal shock loaded surface, which was caused by beryllium oxide grain nucleation and subsequent erosion of the weakly bound beryllium oxide particles. In contrast, the steady state heated surface exhibited a more homogeneous beryllium oxide layer featuring small pits with diameters of tens of nm and showed the beryllium oxide grain nucleation in a beginning stage. The experiment demonstrated that thermal shock loading conditions can significantly accelerate the beryllium oxide grain nucleation. The resulting surface morphology change can potentially alter the fusion application relevant erosion, absorption, and retention characteristics of beryllium.

Voltage-sensitive styryl dyes as singlet oxygen targets on the surface of bilayer lipid membrane.

PubMed

Sokolov, V S; Gavrilchik, A N; Kulagina, A O; Meshkov, I N; Pohl, P; Gorbunova, Yu G

2016-08-01

Photosensitizers are widely used as photodynamic therapeutic agents killing cancer cells by photooxidation of their components. Development of new effective photosensitive molecules requires profound knowledge of possible targets for reactive oxygen species, especially for its singlet form. Here we studied photooxidation of voltage-sensitive styryl dyes (di-4-ANEPPS, di-8-ANEPPS, RH-421 and RH-237) by singlet oxygen on the surface of bilayer lipid membranes commonly used as cell membrane models. Oxidation was induced by irradiation of a photosensitizer (aluminum phthalocyanine tetrasulfonate) and monitored by the change of dipole potential on the surface of the membrane. We studied the drop of the dipole potential both in the case when the dye molecules were adsorbed on the same side of the lipid bilayer as the photosensitizer (cis-configuration) and in the case when they were adsorbed on the opposite side (trans-configuration). Based on a simple model, we determined the rate of oxidation of the dyes from the kinetics of change of the potential during and after irradiation. This rate is proportional to steady-state concentration of singlet oxygen in the membrane under irradiation. Comparison of the oxidation rates of various dyes reveals that compounds of ANEPPS series are more sensitive to singlet oxygen than RH type dyes, indicating that naphthalene group is primarily responsible for their oxidation. Copyright © 2016 Elsevier B.V. All rights reserved.

Field-controllable second harmonic generation at a graphene oxide heterointerface

NASA Astrophysics Data System (ADS)

Fernandes, Gustavo E.; Kim, Jin Ho; Osgood, Richard, III; Xu, Jimmy

2018-03-01

We report on the voltage-dependent SHG signal obtained in a reduced-graphene oxide (rGO)/p-type Si heterointerface. A simple qualitative model considering the interaction between the heterointerface depletion region potential and the naturally occurring surface dipole layer on the rGO is introduced to account for the characteristics of the SHG signal, specifically, a minimum point at ≈ -3 V bias on the rGO side of the interface. This feature-rich system has the potential to provide field-controllable surface-dipole moments and second-order nonlinearities, which may find applications in tunable nonlinear photonic devices for realizing second-harmonic generation and optical-rectification.

Effects of the surface mobility on the oxidation of adsorbed CO on platinum electrodes in alkaline media. The role of the adlayer and surface defects.

PubMed

Herrero, Enrique; Chen, Qing-Song; Hernández, Javier; Sun, Shi-Gang; Feliu, Juan M

2011-10-06

The oxidation of adsorbed CO on Pt single crystal electrodes has been studied in alkaline media. The surfaces used in this study were the Pt(111) electrode and vicinal stepped and kinked surfaces with (111) terraces. The kinked surfaces have either (110) steps broken by (100) kinks or (100) steps broken by (110) kinks and different kink densities. The voltammetric profiles for the CO stripping on those electrodes show peaks corresponding to the oxidation of CO on the (111) terraces, on the (100) steps/kinks and on the (110) steps/kinks at very distinctive potentials. Additionally, the stripping voltammograms always present a prewave. The analysis of the results with the different stepped and kinked surfaces indicates that the presence of the prewave is not associated with defects or kinks in the electrode surface. Also, the clear separation of the CO stripping process in different peak contributions indicates that the mobility of CO on the surface is very low. Using partial CO stripping experiments and studies at different pH, it has been proposed that the low mobility is a consequence of the negative absolute potential at which the adlayers are formed in alkaline media. Also, the surface diffusion coefficient for CO in these media has been estimated from the dependence of the stripping charge of the peaks with the scan rate of the voltammetry.

Thrombin-Binding Aptamer Quadruplex Formation: AFM and Voltammetric Characterization

PubMed Central

Diculescu, Victor Constantin; Chiorcea-Paquim, Ana-Maria; Eritja, Ramon; Oliveira-Brett, Ana Maria

2010-01-01

The adsorption and the redox behaviour of thrombin-binding aptamer (TBA) and extended TBA (eTBA) were studied using atomic force microscopy and voltammetry at highly oriented pyrolytic graphite and glassy carbon. The different adsorption patterns and degree of surface coverage were correlated with the sequence base composition, presence/absence of K+, and voltammetric behaviour of TBA and eTBA. In the presence of K+, only a few single-stranded sequences present adsorption, while the majority of the molecules forms stable and rigid quadruplexes with no adsorption. Both TBA and eTBA are oxidized and the only anodic peak corresponds to guanine oxidation. Upon addition of K+ ions, TBA and eTBA fold into a quadruplex, causing the decrease of guanine oxidation peak and occurrence of a new peak at a higher potential due to the oxidation of G-quartets. The higher oxidation potential of G-quartets is due to the greater difficulty of electron transfer from the inside of the quadruplex to the electrode surface than electron transfer from the more flexible single strands. PMID:20798847

Involvement of flocculin in negative potential-applied ITO electrode adhesion of yeast cells

PubMed Central

Koyama, Sumihiro; Tsubouchi, Taishi; Usui, Keiko; Uematsu, Katsuyuki; Tame, Akihiro; Nogi, Yuichi; Ohta, Yukari; Hatada, Yuji; Kato, Chiaki; Miwa, Tetsuya; Toyofuku, Takashi; Nagahama, Takehiko; Konishi, Masaaki; Nagano, Yuriko; Abe, Fumiyoshi

2015-01-01

The purpose of this study was to develop novel methods for attachment and cultivation of specifically positioned single yeast cells on a microelectrode surface with the application of a weak electrical potential. Saccharomyces cerevisiae diploid strains attached to an indium tin oxide/glass (ITO) electrode to which a negative potential between −0.2 and −0.4 V vs. Ag/AgCl was applied, while they did not adhere to a gallium-doped zinc oxide/glass electrode surface. The yeast cells attached to the negative potential-applied ITO electrodes showed normal cell proliferation. We found that the flocculin FLO10 gene-disrupted diploid BY4743 mutant strain (flo10Δ /flo10Δ) almost completely lost the ability to adhere to the negative potential-applied ITO electrode. Our results indicate that the mechanisms of diploid BY4743 S. cerevisiae adhesion involve interaction between the negative potential-applied ITO electrode and the Flo10 protein on the cell wall surface. A combination of micropatterning techniques of living single yeast cell on the ITO electrode and omics technologies holds potential of novel, highly parallelized, microchip-based single-cell analysis that will contribute to new screening concepts and applications. PMID:26187908

Osteogenic potential of in situ TiO2 nanowire surfaces formed by thermal oxidation of titanium alloy substrate

NASA Astrophysics Data System (ADS)

Tan, A. W.; Ismail, R.; Chua, K. H.; Ahmad, R.; Akbar, S. A.; Pingguan-Murphy, B.

2014-11-01

Titanium dioxide (TiO2) nanowire surface structures were fabricated in situ by a thermal oxidation process, and their ability to enhance the osteogenic potential of primary osteoblasts was investigated. Human osteoblasts were isolated from nasal bone and cultured on a TiO2 nanowires coated substrate to assess its in vitro cellular interaction. Bare featureless Ti-6Al-4V substrate was used as a control surface. Initial cell adhesion, cell proliferation, cell differentiation, cell mineralization, and osteogenic related gene expression were examined on the TiO2 nanowire surfaces as compared to the control surfaces after 2 weeks of culturing. Cell adhesion and cell proliferation were assayed by field emission scanning electron microscope (FESEM) and Alamar Blue reduction assay, respectively. The nanowire surfaces promoted better cell adhesion and spreading than the control surface, as well as leading to higher cell proliferation. Our results showed that osteoblasts grown onto the TiO2 nanowire surfaces displayed significantly higher production levels of alkaline phosphatase (ALP), extracellular (ECM) mineralization and genes expression of runt-related transcription factor (Runx2), bone sialoprotein (BSP), ostoepontin (OPN) and osteocalcin (OCN) compared to the control surfaces. This suggests the potential use of such surface modification on Ti-6Al-4V substrates as a promising means to improve the osteointegration of titanium based implants.

Regulation of Methane Oxidation in a Freshwater Wetland by Water Table Changes and Anoxia

NASA Technical Reports Server (NTRS)

Roslev, Peter; King, Gary M.

1996-01-01

The effects of water table fluctuations and anoxia on methane emission and methane oxidation were studied in a freshwater marsh. Seasonal aerobic methane oxidation rates varied between 15% and 76% of the potential diffusive methane flux (diffusive flux in the absence of aerobic oxidation). On an annual basis, approximately 43% of the methane diffusing into the oxic zone was oxidized before reaching the atmosphere. The highest methane oxidation was observed when the water table was below the peat surface. This was confirmed in laboratory experiments where short-term decreases in water table levels increased methane oxidation but also net methane emission. Although methane emission was generally not observed during the winter, stems of soft rush (Juncus effusus) emitted methane when the marsh was ice covered. Indigenous methanotrophic bacteria from the wetiand studied were relatively anoxia tolerant. Surface peat incubated under anoxic conditions maintained 30% of the initial methane oxidation capacity after 32 days of anoxia. Methanotrophs from anoxic peat initiated aerobic methane oxidation relatively quickly after oxygen addition (1-7 hours). These results were supported by culture experiments with the methanotroph Methylosinus trichosporium OB3b. This organism maintained a greater capacity for aerobic methane oxidation when starved under anoxic compared to oxic conditions. Anoxic incubation of M. trichosporium OB3b in the presence of sulfide (2 mM) and a low redox potential (-110 mV) did not decrease the capacity for methane oxidation relative to anoxic cultures incubated without sulfide. The results suggest that aerobic methane oxidation was a major regulator of seasonal methane emission front the investigated wetland. The observed water table fluctuations affected net methane oxidation presumably due to associated changes in oxygen gradients. However, changes from oxic to anoxic conditions in situ had relatively little effect on survival of the methanotrophic bacteria and thus on methane oxidation potential per se.

Environmental and taxonomic bacterial diversity of anaerobic uranium(IV) bio-oxidation.

PubMed

Weber, Karrie A; Thrash, J Cameron; Van Trump, J Ian; Achenbach, Laurie A; Coates, John D

2011-07-01

Microorganisms in diverse terrestrial surface and subsurface environments can anaerobically catalyze the oxidative dissolution of uraninite. While a limited quantity (∼5 to 12 μmol liter(-1)) of uranium is oxidatively dissolved in pure culture studies, the metabolism is coupled to electron transport, providing the potential of uraninite to support indigenous microbial populations and to solubilize uranium.

Electrocatalytic oxidation of cellulose at a gold electrode.

PubMed

Sugano, Yasuhito; Latonen, Rose-Marie; Akieh-Pirkanniemi, Marceline; Bobacka, Johan; Ivaska, Ari

2014-08-01

The electrochemical properties of cellulose dissolved in NaOH solution at a Au surface were investigated by cyclic voltammetry, FTIR spectroscopy, the electrochemical quartz crystal microbalance technique, and electrochemical impedance spectroscopy. The reaction products were characterized by SEM, TEM, and FTIR and NMR spectroscopy. The results imply that cellulose is irreversibly oxidized. Adsorption and desorption of hydroxide ions at the Au surface during potential cycling have an important catalytic role in the reaction (e.g., approach of cellulose to the electrode surface, electron transfer, adsorption/desorption of the reaction species at the electrode surface). Moreover, two types of cellulose derivatives were obtained as products. One is a water-soluble cellulose derivative in which some hydroxyl groups are oxidized to carboxylic groups. The other derivative is a water-insoluble hybrid material composed of cellulose and Au nanoparticles (≈4 nm). Furthermore, a reaction scheme of the electrocatalytic oxidation of cellulose at a gold electrode in a basic medium is proposed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, characterization, applications, and challenges of iron oxide nanoparticles

PubMed Central

Ali, Attarad; Zafar, Hira; Zia, Muhammad; ul Haq, Ihsan; Phull, Abdul Rehman; Ali, Joham Sarfraz; Hussain, Altaf

2016-01-01

Recently, iron oxide nanoparticles (NPs) have attracted much consideration due to their unique properties, such as superparamagnetism, surface-to-volume ratio, greater surface area, and easy separation methodology. Various physical, chemical, and biological methods have been adopted to synthesize magnetic NPs with suitable surface chemistry. This review summarizes the methods for the preparation of iron oxide NPs, size and morphology control, and magnetic properties with recent bioengineering, commercial, and industrial applications. Iron oxides exhibit great potential in the fields of life sciences such as biomedicine, agriculture, and environment. Nontoxic conduct and biocompatible applications of magnetic NPs can be enriched further by special surface coating with organic or inorganic molecules, including surfactants, drugs, proteins, starches, enzymes, antibodies, nucleotides, nonionic detergents, and polyelectrolytes. Magnetic NPs can also be directed to an organ, tissue, or tumor using an external magnetic field for hyperthermic treatment of patients. Keeping in mind the current interest in iron NPs, this review is designed to report recent information from synthesis to characterization, and applications of iron NPs. PMID:27578966

Gamma inert sterilization: a solution to polyethylene oxidation?

PubMed

Medel, Francisco J; Kurtz, Steven M; Hozack, William J; Parvizi, Javad; Purtill, James J; Sharkey, Peter F; MacDonald, Daniel; Kraay, Matthew J; Goldberg, Victor; Rimnac, Clare M

2009-04-01

In the 1990s, oxidation was found to occur in ultra-high molecular weight polyethylene total joint replacement components following gamma irradiation and prolonged shelf aging in air. Orthopaedic manufacturers developed barrier packaging to reduce oxidation during and after radiation sterilization. The present study explores the hypothesis that polyethylene components sterilized in a low-oxygen environment undergo similar in vivo oxidative mechanisms as inserts sterilized in air. In addition, the potential influence of the different sterilization processes on the wear performance of the polyethylene components was examined. An analysis of oxidation, wear, and surface damage was performed for forty-eight acetabular liners and 123 tibial inserts. The mean implantation time was 12.3+/-3.7 years for thirty-one acetabular liners that had been gamma sterilized in air and 4.0+/-2.5 years for the seventeen acetabular liners that had been gamma sterilized in inert gas. The mean implantation time was 11.0+/-3.2 years for the twenty-six tibial inserts that had been sterilized in air and 2.8+/-2.2 years for the ninety-seven tibial inserts that had been gamma sterilized in inert gas. Oxidation and hydroperoxide levels were characterized in loaded and unloaded regions of the inserts. Measurable oxidation and oxidation potential were observed in all cohorts. The oxidation and hydroperoxide levels were regional. Surfaces with access to body fluids were more heavily oxidized than protected bearing surfaces were. This variation appeared to be greater in historical (gamma-in-air-sterilized) components. Regarding wear performance, historical and conventional acetabular liners showed similar wear penetration rates, whereas a low incidence of delamination was confirmed for the conventional tibial inserts in the first decade of implantation. The present study explores the impact of industry-wide changes in sterilization practices for polyethylene. We found lower oxidation and oxidation potential in the conventional acetabular liners and tibial inserts that had been gamma sterilized in inert gas as compared with the historical components that had been gamma sterilized in air. However, we also found strong evidence that conventional components undergo mechanisms of in vivo oxidation similar to those observed following gamma irradiation in air. In addition, gamma sterilization in inert gas did not provide polyethylene with a significant improvement in terms of wear resistance as compared with gamma sterilization in air, except for a lower incidence of delamination in the first decade of implantation for tibial inserts.

Iridium Oxide pH Sensor Based on Stainless Steel Wire for pH Mapping on Metal Surface

NASA Astrophysics Data System (ADS)

Shahrestani, S.; Ismail, M. C.; Kakooei, S.; Beheshti, M.; Zabihiazadboni, M.; Zavareh, M. A.

2018-03-01

A simple technique to fabricate the iridium oxide pH sensor is useful in several applications such as medical, food processing and engineering material where it is able to detect the changes of pH. Generally, the fabrication technique can be classified into three types: electro-deposition iridium oxide film (EIrOF), activated iridium oxide film (AIROF) and sputtering iridium oxide film (SIROF). This study focuses on fabricating electrode, calibration and test. Electro-deposition iridium oxide film is a simple and effective method of fabricating this kind of sensor via cyclic voltammetry process. The iridium oxide thick film was successfully electrodeposited on the surface of stainless steel wire with 500 cycles of sweep potential. A further analysis under FESEM shows detailed image of iridium oxide film which has cauliflower-liked microstructure. EDX analysis shows the highest element present are iridium and oxygen which concluded that the process is successful. The iridium oxide based pH sensor has shown a good performance in comparison to conventional glass pH sensor when it is being calibrated in buffer solutions with 2, 4, 7 and 9 pH values. The iridium oxide pH sensor is specifically designed to measure the pH on the surface of metal plate.

Fabrication of super slippery sheet-layered and porous anodic aluminium oxide surfaces and its anticorrosion property

NASA Astrophysics Data System (ADS)

Song, Tingting; Liu, Qi; Liu, Jingyuan; Yang, Wanlu; Chen, Rongrong; Jing, Xiaoyan; Takahashi, Kazunobu; Wang, Jun

2015-11-01

Inspired by natural plants such as Nepenthes pitcher plants, super slippery surfaces have been developed to improve the attributes of repellent surfaces. In this report, super slippery porous anodic aluminium oxide (AAO) surfaces have fabricated by a simple and reproducible method. Firstly, the aluminium substrates were treated by an anodic process producing micro-nano structured sheet-layered pores, and then immersed in Methyl Silicone Oil, Fluororalkylsilane (FAS) and DuPont Krytox, respectively, generating super slippery surfaces. Such a good material with excellent anti-corrosion property through a simple and repeatable method may be potential candidates for metallic application in anti-corrosion and extreme environment.

Experimental and Computational Evidence of Highly Active Fe Impurity Sites on the Surface of Oxidized Au for the Electrocatalytic Oxidation of Water in Basic Media

DOE PAGES

Klaus, Shannon; Trotochaud, Lena; Cheng, Mu-Jeng; ...

2015-10-22

Addition of Fe to Ni- and Co-based (oxy)hydroxides has been shown to enhance the activity of these materials for electrochemical oxygen evolution. Here we show that Fe cations bound to the surface of oxidized Au exhibit enhanced oxygen evolution reaction (OER) activity. We find that the OER activity increases with increasing surface concentration of Fe. Density functional theory analysis of the OER energetics reveals that oxygen evolution over Fe cations bound to a hydroxyl-terminated oxidized Au (Fe-Au 2O 3) occurs at an overpotential ~0.3V lower than over hydroxylated Au 2O 3 (0.82V). This finding agrees well with experimental observations andmore » is a consequence of the more optimal binding energetics of OER reaction intermediates at Fe cations bound to the surface of Au 2O 3. These findings suggest that the enhanced OER activity reported recently upon low-potential cycling of Au may be due to surface Fe impurities rather than to "superactive" Au(III) surfaquo species.« less

Temporal variation of aerobic methane oxidation over a tidal cycle in a wetland of northern Taiwan.

NASA Astrophysics Data System (ADS)

Lee, T. Y.; Wang, P. L.; Lin, L. H.

2017-12-01

Aerobic methanotrophy plays an important role in controlling methane emitted from wetlands. However, the activity of aerobic methanotrophy regulated by temporal fluctuation of oxygen and methane supply in tidal wetlands is not well known. This study aims to examine the dynamics of methane fluxes and potential aerobic methane consumption rates in a tidal wetland of northern Taiwan, where the variation of environmental characteristics, such as sulfate and methane concentration in pore water has been demonstrated during a tidal cycle. Two field campaigns were carried out in December of 2016 and March of 2017. Fluxes of methane emission, methane concentrations in surface sediments and oxygen profiles were measured at different tidal phases. Besides, batch incubations were conducted on surface sediments in order to quantify potential microbial methane consumption rates and to derive the kinetic parameters for aerobic methanotrophy. Our results demonstrated temporal changes of the surface methane concentration and the methane emission flux during a tidal cycle, while the oxygen flux into the sediment was kept at a similar magnitude. The methane flux was low when the surface was exposed for both shortest and longest periods of time. The potential aerobic methane oxidation rate was high for sample collected from the surface sediments exposed the longest. No correlation could be found between the potential aerobic methane oxidation rate and either the oxygen downward flux or methane emission flux. The decoupled relationships between these observed rates and fluxes suggest that, rather than aerobic methanotrophy, heterotrophic respirations exert a profound control on oxygen flux, and the methane emission is not only been affected by methane consumption but also methane production at depths. The maximum potential rate and the half saturation concentration determined from the batch incubations were high for the surface sediments collected in low tide, suggesting that aerobic methanotrophy could be modulated to reach peak activity once the influence of saline water is reduced to a low level.

Modeling uranium(VI) adsorption onto montmorillonite under varying carbonate concentrations: A surface complexation model accounting for the spillover effect on surface potential

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tournassat, C.; Tinnacher, R. M.; Grangeon, S.

The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonitemore » edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites (‘spillover’ effect).« less

Modeling uranium(VI) adsorption onto montmorillonite under varying carbonate concentrations: A surface complexation model accounting for the spillover effect on surface potential

DOE PAGES

Tournassat, C.; Tinnacher, R. M.; Grangeon, S.; ...

2017-10-06

The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonitemore » edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites (‘spillover’ effect).« less

A multiphase interfacial model for the dissolution of spent nuclear fuel

NASA Astrophysics Data System (ADS)

Jerden, James L.; Frey, Kurt; Ebert, William

2015-07-01

The Fuel Matrix Dissolution Model (FMDM) is an electrochemical reaction/diffusion model for the dissolution of spent uranium oxide fuel. The model was developed to provide radionuclide source terms for use in performance assessment calculations for various types of geologic repositories. It is based on mixed potential theory and consists of a two-phase fuel surface made up of UO2 and a noble metal bearing fission product phase in contact with groundwater. The corrosion potential at the surface of the dissolving fuel is calculated by balancing cathodic and anodic reactions occurring at the solution interfaces with UO2 and NMP surfaces. Dissolved oxygen and hydrogen peroxide generated by radiolysis of the groundwater are the major oxidizing agents that promote fuel dissolution. Several reactions occurring on noble metal alloy surfaces are electrically coupled to the UO2 and can catalyze or inhibit oxidative dissolution of the fuel. The most important of these is the oxidation of hydrogen, which counteracts the effects of oxidants (primarily H2O2 and O2). Inclusion of this reaction greatly decreases the oxidation of U(IV) and slows fuel dissolution significantly. In addition to radiolytic hydrogen, large quantities of hydrogen can be produced by the anoxic corrosion of steel structures within and near the fuel waste package. The model accurately predicts key experimental trends seen in literature data, the most important being the dramatic depression of the fuel dissolution rate by the presence of dissolved hydrogen at even relatively low concentrations (e.g., less than 1 mM). This hydrogen effect counteracts oxidation reactions and can limit fuel degradation to chemical dissolution, which results in radionuclide source term values that are four or five orders of magnitude lower than when oxidative dissolution processes are operative. This paper presents the scientific basis of the model, the approach for modeling used fuel in a disposal system, and preliminary calculations to demonstrate the application and value of the model.

Immobilization of natural anti-oxidants on carbon nanotubes and aging behavior of ultra-high molecular weight polyethylene-based nanocomposites

NASA Astrophysics Data System (ADS)

Dintcheva, Nadka Tzankova; Arrigo, Rossella; Gambarotti, Cristian; Guenzi, Monica; Carroccio, Sabrina; Cicogna, Francesca; Filippone, Giovanni

2014-05-01

The use of natural antioxidants is an attractive way to formulate nanocomposites with extended durability and with potential applications in bio-medical field. In this work, Vitamin E (VE) in the form of α-tocopherol and Quercetin (Q) are physically immobilized on the outer surface of multi-walled carbon nanotubes (CNTs). Afterward, the CNTs-VE and CNTs-Q are used to formulate thermally stable ultra high molecular weight polyethylene based nanocomposites. The obtained results in the study of the thermo-oxidation behavior suggest a beneficial effect of the natural anti-oxidant carbon nanotubes systems. The unexpected excellent thermo-resistance of the nanocomposites seems to be due to a synergistic effect of the natural anti-oxidant and carbon nanotubes, i.e. strong interaction between CNT surface and anti-oxidant molecules. Particularly, these interactions cause the formation of structural defects onto outer CNT surfaces, which, in turn, increase the CNT radical scavenging activity.

Role of Electrical Double Layer Structure in Ionic Liquid Gated Devices.

PubMed

Black, Jennifer M; Come, Jeremy; Bi, Sheng; Zhu, Mengyang; Zhao, Wei; Wong, Anthony T; Noh, Joo Hyon; Pudasaini, Pushpa R; Zhang, Pengfei; Okatan, Mahmut Baris; Dai, Sheng; Kalinin, Sergei V; Rack, Philip D; Ward, Thomas Zac; Feng, Guang; Balke, Nina

2017-11-22

Ionic liquid gating of transition metal oxides has enabled new states (magnetic, electronic, metal-insulator), providing fundamental insights into the physics of strongly correlated oxides. However, despite much research activity, little is known about the correlation of the structure of the liquids in contact with the transition metal oxide surface, its evolution with the applied electric potential, and its correlation with the measured electronic properties of the oxide. Here, we investigate the structure of an ionic liquid at a semiconducting oxide interface during the operation of a thin film transistor where the electrical double layer gates the device using experiment and theory. We show that the transition between the ON and OFF states of the amorphous indium gallium zinc oxide transistor is accompanied by a densification and preferential spatial orientation of counterions at the oxide channel surface. This process occurs in three distinct steps, corresponding to ion orientations, and consequently, regimes of different electrical conductivity. The reason for this can be found in the surface charge densities on the oxide surface when different ion arrangements are present. Overall, the field-effect gating process is elucidated in terms of the interfacial ionic liquid structure, and this provides unprecedented insight into the working of a liquid gated transistor linking the nanoscopic structure to the functional properties. This knowledge will enable both new ionic liquid design as well as advanced device concepts.

Role of Electrical Double Layer Structure in Ionic Liquid Gated Devices

DOE PAGES

Black, Jennifer M.; Come, Jeremy; Bi, Sheng; ...

2017-10-24

Ionic liquid gating of transition metal oxides has enabled new states (magnetic, electronic, metal–insulator), providing fundamental insights into the physics of strongly correlated oxides. However, despite much research activity, little is known about the correlation of the structure of the liquids in contact with the transition metal oxide surface, its evolution with the applied electric potential, and its correlation with the measured electronic properties of the oxide. Here, we investigate the structure of an ionic liquid at a semiconducting oxide interface during the operation of a thin film transistor where the electrical double layer gates the device using experiment andmore » theory. We show that the transition between the ON and OFF states of the amorphous indium gallium zinc oxide transistor is accompanied by a densification and preferential spatial orientation of counterions at the oxide channel surface. This process occurs in three distinct steps, corresponding to ion orientations, and consequently, regimes of different electrical conductivity. The reason for this can be found in the surface charge densities on the oxide surface when different ion arrangements are present. Overall, the field-effect gating process is elucidated in terms of the interfacial ionic liquid structure, and this provides unprecedented insight into the working of a liquid gated transistor linking the nanoscopic structure to the functional properties. This knowledge will enable both new ionic liquid design as well as advanced device concepts.« less

Role of Electrical Double Layer Structure in Ionic Liquid Gated Devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Black, Jennifer M.; Come, Jeremy; Bi, Sheng

Ionic liquid gating of transition metal oxides has enabled new states (magnetic, electronic, metal–insulator), providing fundamental insights into the physics of strongly correlated oxides. However, despite much research activity, little is known about the correlation of the structure of the liquids in contact with the transition metal oxide surface, its evolution with the applied electric potential, and its correlation with the measured electronic properties of the oxide. Here, we investigate the structure of an ionic liquid at a semiconducting oxide interface during the operation of a thin film transistor where the electrical double layer gates the device using experiment andmore » theory. We show that the transition between the ON and OFF states of the amorphous indium gallium zinc oxide transistor is accompanied by a densification and preferential spatial orientation of counterions at the oxide channel surface. This process occurs in three distinct steps, corresponding to ion orientations, and consequently, regimes of different electrical conductivity. The reason for this can be found in the surface charge densities on the oxide surface when different ion arrangements are present. Overall, the field-effect gating process is elucidated in terms of the interfacial ionic liquid structure, and this provides unprecedented insight into the working of a liquid gated transistor linking the nanoscopic structure to the functional properties. This knowledge will enable both new ionic liquid design as well as advanced device concepts.« less

Model for thickness dependence of radiation charging in MOS structures

NASA Technical Reports Server (NTRS)

Viswanathan, C. R.; Maserjian, J.

1976-01-01

The model considers charge buildup in MOS structures due to hole trapping in the oxide and the creation of sheet charge at the silicon interface. The contribution of hole trapping causes the flatband voltage to increase with thickness in a manner in which square and cube dependences are limiting cases. Experimental measurements on samples covering a 200 - 1000 A range of oxide thickness are consistent with the model, using independently obtained values of hole-trapping parameters. An important finding of our experimental results is that a negative interface charge contribution due to surface states created during irradiation compensates most of the positive charge in the oxide at flatband. The tendency of the surface states to 'track' the positive charge buildup in the oxide, for all thicknesses, applies both in creation during irradiation and in annihilation during annealing. An explanation is proposed based on the common defect origin of hole traps and potential surface states.

Meeting in New Orleans: An Assessment of the Fate of Metal Oxide Nanomaterials in Porous Media

EPA Science Inventory

This work assesses potential aqueous environmental metal oxide nanomaterial self-aggregation through the application of recent developments in surface complexation theory with historical DLVO procedures. Findings include: 1) nanomaterials with a Hamaker constant as large as 1E-1...

Enhanced oxidation of arsenite to arsenate using tunable K+ concentration in the OMS-2 tunnel.

PubMed

Hou, Jingtao; Sha, Zhenjie; Hartley, William; Tan, Wenfeng; Wang, Mingxia; Xiong, Juan; Li, Yuanzhi; Ke, Yujie; Long, Yi; Xue, Shengguo

2018-07-01

Cryptomelane-type octahedral molecular sieve manganese oxide (OMS-2) possesses high redox potential and has attracted much interest in its application for oxidation arsenite (As(III)) species of arsenic to arsenate (As(V)) to decrease arsenic toxicity and promote total arsenic removal. However, coexisting ions such as As(V) and phosphate are ubiquitous and readily bond to manganese oxide surface, consequently passivating surface active sites of manganese oxide and reducing As(III) oxidation. In this study, we present a novel strategy to significantly promote As(III) oxidation activity of OMS-2 by tuning K + concentration in the tunnel. Batch experimental results reveal that increasing K + concentration in the tunnel of OMS-2 not only considerably improved As(III) oxidation kinetics rate from 0.027 to 0.102 min -1 , but also reduced adverse effect of competitive ion on As(III) oxidation. The origin of K + concentration effect on As(III) oxidation was investigated through As(V) and phosphate adsorption kinetics, detection of Mn 2+ release in solution, surface charge characteristics, and density functional theory (DFT) calculations. Experimental results and theoretical calculations confirm that by increasing K + concentration in the OMS-2 tunnel not only does it improve arsenic adsorption on K + doped OMS-2, but also accelerates two electrons transfers from As(III) to each bonded Mn atom on OMS-2 surface, thus considerably improving As(III) oxidation kinetics rate, which is responsible for counteracting the adverse adsorption effects by coexisting ions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Kaolinite-catalyzed air oxidation of hydrazine: Consideration of several compositional, structural and energetic factors in surface activation

NASA Technical Reports Server (NTRS)

Coyne, L. M.; Mariner, R.; Rice, A.

1991-01-01

Clay minerals have been shown to have numerous, curious, energetic properties by virtue of ultra-violet light release which can be triggered by gentle environmental changes such as wetting and dewetting by a variety of liquids, unique among them water and hydrazine. Since both water and hydrazine play multiple key roles in the air-oxidation of hydrazine on kaolinite surfaces, this reaction would seem to have prime potential for studying interrelationships of energy storage, release and chemical reactivity of clay surfaces, capacities basic to either the Bernal or Cairns-Smith roles of minerals in the origin of life. Establishment of the capacity for stored electronic energy to significantly alter surface chemistry is important, regardless of the reaction chosen to demonstrate it. Hydrazine air oxidation is overawingly complex, given the possibilities for step-wise control and monitoring of parameters. In the light of recently extended characterization of the kaolinite and model sheet catalysts we used to study hydrazine oxidation and gamma-irradiated silica, previous studies of hydrazine air-oxidation on aluminosilicate surfaces have been reevaluated. Our former conclusion remains intact that, whereas trace structural and surface contaminants do play some role in the catalysis of oxidation, they are not the only, nor even the dominant, catalytic centers. Initial intermediates in the oxidation can now be proposed which are consistent with production via O(-)-centers as well as ferric iron centers. The greater than square dependence of the initial reaction rate on the weight of the clay is discussed in the light of these various mechanistic possibilities.

Atomic Oxygen Durability of Second Surface Silver Microsheet Glass Concentrators

NASA Technical Reports Server (NTRS)

deGroh, Kim K.; Jaworske, Donald A.; Smith, Daniela C.; Mroz, Thaddeus S.

1996-01-01

Second surface silver microsheet glass concentrators are being developed for potential use in future solar dynamic space power systems. Traditional concentrators are aluminum honeycomb sandwich composites with either aluminum or graphite epoxy face sheets, where a reflective aluminum layer is deposited onto an organic leveling layer on the face sheet. To protect the underlying layers, a SiO2 layer is applied on top of the aluminum reflective layer. These concentrators may be vulnerable to atomic oxygen degradation due to possible atomic oxygen attack of the organic layers at defect sites in the protective and reflective coatings. A second surface microsheet glass concentrator would be inherently more atomic oxygen durable than these first surface concentrators. In addition, a second surface microsheet glass concentrator design provides a smooth optical surface and allows for silver to be used as a reflective layer, which would improve the reflectivity of the concentrator and the performance of the system. A potential threat to the performance of second surface microsheet glass concentrators is atomic oxygen attack of the underlying silver at seams and edges or at micrometeoroid and debris (MMD) impacts sites. Second surface silver microsheet glass concentrator samples were fabricated and tested for atomic oxygen durability. The samples were iteratively exposed to an atomic oxygen environment in a plasma asher. Samples were evaluated for potential degradation at fabrication seams, simulated MMD impact sites, and edges. Optical microscopy was used to evaluate atomic oxygen degradation. Reflectance was obtained for an impacted sample prior to and after atomic oxygen exposure. After an initial atomic oxygen exposure to an effective fluence of approx. 1 x 10(exp 21) atoms/cm(exp 2), oxidation of the silver at defect sites and edges was observed. Exposure to an additional approx. 1 x 10(exp 21) atoms/cm(exp 2) caused no observed increase in oxidation. Oxidation at an impact site caused negligible changes in reflectance. In all cases oxidation was found to be confined to the vicinity of the seams, impact sites, edges or defect sites. Asher to in-space atomic oxygen correlation issues will be addressed.

Surface characterization of anodized zirconium for biomedical applications

NASA Astrophysics Data System (ADS)

Sanchez, A. Gomez; Schreiner, W.; Duffó, G.; Ceré, S.

2011-05-01

Mechanical properties and corrosion resistance of zirconium make this material suitable for biomedical implants. Its good in vivo performance is mainly due to the presence of a protective oxide layer that minimizes corrosion rate, diminishes the amount of metallic ions released to the biological media and facilitates the osseointegration process. Since the implant surface is the region in contact with living tissues, the characteristics of the surface film are of great interest. Surface modification is a route to enhance both biocompatibility and corrosion resistance of permanent implant materials. Anodizing is presented as an interesting process to modify metal surfaces with good reproducibility and independence of the geometry. In this work the surface of zirconium before and after anodizing in 1 mol/L phosphoric acid solution at a fixed potential between 3 and 30 V, was characterized by means of several surface techniques. It was found that during anodization the surface oxide grows with an inhomogeneous coverage on zirconium surface, modifying the topography. The incorporation of P from the electrolyte to the surface oxide during the anodizing process changes the surface chemistry. After 30 days of immersion in Simulated Body Fluid (SBF) solution, Ca-P rich compounds were present on anodized zirconium.

Efficient oxidation and sorption of arsenite using a novel titanium(IV)-manganese(IV) binary oxide sorbent.

PubMed

Zhang, Wei; Liu, Caihong; Zheng, Tong; Ma, Jun; Zhang, Gaosheng; Ren, Guohui; Wang, Lu; Liu, Yulei

2018-04-19

Owing to the high toxicity and mobility, the removal of arsenite (As(III)) is significantly more difficult than arsenate (As(V)), thus representing a major challenge in arsenite-contaminated water treatment. For efficient elimination of As(III), we successfully fabricated a novel Ti-Mn binary oxide via a simultaneous oxidation and coprecipitation process. The amorphous oxide was aggregated from nanosized particles with a high specific surface area of 349.5 m 2 /g. It could effectively oxidize As(III) to As(V) and had a high As(III) sorption capacity of 107.0 mg/g. As(III) sorption occurred rapidly and equilibrium was achieved within 24 h. The kinetic data was well fitted by the pseudo-second-order equation, indicating a chemical sorption process. The material was almost independent upon the presence of competitive ions. The As(III) removal by the sorbent is a combined process coupled oxidation with sorption, where the MnO 2 content is mainly responsible for oxidizing As(III) to As(V) and the formed As(V) is then adsorbed onto the surface of amorphous TiO 2 content, through replacing the surface hydroxyl group or the adsorbed As(III) and forming inner-sphere surface complexes. Furthermore, the arsenic-containing oxide could be effectively regenerated and reused. The bi-functional sorbent could be used as a potentially attractive sorbent for As(III) removal in drinking water treatment and environmental remediation. Copyright © 2018. Published by Elsevier B.V.

Oxidation and emittance of superalloys in heat shield applications

NASA Technical Reports Server (NTRS)

Wiedemann, K. E.; Clark, R. K.; Unnam, J.

1986-01-01

Recently developed superalloys that form alumina coatings have a high potential for heat shield applications for advanced aerospace vehicles at temperatures above 1095C. Both INCOLOY alloy MA 956 (of the Inco Alloys International, Inc.), an iron-base oxide-dispersion-strengthened alloy, and CABOT alloy No. 214 (of the Cabot Corporation), an alumina-forming nickel-chromium alloy, have good oxidation resistance and good elevated temperature strength. The oxidation resistance of both alloys has been attributed to the formation of a thin alumina layer (alpha-Al2O3) at the surface. Emittance and oxidation data were obtained for simulated Space Shuttle reentry conditions using a hypersonic arc-heated wind tunnel. The surface oxides and substrate alloys were characterized using X-ray diffraction and scanning and transmission electron microscopy with an energy-dispersive X-ray analysis unit. The mass loss and emittance characteristics of the two alloys are discussed.

Molybdenum, molybdenum oxides, and their electrochemistry.

PubMed

Saji, Viswanathan S; Lee, Chi-Woo

2012-07-01

The electrochemical behaviors of molybdenum and its oxides, both in bulk and thin film dimensions, are critical because of their widespread applications in steels, electrocatalysts, electrochromic materials, batteries, sensors, and solar cells. An important area of current interest is electrodeposited CIGS-based solar cells where a molybdenum/glass electrode forms the back contact. Surprisingly, the basic electrochemistry of molybdenum and its oxides has not been reviewed with due attention. In this Review, we assess the scattered information. The potential and pH dependent active, passive, and transpassive behaviors of molybdenum in aqueous media are explained. The major surface oxide species observed, reversible redox transitions of the surface oxides, pseudocapacitance and catalytic reduction are discussed along with carefully conducted experimental results on a typical molybdenum glass back contact employed in CIGS-based solar cells. The applications of molybdenum oxides and the electrodeposition of molybdenum are briefly reviewed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Perchlorate Formation on Mars Through Surface Radiolysis-Initiated Atmospheric Chemistry: A Potential Mechanism

NASA Technical Reports Server (NTRS)

Wilson, Eric H.; Atreya, Sushil K.; Kaiser, Ralf I.; Mahaffy, Paul R.

2016-01-01

Recent observations of the Martian surface by the Phoenix lander and the Sample Analysis at Mars indicate the presence of perchlorate (ClO4). The abundance and isotopic composition of these perchlorates suggest that the mechanisms responsible for their formation in the Martian environment may be unique in our solar system. With this in mind, we propose a potential mechanism for the production of Martian perchlorate: the radiolysis of the Martian surface by galactic cosmic rays, followed by the sublimation of chlorine oxides into the atmosphere and their subsequent synthesis to form perchloric acid (HClO4) in the atmosphere, and the surface deposition and subsequent mineralization of HClO4 in the regolith to form surface perchlorates. To evaluate the viability of this mechanism, we employ a one-dimensional chemical model, examining chlorine chemistry in the context of Martian atmospheric chemistry. Considering the chlorine oxide, OClO, we find that an OClO flux as low as 3.2 x 10(exp 7) molecules/sq cm/s sublimated into the atmosphere from the surface could produce sufficient HClO4 to explain the perchlorate concentration on Mars, assuming an accumulation depth of 30 cm and integrated over the Amazonian period. Radiolysis provides an efficient pathway for the oxidation of chlorine, bypassing the efficient Cl/HCl recycling mechanism that characterizes HClO4 formation mechanisms proposed for the Earth but not Mars.

Reactions of singlet oxygen with pine pollen.

NASA Technical Reports Server (NTRS)

Dowty, B.; Laseter, J. L.; Griffin, G. W.; Politzer, I. R.; Walkinshaw, C. H.

1973-01-01

A study was initiated to determine whether viable atmospheric particles such as plant pollens and fungal spores containing unsaturated lipids can interact with singlet oxygen to give oxygenated products that are potentially toxic. The results obtained confirm that surface and near surface components of common viable particulate matter in the atmosphere may be subject to rapid oxidation by singlet oxygen, leading to products which are probably allylic hydroperoxides. In connection with increasing atmospheric pollution, it is important to note that materials toxic to mammalian lung tissue may be oxidatively produced on the surfaces of viable particulate matter.

Methanol electro-oxidation on platinum modified tungsten carbides in direct methanol fuel cells: a DFT study.

PubMed

Sheng, Tian; Lin, Xiao; Chen, Zhao-Yang; Hu, P; Sun, Shi-Gang; Chu, You-Qun; Ma, Chun-An; Lin, Wen-Feng

2015-10-14

In exploration of low-cost electrocatalysts for direct methanol fuel cells (DMFCs), Pt modified tungsten carbide (WC) materials are found to be great potential candidates for decreasing Pt usage whilst exhibiting satisfactory reactivity. In this work, the mechanisms, onset potentials and activity for electrooxidation of methanol were studied on a series of Pt-modified WC catalysts where the bare W-terminated WC(0001) substrate was employed. In the surface energy calculations of a series of Pt-modified WC models, we found that the feasible structures are mono- and bi-layer Pt-modified WCs. The tri-layer Pt-modified WC model is not thermodynamically stable where the top layer Pt atoms tend to accumulate and form particles or clusters rather than being dispersed as a layer. We further calculated the mechanisms of methanol oxidation on the feasible models via methanol dehydrogenation to CO involving C-H and O-H bonds dissociating subsequently, and further CO oxidation with the C-O bond association. The onset potentials for the oxidation reactions over the Pt-modified WC catalysts were determined thermodynamically by water dissociation to surface OH* species. The activities of these Pt-modified WC catalysts were estimated from the calculated kinetic data. It has been found that the bi-layer Pt-modified WC catalysts may provide a good reactivity and an onset oxidation potential comparable to pure Pt and serve as promising electrocatalysts for DMFCs with a significant decrease in Pt usage.

Benzene oxidation at diamond electrodes: comparison of microcrystalline and nanocrystalline diamonds.

PubMed

Pleskov, Yu V; Krotova, M D; Elkin, V V; Varnin, V P; Teremetskaya, I G; Saveliev, A V; Ralchenko, V G

2012-08-27

A comparative study of benzene oxidation at boron-doped diamond (BDD) and nitrogenated nanocrystalline diamond (NCD) anodes in 0.5 M K(2)SO(4) aqueous solution is conducted by using cyclic voltammetry and electrochemical impedance spectroscopy. It is shown by measurements of differential capacitance and anodic current that during the benzene oxidation at the BDD electrode, adsorption of a reaction intermediate occurs, which partially blocks the electrode surface and lowers the anodic current. At the NCD electrode, benzene is oxidized concurrently with oxygen evolution, a (quinoid) intermediate being adsorbed at the electrode. The adsorption and the electrode surface blocking are reflected in the impedance-frequency and impedance-potential complex-plane plots. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanism of photocatalytic water oxidation on small TiO 2 nanoparticles

DOE PAGES

Muuronen, Mikko; Parker, Shane M.; Berardo, Enrico; ...

2016-12-07

Here, we present the first unconstrained nonadiabatic molecular dynamics (NAMD) simulations of photocatalytic water oxidation by small hydrated TiO 2 nanoparticles using Tully surface hopping and time-dependent density functional theory. The results indicate that ultrafast electron–proton transfer from physisorbed water to the photohole initiates the photo-oxidation on the S 1 potential energy surface. The new mechanism readily explains the observation of mobile hydroxyl radicals in recent experiments. Two key driving forces for the photo-oxidation reaction are identified: localization of the electron–hole pair and stabilization of the photohole by hydrogen bonding interaction. Our findings illustrate the scope of recent advances inmore » NAMD methods and emphasize the importance of explicit simulation of electronic excitations.« less

In Situ Analyses of Methane Oxidation Associated with the Roots and Rhizomes of a Bur Reed, Sparganium Eurycarpum, in a Maine Wetland

NASA Technical Reports Server (NTRS)

King, Gary M.

1996-01-01

Methane oxidation associated with the belowground tissues of a common aquatic macrophyte, the burweed Sparganium euryearpum, was assayed in situ by a chamber technique with acetylene or methyl fluoride as a methanotrophic inhibitor at a headspace concentration of 3 to 4%. Acetylene and methyl fluoride inhibited both methane oxidation and peat methanogenesis. However, inhibition of methanogenesis resulted in no obvious short-term effect on methane fluxes. Since neither inhibitor adversely affected plant metabolism and both inhibited methanotrophy equally well, acetylene was employed for routine assays because of its low cost and ease of use. Root-associated methanotrophy consumed a variable but significant fraction of the total potential methane flux; values varied between 1 and 58% (mean +/- standard deviation, 27.0% +/- 6.0%), with no consistent temporal or spatial pattern during late summer. The absolute amount of methane oxidized was not correlated with the total potential methane flux; this suggested that parameters other than methane availability (e.g., oxygen availability) controlled the rates of methane oxidation. Estimates of diffusive methane flux and oxidation at the peat surface indicated that methane emission occurred primarily through aboveground plant tissues; the absolute magnitude of methane oxidation was also greater in association with roots than at the peat surface. However, the relative extent of oxidation was greater at the latter locus.

LiNbO3 surfaces from a microscopic perspective

NASA Astrophysics Data System (ADS)

Sanna, Simone; Gero Schmidt, Wolf

2017-10-01

A large number of oxides has been investigated in the last twenty years as possible new materials for various applications ranging from opto-electronics to heterogeneous catalysis. In this context, ferroelectric oxides are particularly promising. The electric polarization plays a crucial role at many oxide surfaces, and it largely determines their physical and chemical properties. Ferroelectrics offer in addition the possibility to control/switch the electric polarization and hence the surface chemistry, allowing for the realization of domain-engineered nanoscale devices such as molecular detectors or highly efficient catalysts. Lithium niobate (LiNbO3) is a ferroelectric with a high spontaneous polarization, whose surfaces have a huge and largely unexplored potential. Owing to recent advances in experimental techniques and sample preparation, peculiar and exclusive properties of LiNbO3 surfaces could be demonstrated. For example, water films freeze at different temperatures on differently polarized surfaces, and the chemical etching properties of surfaces with opposite polarization are strongly different. More important, the ferroelectric domain orientation affects temperature dependent surface stabilization mechanisms and molecular adsorption phenomena. Various ab initio theoretical investigations have been performed in order to understand the outcome of these experiments and the origin of the exotic behavior of the lithium niobate surfaces. Thanks to these studies, many aspects of their surface physics and chemistry could be clarified. Yet other puzzling features are still not understood. This review gives a résumé on the present knowledge of lithium niobate surfaces, with a particular view on their microscopic properties, explored in recent years by means of ab initio calculations. Relevant aspects and properties of the surfaces that need further investigation are briefly discussed. The review is concluded with an outlook of challenges and potential payoff for LiNbO3 based applications.

Nitrous Oxide Emissions from Riparian Forest Buffers, Warm-Season and Cool-Season Grass Filters, and Crop Fields

USDA-ARS?s Scientific Manuscript database

Increasing denitrification rates in riparian buffers may be trading the problem of nonpoint source (NPS) pollution of surface waters for atmospheric deterioration and increased global warming potential because denitrification produces nitrous oxide (N2O), a greenhouse gas also involved in stratosphe...

Evaluation of factors affecting nitrous oxide emission and N transformation in a sandy loam soil

USDA-ARS?s Scientific Manuscript database

A better understanding of the complex factors affecting nitrous oxide (N2O) emission and potential mitigation practices will assist in developing strategies to improve the sustainability of agricultural production systems. Using surface soil collected from a pomegranate orchard, a series of laborato...

Oxidation Of Manganese At Kimberley, Gale Crater: More Free Oxygen In Mars' Past?

NASA Technical Reports Server (NTRS)

Lanza, N. L.; Wiens, R. C.; Arvidson, R. E.; Clark, B. C.; Fischer, W. W.; Gellert, R.; Grotzinger, J. P.; Hurowitz, J. A.; McLennan, S. M.; Morris, R. V.;

Oxidative stress during extracorporeal circulation.

PubMed

McDonald, Charles Ian; Fraser, John Francis; Coombes, Jeff S; Fung, Yoke Lin

2014-12-01

There is an increased oxidative stress response in patients having cardiac surgery, haemodialysis or extracorporeal membrane oxygenation that is related to poorer outcomes and increased mortality. Exposure of the patients' blood to the artificial surfaces of these extracorporeal devices, coupled with inflammatory responses, hyperoxia and the pathophysiological aspects of the underlying illness itself, all contribute to this oxidative stress response. Oxidative stress occurs when there is a disruption of redox signalling and loss of control of redox balance. Ongoing oxidative stress occurring during extracorporeal circulation (ECC) results in damage to lipids, proteins and DNA and contributes to morbidity and mortality. This review discusses reactive species generation and the potential clinical consequences of oxidative stress during ECC as well as provides an overview of some current antioxidant compounds that are available to potentially mitigate the oxidative stress response. © The Author 2014. Published by Oxford University Press on behalf of the European Association for Cardio-Thoracic Surgery. All rights reserved.

Atomically precise lateral modulation of a two-dimensional electron liquid in anatase TiO 2 thin films

DOE PAGES

Wang, Zhiming; Zhong, Z.; Walker, S. McKeown; ...

2017-03-10

Engineering the electronic band structure of two-dimensional electron liquids (2DELs) confined at the surface or interface of transition metal oxides is key to unlocking their full potential. Here we describe a new approach to tailoring the electronic structure of an oxide surface 2DEL demonstrating the lateral modulation of electronic states with atomic scale precision on an unprecedented length scale comparable to the Fermi wavelength. To this end, we use pulsed laser deposition to grow anatase TiO 2 films terminated by a (1 x 4) in-plane surface reconstruction. Employing photo-stimulated chemical surface doping we induce 2DELs with tunable carrier densities thatmore » are confined within a few TiO 2 layers below the surface. Subsequent in situ angle resolved photoemission experiments demonstrate that the (1 x 4) surface reconstruction provides a periodic lateral perturbation of the electron liquid. Furthermore, this causes strong backfolding of the electronic bands, opening of unidirectional gaps and a saddle point singularity in the density of states near the chemical potential.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Yong; Axnanda, Stephanus; Crumlin, Ethan J.

Some rcent advances of ambient pressure X-ray photoelectron spectroscopy (AP-XPS) have enabled the chemical composition and the electrical potential profile at a liquid/electrode interface under electrochemical reaction conditions to be directly probed. In this work, we apply this operando technique to study the surface chemical composition evolution on a Co metal electrode in 0.1 M KOH aqueous solution under various electrical biases. It is found that an ~12.2 nm-thick layer of Co(OH) 2 forms at a potential of about -0.4 V Ag/AgCl, and upon increasing the anodic potential to about +0.4 V Ag/AgCl, this layer is partially oxidized into cobaltmore » oxyhydroxide (CoOOH). A CoOOH/Co(OH) 2 mixture layer is formed on the top of the electrode surface. Finally, the oxidized surface layer can be reduced to Co0 at a cathodic potential of -1.35 VAg/Cl. Our observations indicate that the ultrathin layer containing cobalt oxyhydroxide is the active phase for oxygen evolution reaction (OER) on a Co electrode in an alkaline electrolyte, consistent with previous studies.« less

Surface electronic properties of polycrystalline bulk and thin film In2O3(ZnO)k compounds

NASA Astrophysics Data System (ADS)

Hopper, E. Mitchell; Zhu, Qimin; Gassmann, Jürgen; Klein, Andreas; Mason, Thomas O.

2013-01-01

The surface electronic potentials of In2O3(ZnO)k compounds were measured by X-ray and ultraviolet photoelectron spectroscopy. Both thin film (k = 2) and bulk specimens (k = 3, 5, 7, 9) were studied. All bulk specimens exhibited In enrichment at the surface. All samples showed an increase of In core level binding energies compared to pure and Sn-doped In2O3. The work functions and Fermi levels spanned a range similar to those of the basis oxides In2O3 and ZnO, and the ionization potential was similar to that of both In2O3 and ZnO processed under similar conditions (7.7 eV). This ionization potential was independent of both composition and post-deposition oxidation and reduction treatments. Kelvin probe measurements of cleaned and UV-ozone treated specimens under ambient conditions were in agreement with the photoelectron spectroscopy measurements.

Unraveling the Nature of Active Sites in Ethanol Electro-oxidation by Site-Specific Marking of a Pt Catalyst with Isotope-Labeled 13CO.

PubMed

Farias, Manuel J S; Cheuquepán, William; Tanaka, Auro A; Feliu, Juan M

2018-03-15

This works deals with the identification of preferential site-specific activation at a model Pt surface during a multiproduct reaction. The (110)-type steps of a Pt(332) surface were selectively marked by attaching isotope-labeled 13 CO molecules to them, and ethanol oxidation was probed by in situ Foureir transfrom infrared spectroscopy in order to precisely determine the specific sites at which CO 2 , acetic acid, and acetaldehyde were preferentially formed. The (110) steps were active for splitting the C-C bond, but unexpectedly, we provide evidence that the pathway of CO 2 formation was preferentially activated at (111) terraces, rather than at (110) steps. Acetaldehyde was formed at (111) terraces at potentials comparable to those for CO 2 formation also at (111) terraces, while the acetic acid formation pathway became active only when the (110) steps were released by the oxidation of adsorbed 13 CO, at potentials higher than for the formation of CO 2 at (111) terraces of the stepped surface.

Chemically Layered Porous Solids

NASA Technical Reports Server (NTRS)

Koontz, Steve

1991-01-01

Aerogels and other porous solids in which surfaces of pores have chemical properties varying with depth below macroscopic surfaces prepared by sequences of chemical treatments. Porous glass or silica bead treated to make two depth zones having different chemical properties. Beads dropped along tube filled with flowing gas containing atomic oxygen, generated in microwave discharge. General class of materials treatable include oxides of aluminum, silicon, zirconium, tin, titanium, and nickel, and mixtures of these oxides. Potential uses of treated materials include chromatographic separations, membrane separations, controlled releases of chemicals, and catalysis.

Iron oxide surfaces

NASA Astrophysics Data System (ADS)

Parkinson, Gareth S.

2016-03-01

The current status of knowledge regarding the surfaces of the iron oxides, magnetite (Fe3O4), maghemite (γ-Fe2O3), haematite (α-Fe2O3), and wüstite (Fe1-xO) is reviewed. The paper starts with a summary of applications where iron oxide surfaces play a major role, including corrosion, catalysis, spintronics, magnetic nanoparticles (MNPs), biomedicine, photoelectrochemical water splitting and groundwater remediation. The bulk structure and properties are then briefly presented; each compound is based on a close-packed anion lattice, with a different distribution and oxidation state of the Fe cations in interstitial sites. The bulk defect chemistry is dominated by cation vacancies and interstitials (not oxygen vacancies) and this provides the context to understand iron oxide surfaces, which represent the front line in reduction and oxidation processes. Fe diffuses in and out from the bulk in response to the O2 chemical potential, forming sometimes complex intermediate phases at the surface. For example, α-Fe2O3 adopts Fe3O4-like surfaces in reducing conditions, and Fe3O4 adopts Fe1-xO-like structures in further reducing conditions still. It is argued that known bulk defect structures are an excellent starting point in building models for iron oxide surfaces. The atomic-scale structure of the low-index surfaces of iron oxides is the major focus of this review. Fe3O4 is the most studied iron oxide in surface science, primarily because its stability range corresponds nicely to the ultra-high vacuum environment. It is also an electrical conductor, which makes it straightforward to study with the most commonly used surface science methods such as photoemission spectroscopies (XPS, UPS) and scanning tunneling microscopy (STM). The impact of the surfaces on the measurement of bulk properties such as magnetism, the Verwey transition and the (predicted) half-metallicity is discussed. The best understood iron oxide surface at present is probably Fe3O4(100); the structure is known with a high degree of precision and the major defects and properties are well characterised. A major factor in this is that a termination at the Feoct-O plane can be reproducibly prepared by a variety of methods, as long as the surface is annealed in 10-7-10-5 mbar O2 in the final stage of preparation. Such straightforward preparation of a monophase termination is generally not the case for iron oxide surfaces. All available evidence suggests the oft-studied (√2×√2)R45° reconstruction results from a rearrangement of the cation lattice in the outermost unit cell in which two octahedral cations are replaced by one tetrahedral interstitial, a motif conceptually similar to well-known Koch-Cohen defects in Fe1-xO. The cation deficiency results in Fe11O16 stoichiometry, which is in line with the chemical potential in ultra-high vacuum (UHV), which is close to the border between the Fe3O4 and Fe2O3 phases. The Fe3O4(111) surface is also much studied, but two different surface terminations exist close in energy and can coexist, which makes sample preparation and data interpretation somewhat tricky. Both the Fe3O4(100) and Fe3O4(111) surfaces exhibit Fe-rich terminations as the sample selvedge becomes reduced. The Fe3O4(110) surface forms a one-dimensional (1×3) reconstruction linked to nanofaceting, which exposes the more stable Fe3O4(111) surface. α-Fe2O3(0001) is the most studied haematite surface, but difficulties preparing stoichiometric surfaces under UHV conditions have hampered a definitive determination of the structure. There is evidence for at least three terminations: a bulk-like termination at the oxygen plane, a termination with half of the cation layer, and a termination with ferryl groups. When the surface is reduced the so-called "bi-phase" structure is formed, which eventually transforms to a Fe3O4(111)-like termination. The structure of the bi-phase surface is controversial; a largely accepted model of coexisting Fe1-xO and α-Fe2O3(0001) islands was recently challenged and a new structure based on a thin film of Fe3O4(111) on α-Fe2O3(0001) was proposed. The merits of the competing models are discussed. The α-Fe2O3(1 1 bar02) "R-cut" surface is recommended as an excellent prospect for future study given its apparent ease of preparation and its prevalence in nanomaterial. In the latter sections the literature regarding adsorption on iron oxides is reviewed. First, the adsorption of molecules (H2, H2O, CO, CO2, O2, HCOOH, CH3OH, CCl4, CH3I, C6H6, SO2, H2S, ethylbenzene, styrene, and Alq3) is discussed, and an attempt is made to relate this information to the reactions in which iron oxides are utilized as a catalyst (water-gas shift, Fischer-Tropsch, dehydrogenation of ethylbenzene to styrene) or catalyst supports (CO oxidation). The known interactions of iron oxide surfaces with metals are described, and it is shown that the behaviour is determined by whether the metal forms a stable ternary phase with the iron oxide. Those that do not, (e.g. Au, Pt, Ag, Pd) prefer to form three-dimensional particles, while the remainder (Ni, Co, Mn, Cr, V, Cu, Ti, Zr, Sn, Li, K, Na, Ca, Rb, Cs, Mg, Ca) incorporate within the oxide lattice. The incorporation temperature scales with the heat of formation of the most stable metal oxide. A particular effort is made to underline the mechanisms responsible for the extraordinary thermal stability of isolated metal adatoms on Fe3O4 surfaces, and the potential application of this model system to understand single atom catalysis and sub-nano cluster catalysis is discussed. The review ends with a brief summary, and a perspective is offered including exciting lines of future research.

Effect of Reacting Surface Density on the Overall Graphite Oxidation Rate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang H. Oh; Eung Kim; Jong Lim

2009-05-01

Graphite oxidation in an air-ingress accident is presently a very important issue for the reactor safety of the very high temperature gas cooled-reactor (VHTR), the concept of the next generation nuclear plant (NGNP) because of its potential problems such as mechanical degradation of the supporting graphite in the lower plenum of the VHTR might lead to core collapse if the countermeasure is taken carefully. The oxidation process of graphite has known to be affected by various factors, including temperature, pressure, oxygen concentration, types of graphite, graphite shape and size, flow distribution, etc. However, our recent study reveals that the internalmore » pore characteristics play very important roles in the overall graphite oxidation rate. One of the main issues regarding graphite oxidation is the potential core collapse problem that may occur following the degradation of graphite mechanical strength. In analyzing this phenomenon, it is very important to understand the relationship between the degree of oxidization and strength degradation. In addition, the change of oxidation rate by graphite oxidation degree characterization by burn-off (ratio of the oxidized graphite density to the original density) should be quantified because graphite strength degradation is followed by graphite density decrease, which highly affects oxidation rates and patterns. Because the density change is proportional to the internal pore surface area, they should be quantified in advance. In order to understand the above issues, the following experiments were performed: (1)Experiment on the fracture of the oxidized graphite and validation of the previous correlations, (2) Experiment on the change of oxidation rate using graphite density and data collection, (3) Measure the BET surface area of the graphite. The experiments were performed using H451 (Great Lakes Carbon Corporation) and IG-110 (Toyo Tanso Co., Ltd) graphite. The reason for the use of those graphite materials is because their chemical and mechanical characteristics are well identified by the previous investigations, and therefore it was convenient for us to access the published data, and to apply and validate our new methodologies. This paper presents preliminary results of compressive strength vs. burn-off and surface area density vs. burn-off, which can be used for the nuclear graphite selection for the NGNP.« less

Influence of Adsorbed Hydroxyl and Carbon Monoxide on Potential-Induced Reconstruction of Au(100) as Examined by Scanning Tunneling Microscopy

DTIC Science & Technology

1994-02-01

years have witnessed substantial advances in our knowledge of metal reconstruction in electrochemical systems, primarily for low-index gold surfaces in...index gold surfaces, reconstruction can be formed or removed by applying electrode potentials corresponding to negative or positive electronic charge...potential and gold oxidation regions, for Au(100) in 0.1 M KOH, obtained in a conventional electrochemical cell (solid trace). The voltammetric

Engineering p-n junctions and bandgap tuning of InSe nanolayers by controlled oxidation

NASA Astrophysics Data System (ADS)

Balakrishnan, Nilanthy; Kudrynskyi, Zakhar R.; Smith, Emily F.; Fay, Michael W.; Makarovsky, Oleg; Kovalyuk, Zakhar D.; Eaves, Laurence; Beton, Peter H.; Patanè, Amalia

2017-06-01

Exploitation of two-dimensional (2D) van der Waals (vdW) crystals can be hindered by the deterioration of the crystal surface over time due to oxidation. On the other hand, the existence of a stable oxide at room temperature can offer prospects for several applications. Here we report on the chemical reactivity of γ-InSe, a recent addition to the family of 2D vdW crystals. We demonstrate that, unlike other 2D materials, InSe nanolayers can be chemically stable under ambient conditions. However, both thermal- and photo-annealing in air induces the oxidation of the InSe surface, which converts a few surface layers of InSe into In2O3, thus forming an InSe/In2O3 heterostructure with distinct and interesting electronic properties. The oxidation can be activated in selected areas of the flake by laser writing or prevented by capping the InSe surface with an exfoliated flake of hexagonal boron nitride. We exploit the controlled oxidation of p-InSe to fabricate p-InSe/n-In2O3 junction diodes with room temperature electroluminescence and spectral response from the near-infrared to the visible and near-ultraviolet ranges. These findings reveal the limits and potential of thermal- and photo-oxidation of InSe in future technologies.

Double layer of platinum electrodes: Non-monotonic surface charging phenomena and negative double layer capacitance

NASA Astrophysics Data System (ADS)

Huang, Jun; Zhou, Tao; Zhang, Jianbo; Eikerling, Michael

2018-01-01

In this study, a refined double layer model of platinum electrodes accounting for chemisorbed oxygen species, oriented interfacial water molecules, and ion size effects in solution is presented. It results in a non-monotonic surface charging relation and a peculiar capacitance vs. potential curve with a maximum and possibly negative values in the potential regime of oxide-formation.

Oxidation of ammonia and methane in an alkaline, saline lake

USGS Publications Warehouse

Joye, S.B.; Connell, T.L.; Miller, L.G.; Oremland, R.S.; Jellison, R.S.

1999-01-01

The oxidation of ammonia (NH3) and methane (CH4) was investigated in an alkaline saline lake, Mono Lake, California (U.S.A.). Ammonia oxidation was examined in April and July 1995 by comparing dark 14CO2 fixation rates in the presence or absence of methyl fluoride (MeF), an inhibitor of NH3 oxidation. Ammonia oxidizer-mediated dark 14CO2 fixation rates were similar in surface (5-7 m) and oxycline (11-15 m) waters, ranging between 70-340 and 89-186 nM d-1, respectively, or 1-7% of primary production by phytoplankton. Ammonia oxidation rates ranged between 580-2,830 nM d-1 in surface waters and 732-1,548 nM d-1 in oxycline waters. Methane oxidation was examined using a 14CH4 tracer technique in July 1994, April 1995, and July 1995. Methane oxidation rates were consistently higher in July, and rates in oxycline and anaerobic bottom waters (0.5-37 and 7-48 nM d-1, respectively) were 10-fold higher than those in aerobic surface waters (0.04-3.8 nM d-1). The majority of CH4 oxidation, in terms of integrated activity, occurred within anoxic bottom waters. Water column oxidation reduced the potential lake-atmosphere CH4 flux by a factor of two to three. Measured oxidation rates and water column concentrations were used to estimate the biological turnover times of NH3 and CH4. The NH3 pool turns over rapidly, on time scales of 0.8 d in surface waters and 10 d within the oxycline, while CH4 is cycled on 103-d time scales in surface waters and 102-d time scales within oxycline and bottom waters. Our data suggest an important role for NH3 oxidation in alkaline, saline lakes since the process converts volatile NH3 to soluble NO2-, thereby reducing loss via lake-atmosphere exchange and maintaining nitrogen in a form that is readily available to phytoplankton.

Review of Fabrication Methods, Physical Properties, and Applications of Nanostructured Copper Oxides Formed via Electrochemical Oxidation.

PubMed

Stepniowski, Wojciech J; Misiolek, Wojciech Z

2018-05-29

Typically, anodic oxidation of metals results in the formation of hexagonally arranged nanoporous or nanotubular oxide, with a specific oxidation state of the transition metal. Recently, the majority of transition metals have been anodized; however, the formation of copper oxides by electrochemical oxidation is yet unexplored and offers numerous, unique properties and applications. Nanowires formed by copper electrochemical oxidation are crystalline and composed of cuprous (CuO) or cupric oxide (Cu₂O), bringing varied physical and chemical properties to the nanostructured morphology and different band gaps: 1.44 and 2.22 eV, respectively. According to its Pourbaix (potential-pH) diagram, the passivity of copper occurs at ambient and alkaline pH. In order to grow oxide nanostructures on copper, alkaline electrolytes like NaOH and KOH are used. To date, no systemic study has yet been reported on the influence of the operating conditions, such as the type of electrolyte, its temperature, and applied potential, on the morphology of the grown nanostructures. However, the numerous reports gathered in this paper will provide a certain view on the matter. After passivation, the formed nanostructures can be also post-treated. Post-treatments employ calcinations or chemical reactions, including the chemical reduction of the grown oxides. Nanostructures made of CuO or Cu₂O have a broad range of potential applications. On one hand, with the use of surface morphology, the wetting contact angle is tuned. On the other hand, the chemical composition (pure Cu₂O) and high surface area make such materials attractive for renewable energy harvesting, including water splitting. While compared to other fabrication techniques, self-organized anodization is a facile, easy to scale-up, time-efficient approach, providing high-aspect ratio one-dimensional (1D) nanostructures. Despite these advantages, there are still numerous challenges that have to be faced, including the strict control of the chemical composition and morphology of the grown nanostructures, their uniformity, and understanding the mechanism of their growth.

Factors Driving Potential Ammonia Oxidation in Canadian Arctic Ecosystems: Does Spatial Scale Matter?

PubMed Central

Banerjee, Samiran

2012-01-01

Ammonia oxidation is a major process in nitrogen cycling, and it plays a key role in nitrogen limited soil ecosystems such as those in the arctic. Although mm-scale spatial dependency of ammonia oxidizers has been investigated, little is known about the field-scale spatial dependency of aerobic ammonia oxidation processes and ammonia-oxidizing archaeal and bacterial communities, particularly in arctic soils. The purpose of this study was to explore the drivers of ammonia oxidation at the field scale in cryosols (soils with permafrost within 1 m of the surface). We measured aerobic ammonia oxidation potential (both autotrophic and heterotrophic) and functional gene abundance (bacterial amoA and archaeal amoA) in 279 soil samples collected from three arctic ecosystems. The variability associated with quantifying genes was substantially less than the spatial variability observed in these soils, suggesting that molecular methods can be used reliably evaluate spatial dependency in arctic ecosystems. Ammonia-oxidizing archaeal and bacterial communities and aerobic ammonia oxidation were spatially autocorrelated. Gene abundances were spatially structured within 4 m, whereas biochemical processes were structured within 40 m. Ammonia oxidation was driven at small scales (<1m) by moisture and total organic carbon, whereas gene abundance and other edaphic factors drove ammonia oxidation at medium (1 to 10 m) and large (10 to 100 m) scales. In these arctic soils heterotrophs contributed between 29 and 47% of total ammonia oxidation potential. The spatial scale for aerobic ammonia oxidation genes differed from potential ammonia oxidation, suggesting that in arctic ecosystems edaphic, rather than genetic, factors are an important control on ammonia oxidation. PMID:22081570

Potential for iron oxides to control metal releases in CO2 sequestration scenarios

USGS Publications Warehouse

Berger, P.M.; Roy, W.R.

2011-01-01

The potential for the release of metals into groundwater following the injection of carbon dioxide (CO2) into the subsurface during carbon sequestration projects remains an open research question. Changing the chemical composition of even the relatively deep formation brines during CO2 injection and storage may be of concern because of the recognized risks associated with the limited potential for leakage of CO2-impacted brine to the surface. Geochemical modeling allows for proactive evaluation of site geochemistry before CO2 injection takes place to predict whether the release of metals from iron oxides may occur in the reservoir. Geochemical modeling can also help evaluate potential changes in shallow aquifers were CO2 leakage to occur near the surface. In this study, we created three batch-reaction models that simulate chemical changes in groundwater resulting from the introduction of CO2 at two carbon sequestration sites operated by the Midwest Geological Sequestration Consortium (MGSC). In each of these models, we input the chemical composition of groundwater samples into React??, and equilibrated them with selected mineral phases and CO 2 at reservoir pressure and temperature. The model then simulated the kinetic reactions with other mineral phases over a period of up to 100 years. For two of the simulations, the water was also at equilibrium with iron oxide surface complexes. The first model simulated a recently completed enhanced oil recovery (EOR) project in south-central Illinois in which the MGSC injected into, and then produced CO2, from a sandstone oil reservoir. The MGSC afterwards periodically measured the brine chemistry from several wells in the reservoir for approximately two years. The sandstone contains a relatively small amount of iron oxide, and the batch simulation for the injection process showed detectable changes in several aqueous species that were attributable to changes in surface complexation sites. After using the batch reaction configuration to match measured geochemical changes due to CO2 injection, we modeled potential changes in groundwater chemistry at the Illinois Basin - Decatur Project (IBDP) site in Decatur, Illinois, USA. At the IBDP, the MGSC will inject 1 million tonnes of CO2 over the course of three years at a depth of about 2 km below the surface into the Mt. Simon Formation. Sections of the Mt. Simon Formation contain up to 10 percent iron oxide, and therefore surface complexes on iron oxides should play a major role in controlling brine chemistry. The batch simulation of this system showed a significant decrease in pH after the injection of CO2 with corresponding changes in brine chemistry resulting from both mineral precipitation/dissolution reactions and changes in the chemistry on iron oxide surfaces. To ensure the safety of shallow drinking water sources, there are several shallow monitoring wells at the IBDP that the MGSC samples regularly to determine baseline chemical concentrations. Knowing what geochemical parameters are most sensitive to CO2 disturbances allows us to focus monitoring efforts. Modeling a major influx of CO2 into the shallow groundwater allowed us to determine that were an introduction of CO2 to occur, the only immediate effect will be dolomite dissolution and calcite precipitation. ?? 2011 Published by Elsevier Ltd.

Kinetics of Photoelectrochemical Oxidation of Methanol on Hematite Photoanodes

PubMed Central

2017-01-01

The kinetics of photoelectrochemical (PEC) oxidation of methanol, as a model organic substrate, on α-Fe2O3 photoanodes are studied using photoinduced absorption spectroscopy and transient photocurrent measurements. Methanol is oxidized on α-Fe2O3 to formaldehyde with near unity Faradaic efficiency. A rate law analysis under quasi-steady-state conditions of PEC methanol oxidation indicates that rate of reaction is second order in the density of surface holes on hematite and independent of the applied potential. Analogous data on anatase TiO2 photoanodes indicate similar second-order kinetics for methanol oxidation with a second-order rate constant 2 orders of magnitude higher than that on α-Fe2O3. Kinetic isotope effect studies determine that the rate constant for methanol oxidation on α-Fe2O3 is retarded ∼20-fold by H/D substitution. Employing these data, we propose a mechanism for methanol oxidation under 1 sun irradiation on these metal oxide surfaces and discuss the implications for the efficient PEC methanol oxidation to formaldehyde and concomitant hydrogen evolution. PMID:28735533

High quality HfO{sub 2}/p-GaSb(001) metal-oxide-semiconductor capacitors with 0.8 nm equivalent oxide thickness

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barth, Michael; Datta, Suman, E-mail: sdatta@engr.psu.edu; Bruce Rayner, G.

2014-12-01

We investigate in-situ cleaning of GaSb surfaces and its effect on the electrical performance of p-type GaSb metal-oxide-semiconductor capacitor (MOSCAP) using a remote hydrogen plasma. Ultrathin HfO{sub 2} films grown by atomic layer deposition were used as a high permittivity gate dielectric. Compared to conventional ex-situ chemical cleaning methods, the in-situ GaSb surface treatment resulted in a drastic improvement in the impedance characteristics of the MOSCAPs, directly evidencing a much lower interface trap density and enhanced Fermi level movement efficiency. We demonstrate that by using a combination of ex-situ and in-situ surface cleaning steps, aggressively scaled HfO{sub 2}/p-GaSb MOSCAP structuresmore » with a low equivalent oxide thickness of 0.8 nm and efficient gate modulation of the surface potential are achieved, allowing to push the Fermi level far away from the valence band edge high up into the band gap of GaSb.« less

Evaluation of ferrolysis in arsenate adsorption on the paddy soil derived from an Oxisol.

PubMed

Jiang, Jun; Dai, Zhaoxia; Sun, Rui; Zhao, Zhenjie; Dong, Ying; Hong, Zhineng; Xu, Renkou

2017-07-01

Iron oxides are dominant effective adsorbents for arsenate in iron oxide-rich variable charge soils. Oxisol-derived paddy soils undergo intensive ferrolysis, which results in high leaching and transformation of iron oxides. However, little information is available concerning the effect of ferrolysis on arsenate adsorption by paddy soil and parent Oxisol. In the present study, we examined the arsenate affinity of soils using arsenate adsorption/desorption isotherms, zeta potential, adsorption kinetics, pH effect and phosphate competition experiments. Results showed that ferrolysis in an alternating flooding-drying Oxisol-derived paddy soil resulted in a significant decrease of free iron oxides and increase of amorphous iron oxides in the surface and subsurface layers. There were more reactive sites exposed on amorphous than on crystalline iron oxides. Therefore, disproportionate ratios of arsenate adsorption capacities and contents of free iron oxides were observed in the studied Oxisols compared with paddy soils. The Gibbs free energy values corroborated that both electrostatic and non-electrostatic adsorption mechanisms contributed to the arsenate adsorption by bulk soils, and the kinetic adsorption data further suggested that the rate-limiting step was chemisorption. The zeta potential of soil colloids decreased after arsenate was adsorbed on the surfaces, forming inner-sphere complexes and thus transferring their negative charges to the soil particle surfaces. The adsorption/desorption isotherms showed that non-electrostatic adsorption was the main mechanism responsible for arsenate binding to the Oxisol and derived paddy soils, representing 91.42-94.65% of the adsorption capacities. Further studies revealed that arsenate adsorption was greatly inhibited by increasing suspension pH and incorporation of phosphate. Copyright © 2017 Elsevier Ltd. All rights reserved.

Saturn Magnetospheric Impact on Surface Molecular Chemistry and Astrobiological Potential of Enceladus

NASA Technical Reports Server (NTRS)

Cooper, Paul D.; Cooper, John F.; Sittler, Edward C.; Burger, Matthew H.; Sturner, Steven J.; Rymer, Abigail M.

2008-01-01

The active south polar surface of Enceladus is exposed to strong chemical processing by direct interaction with charged plasma and energetic particles in the local magnetospheric environment of this icy moon. Chemical oxidation activity is suggested by detection of H202 at the surface in this region and less directly by substantial presence of C02, CO, and N2 in the plume gases. Molecular composition of the uppermost surface, including ejecta from plume activity, is radiolytically transformed mostly by penetrating energetic electrons with lesser effects from more depleted populations of energetic protons. The main sources of molecular plasma ions and E-ring dust grains in the magnetospheric environment are the cryovolcanic plume emissions from Enceladus. These molecular ions and the dust grains are chemically processed by magnetospheric interactions that further impact surface chemistry on return to Enceladus. For example, H20 neutrals dominating the emitted plume gas return to the surface mostly as H30+ ions after magnetospheric processing. Surface oxidant loading is further increased by return of radiolytically processed ice grains from the E-ring. Plume frost deposition and micrometeoroid gardening protect some fraction of newly produced molecular species from destruction by further irradiation. The evident horizontal and vertical mobility of surface ices in the south polar region drive mixing of these processed materials into the moon interior with potential impacts on deep ice molecular chemistry and plume gas production. Similarly as suggested previously for Europa, the externally driven source of radiolytic oxidants could affect evolution of life in any subsurface liquid water environments of Enceladus.

Did Mineral Surface Chemistry and Toxicity Contribute to Evolution of Microbial Extracellular Polymeric Substances?

PubMed Central

Campbell, Jay M.; Zhang, Nianli; Hickey, William J.

2012-01-01

Abstract Modern ecological niches are teeming with an astonishing diversity of microbial life in biofilms closely associated with mineral surfaces, which highlights the remarkable success of microorganisms in conquering the challenges and capitalizing on the benefits presented by the mineral–water interface. Biofilm formation capability likely evolved on early Earth because biofilms provide crucial cell survival functions. The potential toxicity of mineral surfaces toward cells and the complexities of the mineral–water–cell interface in determining the toxicity mechanisms, however, have not been fully appreciated. Here, we report a previously unrecognized role for extracellular polymeric substances (EPS), which form biofilms in shielding cells against the toxicity of mineral surfaces. Using colony plating and LIVE/DEAD staining methods in oxide suspensions versus oxide-free controls, we found greater viability of wild-type, EPS-producing strains of Pseudomonas aeruginosa PAO1 compared to their isogenic knockout mutant with defective biofilm-producing capacity. Oxide toxicity was specific to its surface charge and particle size. High resolution transmission electron microscopy (HRTEM) images and assays for highly reactive oxygen species (hROS) on mineral surfaces suggested that EPS shield via both physical and chemical mechanisms. Intriguingly, qualitative as well as quantitative measures of EPS production showed that toxic minerals induced EPS production in bacteria. By determining the specific toxicity mechanisms, we provide insight into the potential impact of mineral surfaces in promoting increased complexity of cell surfaces, including EPS and biofilm formation, on early Earth. Key Words: Mineral toxicity—Bacteria—EPS evolution—Biofilms—Cytotoxicity—Silica—Anatase—Alumina. Astrobiology 12, 785–798. PMID:22934560

Comparison of Degrees of Potential-Energy-Surface Anharmonicity for Complexes and Clusters with Hydrogen Bonds

NASA Astrophysics Data System (ADS)

Kozlovskaya, E. N.; Doroshenko, I. Yu.; Pogorelov, V. E.; Vaskivskyi, Ye. V.; Pitsevich, G. A.

2018-01-01

Previously calculated multidimensional potential-energy surfaces of the MeOH monomer and dimer, water dimer, malonaldehyde, formic acid dimer, free pyridine-N-oxide/trichloroacetic acid complex, and protonated water dimer were analyzed. The corresponding harmonic potential-energy surfaces near the global minima were constructed for series of clusters and complexes with hydrogen bonds of different strengths based on the behavior of the calculated multidimensional potential-energy surfaces. This enabled the introduction of an obvious anharmonicity parameter for the calculated potential-energy surfaces. The anharmonicity parameter was analyzed as functions of the size of the analyzed area near the energy minimum, the number of points over which energies were compared, and the dimensionality of the solved vibrational problem. Anharmonicity parameters for potential-energy surfaces in complexes with strong, medium, and weak H-bonds were calculated under identical conditions. The obtained anharmonicity parameters were compared with the corresponding diagonal anharmonicity constants for stretching vibrations of the bridging protons and the lengths of the hydrogen bridges.

Zeta potentials in the flotation of oxide and silicate minerals.

PubMed

Fuerstenau, D W; Pradip

2005-06-30

Adsorption of collectors and modifying reagents in the flotation of oxide and silicate minerals is controlled by the electrical double layer at the mineral-water interface. In systems where the collector is physically adsorbed, flotation with anionic or cationic collectors depends on the mineral surface being charged oppositely. Adjusting the pH of the system can enhance or prevent the flotation of a mineral. Thus, the point of zero charge (PZC) of the mineral is the most important property of a mineral in such systems. The length of the hydrocarbon chain of the collector is important because of chain-chain association enhances the adsorption once the surfactant ions aggregate to form hemimicelles at the surface. Strongly chemisorbing collectors are able to induce flotation even when collector and the mineral surface are charged similarly, but raising the pH sufficiently above the PZC can repel chemisorbing collectors from the mineral surface. Zeta potentials can be used to delineate interfacial phenomena in these various systems.

Electrochemically Driven Deactivation and Recovery in PrBaCo2 O5+δ Oxygen Electrodes for Reversible Solid Oxide Fuel Cells.

PubMed

Zhu, Lin; Wei, Bo; Wang, Zhihong; Chen, Kongfa; Zhang, Haiwu; Zhang, Yaohui; Huang, Xiqiang; Lü, Zhe

2016-09-08

The understanding of surface chemistry changes on oxygen electrodes is critical for the development of reversible solid oxide fuel cell (RSOFC). Here, we report for the first time that the electrochemical potentials can drastically affect the surface composition and hence the electrochemical activity and stability of PrBaCo2 O5+δ (PBCO) electrodes. Anodic polarization degrades the activity of the PBCO electrode, whereas the cathodic bias could recover its performance. Alternating anodic/cathodic polarization for 180 h confirms this behavior. Microstructure and chemical analysis clearly show that anodic bias leads to the accumulation and segregation of insulating nanosized BaO on the electrode surface, whereas cathodic polarization depletes the surface species. Therefore, a mechanism based on the segregation and incorporation of BaO species under electrochemical potentials is considered to be responsible for the observed deactivation and recovery process, respectively. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ab Initio Cluster Calculations for the Adsorption of Small Molecules on Oxide Surfaces - from Single Molecules to Monolayers

NASA Astrophysics Data System (ADS)

Pykavy, M.; Staemmler, V.; Rittner, F.

2000-04-01

Quantum chemical ab initio cluster calculations were performed for the adsorption of small molecules on metal oxide surfaces. Two systems were studied in detail: The adsorption of N2 on the (110) surface plane of TiO2 (rutile) and the adsorption of CO on the polar (0001) surface of Cr2O3. In both cases a full five-dimensional potential for the interaction of a single molecule with the respective surface was calculated. For N2/TiO2 (110) the minimum was found for the end-on adsorption of N2 atop a coordinately unsaturated surface Ti atom, with an adsorption energy of (35 ± 5) kJ/mol. In the case of CO/Cr2O3 (0001) the CO molecule is adsorbed strongly tilted (almost side-on) along a line connecting two Cr3+ ions at the surface; the calculated adsorption energy is 22 kJ/mol. In conjunction with empirical pair potentials for the N2/N2 and CO/CO interaction in the gas phase, Monte Carlo simulations were carried out to determine adsorption isotherms and the geometric structure of adsorbed monolayers.

Search for life on Mars.

PubMed

Brack, A; Clancy, P; Fitton, B; Hoffmann, B; Horneck, G; Kurat, G; Maxwell, J; Ori, G; Pillinger, C; Raulin, F; Thomas, N; Westall, F

1998-06-01

A multi-user integrated suite of instruments designed to optimize the search for evidence of life on Mars is described. The package includes: -Surface inspection and surface environment analysis to identify the potential Mars landing sites, to inspect the surface geology and mineralogy, to search for visible surficial microbial macrofossils, to study the surface radiation budget and surface oxidation processes, to search for niches for extant life. -Subsurface sample acquisition by core drilling -Analysis of surface and subsurface minerals and organics to characterize the surface mineralogy, to analyse the surface and subsurface oxidants, to analyse the mineralogy of subsurface aliquots, to analyse the organics present in the subsurface aliquots (elemental and molecular composition, isotopes, chirality). -Macroscopic and microscopic inspection of subsurface aliquots to search for life's indicators (paleontological, biological, mineralogical) and to characterize the mineralogy of the subsurface aliquots. The study is led by ESA Manned Spaceflight and Microgravity Directorate.

Carbon monoxide as a metabolic energy source for extremely halophilic microbes: implications for microbial activity in Mars regolith.

PubMed

King, Gary M

2015-04-07

Carbon monoxide occurs at relatively high concentrations (≥800 parts per million) in Mars' atmosphere, where it represents a potentially significant energy source that could fuel metabolism by a localized putative surface or near-surface microbiota. However, the plausibility of CO oxidation under conditions relevant for Mars in its past or at present has not been evaluated. Results from diverse terrestrial brines and saline soils provide the first documentation, to our knowledge, of active CO uptake at water potentials (-41 MPa to -117 MPa) that might occur in putative brines at recurrent slope lineae (RSL) on Mars. Results from two extremely halophilic isolates complement the field observations. Halorubrum str. BV1, isolated from the Bonneville Salt Flats, Utah (to our knowledge, the first documented extremely halophilic CO-oxidizing member of the Euryarchaeota), consumed CO in a salt-saturated medium with a water potential of -39.6 MPa; activity was reduced by only 28% relative to activity at its optimum water potential of -11 MPa. A proteobacterial isolate from hypersaline Mono Lake, California, Alkalilimnicola ehrlichii MLHE-1, also oxidized CO at low water potentials (-19 MPa), at temperatures within ranges reported for RSL, and under oxic, suboxic (0.2% oxygen), and anoxic conditions (oxygen-free with nitrate). MLHE-1 was unaffected by magnesium perchlorate or low atmospheric pressure (10 mbar). These results collectively establish the potential for microbial CO oxidation under conditions that might obtain at local scales (e.g., RSL) on contemporary Mars and at larger spatial scales earlier in Mars' history.

Carbon monoxide as a metabolic energy source for extremely halophilic microbes: Implications for microbial activity in Mars regolith

PubMed Central

King, Gary M.

2015-01-01

Carbon monoxide occurs at relatively high concentrations (≥800 parts per million) in Mars’ atmosphere, where it represents a potentially significant energy source that could fuel metabolism by a localized putative surface or near-surface microbiota. However, the plausibility of CO oxidation under conditions relevant for Mars in its past or at present has not been evaluated. Results from diverse terrestrial brines and saline soils provide the first documentation, to our knowledge, of active CO uptake at water potentials (−41 MPa to −117 MPa) that might occur in putative brines at recurrent slope lineae (RSL) on Mars. Results from two extremely halophilic isolates complement the field observations. Halorubrum str. BV1, isolated from the Bonneville Salt Flats, Utah (to our knowledge, the first documented extremely halophilic CO-oxidizing member of the Euryarchaeota), consumed CO in a salt-saturated medium with a water potential of −39.6 MPa; activity was reduced by only 28% relative to activity at its optimum water potential of −11 MPa. A proteobacterial isolate from hypersaline Mono Lake, California, Alkalilimnicola ehrlichii MLHE-1, also oxidized CO at low water potentials (−19 MPa), at temperatures within ranges reported for RSL, and under oxic, suboxic (0.2% oxygen), and anoxic conditions (oxygen-free with nitrate). MLHE-1 was unaffected by magnesium perchlorate or low atmospheric pressure (10 mbar). These results collectively establish the potential for microbial CO oxidation under conditions that might obtain at local scales (e.g., RSL) on contemporary Mars and at larger spatial scales earlier in Mars’ history. PMID:25831529

Porous TiO₂ surface formed on nickel-titanium alloy by plasma electrolytic oxidation: a prospective polymer-free reservoir for drug eluting stent applications.

PubMed

Huan, Zhiguang; Fratila-Apachitei, Lidy E; Apachitei, Iulian; Duszczyk, Jurek

2013-07-01

In this study, a porous oxide layer was formed on the surface of nickel-titanium alloy (NiTi) by plasma electrolytic oxidation (PEO) with the aim to produce a polymer-free drug carrier for drug eluting stent (DES) applications. The oxidation was performed galvanostatically in concentrated phosphoric acid electrolyte at low temperature. It was found that the response of NiTi substrate during the PEO process was different from that of bulk Ti, since the presence of large amount of Ni delayed the initial formation of a compact oxide layer that is essential for the PEO to take place. Under optimized PEO conditions, the resultant surface showed porosity, pore density and oxide layer thickness of 14.11%, 2.40 × 10⁵ pores/mm² and 0.8 μm, respectively. It was additionally noted that surface roughness after PEO did not significantly increase as compared with that of original NiTi substrate and the EDS analyses revealed a decrease in Ni/Ti ratio on the surface after PEO. The cross-section morphology showed no discontinuity between the PEO layer and the NiTi substrate. Furthermore, wettability and surface free energy of the NiTi substrate increased significantly after PEO treatment. The PEO process could be successfully translated to NiTi stent configuration proving for the first time its feasibility for such a medical device and offering potential for development of alternative, polymer-free drug carriers for NiTi DES. Copyright © 2013 Wiley Periodicals, Inc.

Porous Structures in Stacked, Crumpled and Pillared Graphene-Based 3D Materials.

PubMed

Guo, Fei; Creighton, Megan; Chen, Yantao; Hurt, Robert; Külaots, Indrek

2014-01-01

Graphene, an atomically thin material with the theoretical surface area of 2600 m 2 g -1 , has great potential in the fields of catalysis, separation, and gas storage if properly assembled into functional 3D materials at large scale. In ideal non-interacting ensembles of non-porous multilayer graphene plates, the surface area can be adequately estimated using the simple geometric law ~ 2600 m 2 g -1 /N, where N is the number of graphene sheets per plate. Some processing operations, however, lead to secondary plate-plate stacking, folding, crumpling or pillaring, which give rise to more complex structures. Here we show that bulk samples of multilayer graphene plates stack in an irregular fashion that preserves the 2600/N surface area and creates regular slot-like pores with sizes that are multiples of the unit plate thickness. In contrast, graphene oxide deposits into films with massive area loss (2600 to 40 m 2 g -1 ) due to nearly perfect alignment and stacking during the drying process. Pillaring graphene oxide sheets by co-deposition of colloidal-phase particle-based spacers has the potential to partially restore the large monolayer surface. Surface areas as high as 1000 m 2 g -1 are demonstrated here through colloidal-phase deposition of graphene oxide with water-dispersible aryl-sulfonated ultrafine carbon black as a pillaring agent.

Electrode Cultivation and Interfacial Electron Transport in Subsurface Microorganisms

NASA Astrophysics Data System (ADS)

Karbelkar, A. A.; Jangir, Y.; Reese, B. K.; Wanger, G.; Anderson, C.; El-Naggar, M.; Amend, J.

2016-12-01

Continental subsurface environments can present significant energetic challenges to the resident microorganisms. While these environments are geologically diverse, potentially allowing energy harvesting by microorganisms that catalyze redox reactions, many of the abundant electron donors and acceptors are insoluble and therefore not directly bioavailable. Microbes can use extracellular electron transfer (EET) as a metabolic strategy to interact with redox active surfaces. This process can be mimicked on electrode surfaces and hence can lead to enrichment and quantification of subsurface microorganisms A primary bioelectrochemical enrichment with different oxidizing and reducing potentials set up in a single bioreactor was applied in situ to subsurface microorganisms residing in iron oxide rich deposits in the Sanford Underground Research Facility. Secondary enrichment revealed a plethora of classified and unclassified subsurface microbiota on both oxidizing and reducing potentials. From this enrichment, we have isolated a Gram-positive Bacillus along with Gram-negative Cupriavidus and Anaerospora strains (as electrode reducers) and Comamonas (as an electrode oxidizer). The Bacillus and Comamonas isolates were subjected to a detailed electrochemical characterization in half-reactors at anodic and cathodic potentials, respectively. An increase in cathodic current upon inoculation and cyclic voltammetry measurements confirm the hypothesis that Comamonas is capable of electron uptake from electrodes. In addition, measurements of Bacillus on anodes hint towards novel mechanisms that allow EET from Gram-positive bacteria. This study suggests that electrochemical approaches are well positioned to dissect such extracellular interactions that may be prevalent in the subsurface, while using physical electrodes to emulate the microhabitats, redox and geochemical gradients, and the spatially dependent interspecies interactions encountered in the subsurface. Electrochemical characterization of isolated strains can help us establish the possible mechanisms of EET, and hence provide an insight on survival strategies of subsurface microbiota in extreme environments. Continental subsurface environments can present significant energetic challenges to the resident microorganisms. While these environments are geologically diverse, potentially allowing energy harvesting by microorganisms that catalyze redox reactions, many of the abundant electron donors and acceptors are insoluble and therefore not directly bioavailable. Microbes can use extracellular electron transfer (EET) as a metabolic strategy to interact with redox active surfaces. This process can be mimicked on electrode surfaces and hence can lead to enrichment and quantification of subsurface microorganisms A primary bioelectrochemical enrichment with different oxidizing and reducing potentials set up in a single bioreactor was applied in situ to subsurface microorganisms residing in iron oxide rich deposits in the Sanford Underground Research Facility. Secondary enrichment revealed a plethora of classified and unclassified subsurface microbiota on both oxidizing and reducing potentials. From this enrichment, we have isolated a Gram-positive Bacillus along with Gram-negative Cupriavidus and Anaerospora strains (as electrode reducers) and Comamonas (as an electrode oxidizer). The Bacillus and Comamonas isolates were subjected to a detailed electrochemical characterization in half-reactors at anodic and cathodic potentials, respectively. An increase in cathodic current upon inoculation and cyclic voltammetry measurements confirm the hypothesis that Comamonas is capable of electron uptake from electrodes. In addition, measurements of Bacillus on anodes hint towards novel mechanisms that allow EET from Gram-positive bacteria. This study suggests that electrochemical approaches are well positioned to dissect such extracellular interactions that may be prevalent in the subsurface, while using physical electrodes to emulate the microhabitats, redox and geochemical gradients, and the spatially dependent interspecies interactions encountered in the subsurface. Electrochemical characterization of isolated strains can help us establish the possible mechanisms of EET, and hence provide an insight on survival strategies of subsurface microbiota in extreme environments.

Dynamic Cooperation of Hydrogen Binding and π Stacking in ssDNA Adsorption on Graphene Oxide.

PubMed

Xu, Zhen; Lei, Xiaoling; Tu, Yusong; Tan, Zhi-Jie; Song, Bo; Fang, Haiping

2017-09-21

Functional nanoscale structures consisting of a DNA molecule coupled to graphene or graphene oxide (GO) have great potential for applications in biosensors, biomedicine, nanotechnology, and materials science. Extensive studies using the most sophisticated experimental techniques and theoretical methods have still not clarified the dynamic process of single-stranded DNA (ssDNA) adsorbed on GO surfaces. Based on a molecular dynamics simulation, this work shows that an ssDNA segment could be stably adsorbed on a GO surface through hydrogen bonding and π-π stacking interactions, with preferential binding to the oxidized rather than to the unoxidized region of the GO surface. The adsorption process shows a dynamic cooperation adsorption behavior; the ssDNA segment first captures the oxidized groups of the GO surface by hydrogen bonding interaction, and then the configuration relaxes to maximize the π-π stacking interactions between the aromatic rings of the nucleobases and those of the GO surface. We attributed this behavior to the faster forming hydrogen bonding interaction compared to π-π stacking; the π-π stacking interaction needs more relaxation time to regulate the configuration of the ssDNA segment to fit the aromatic rings on the GO surface. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Natural and pyrogenic humic acids at goethite and natural oxide surfaces interacting with phosphate.

PubMed

Hiemstra, Tjisse; Mia, Shamim; Duhaut, Pierre-Benoît; Molleman, Bastiaan

2013-08-20

Fulvic and humic acids have a large variability in binding to metal (hydr) oxide surfaces and interact differently with oxyanions, as examined here experimentally. Pyrogenic humic acid has been included in our study since it will be released to the environment in the case of large-scale application of biochar, potentially creating Darks Earths or Terra Preta soils. A surface complexation approach has been developed that aims to describe the competitive behavior of natural organic matter (NOM) in soil as well as model systems. Modeling points unexpectedly to a strong change of the molecular conformation of humic acid (HA) with a predominant adsorption in the Stern layer domain at low NOM loading. In soil, mineral oxide surfaces remain efficiently loaded by mineral-protected organic carbon (OC), equivalent with a layer thickness of ≥ ~0.5 nm that represents at least 0.1-1.0% OC, while surface-associated OC may be even three times higher. In natural systems, surface complexation modeling should account for this pervasive NOM coverage. With our charge distribution model for NOM (NOM-CD), the pH-dependent oxyanion competition of the organo-mineral oxide fraction can be described. For pyrogenic HA, a more than 10-fold increase in dissolved phosphate is predicted at long-term applications of biochar or black carbon.

DNA damage and oxidative stress in human liver cell L-02 caused by surface water extracts during drinking water treatment in a waterworks in China.

PubMed

Xie, Shao-Hua; Liu, Ai-Lin; Chen, Yan-Yan; Zhang, Li; Zhang, Hui-Juan; Jin, Bang-Xiong; Lu, Wen-Hong; Li, Xiao-Yan; Lu, Wen-Qing

2010-04-01

Because of the daily and life-long exposure to disinfection by-products formed during drinking water treatment, potential adverse human health risk of drinking water disinfection is of great concern. Toxicological studies have shown that drinking water treatment increases the genotoxicity of surface water. Drinking water treatment is comprised of different potabilization steps, which greatly influence the levels of genotoxic products in the surface water and thus may alter the toxicity and genotoxicity of surface water. The aim of the present study was to understand the influence of specific steps on toxicity and genotoxicity during the treatment of surface water in a water treatment plant using liquid chlorine as the disinfectant in China. An integrated approach of the comet and oxidative stress assays was used in the study, and the results showed that both the prechlorination and postchlorination steps increased DNA damage and oxidative stress caused by water extracts in human derived L-02 cells while the tube settling and filtration steps had the opposite effect. This research also highlighted the usefulness of an integrated approach of the comet and oxidative stress assays in evaluating the genotoxicity of surface water during drinking water treatment. Copyright 2009 Wiley-Liss, Inc.

Enhancing antimicrobial activity of TiO2/Ti by torularhodin bioinspired surface modification.

PubMed

Ungureanu, Camelia; Dumitriu, Cristina; Popescu, Simona; Enculescu, Monica; Tofan, Vlad; Popescu, Marian; Pirvu, Cristian

2016-02-01

Implant-associated infections are a major cause of morbidity and mortality. This study was performed using titanium samples coated by anodization with a titanium dioxide (TiO2) shielded nanotube layer. TiO2/Ti surface was modified by simple immersion in torularhodin solution and by using a mussel-inspired method based on polydopamine as bio adhesive for torularhodin immobilization. SEM analysis revealed tubular microstructures of torularhodin and the PDA ability to function as a catchy anchor between torularhodin and TiO2 surface. Corrosion resistance was associated with TiO2 barrier oxide layer and nano-organized oxide layer and the torularhodin surface modification does not bring significant changes in resistance of the oxide layer. Our results demonstrated that the torularhodin modified TiO2/Ti surface could effectively prevent adhesion and proliferation of Escherichia coli, Staphylococcus aureus, Enterococcus faecalis, Bacillus subtilis, and Pseudomonas aeruginosa. The new modified titanium surface showed good biocompatibility and well-behaved haemocompatibility. This biomaterial with enhanced antimicrobial activity holds great potential for future biomedical applications. Copyright © 2015 Elsevier B.V. All rights reserved.

Potent bactericidal efficacy of copper oxide impregnated non-porous solid surfaces

PubMed Central

2014-01-01

Background The role of fomites and the environment in nosocomial infections is becoming widely recognized. In this paper we discuss the use of Cupron copper oxide impregnated non-porous solid surface in the hospital setting and present in vitro testing data via USA Environmental Protection Agency (EPA) approved testing protocols that demonstrate the efficacy of these products to assist in reduction in environmental contamination and potentially nosocomial infections. Results The two countertops tested passed all the acceptance criteria by the EPA (>99.9% kill within 2 hours of exposure) killing a range of bacterial pathogens on the surface of the countertops even after repeated exposure of the countertops to the pathogen, and multiple wet and dry abrasion cycles. Conclusions Cupron enhanced EOS countertops thus may be an important adjunct to be used in hospital settings to reduce environmental bioburden and potentially nosocomial infections. PMID:24606672

Ultra-High Pressure Homogenization improves oxidative stability and interfacial properties of soy protein isolate-stabilized emulsions.

PubMed

Fernandez-Avila, C; Trujillo, A J

2016-10-15

Ultra-High Pressure Homogenization (100-300MPa) has great potential for technological, microbiological and nutritional aspects of fluid processing. Its effect on the oxidative stability and interfacial properties of oil-in-water emulsions prepared with 4% (w/v) of soy protein isolate and soybean oil (10 and 20%, v/v) were studied and compared to emulsions treated by conventional homogenization (15MPa). Emulsions were characterized by particle size, emulsifying activity index, surface protein concentration at the interface and by transmission electron microscopy. Primary and secondary lipid oxidation products were evaluated in emulsions upon storage. Emulsions with 20% oil treated at 100 and 200MPa exhibited the most oxidative stability due to higher amount of oil and protein surface load at the interface. This manuscript addresses the improvement in oxidative stability in emulsions treated by UHPH when compared to conventional emulsions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Water Adsorption and Dissociation on Polycrystalline Copper Oxides: Effects of Environmental Contamination and Experimental Protocol

DOE PAGES

Trotochaud, Lena; Head, Ashley R.; Pletincx, Sven; ...

2017-11-02

We use ambient-pressure X-ray photoelectron spectroscopy (APXPS) to study chemical changes, including hydroxylation and water adsorption, at copper oxide surfaces from ultrahigh vacuum to ambient relative humidities of ~5%. Polycrystalline CuO and Cu 2O surfaces were prepared by selective oxidation of metallic copper foils. For both oxides, hydroxylation occurs readily, even at high-vacuum conditions. Hydroxylation on both oxides plateaus near ~0.01% relative humidity (RH) at a coverage of ~1 monolayer. In contrast to previous studies, neither oxide shows significant accumulation of molecular water; rather, both surfaces show a high affinity for adventitious carbon contaminants. Results of isobaric and isothermic experimentsmore » are compared, and the strengths and potential drawbacks of each method are discussed. We also provide critical evaluations of the effects of the hot filament of the ion pressure gauge on the reactivity of gas-phase species, the peak fitting procedure on the quantitative analysis of spectra, and rigorous accounting of carbon contamination on data analysis and interpretation. Lastly, this work underscores the importance of considering experimental design and data analysis protocols during APXPS experiments with water vapor in order to minimize misinterpretations arising from these factors.« less

Water Adsorption and Dissociation on Polycrystalline Copper Oxides: Effects of Environmental Contamination and Experimental Protocol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Trotochaud, Lena; Head, Ashley R.; Pletincx, Sven

We use ambient-pressure X-ray photoelectron spectroscopy (APXPS) to study chemical changes, including hydroxylation and water adsorption, at copper oxide surfaces from ultrahigh vacuum to ambient relative humidities of ~5%. Polycrystalline CuO and Cu 2O surfaces were prepared by selective oxidation of metallic copper foils. For both oxides, hydroxylation occurs readily, even at high-vacuum conditions. Hydroxylation on both oxides plateaus near ~0.01% relative humidity (RH) at a coverage of ~1 monolayer. In contrast to previous studies, neither oxide shows significant accumulation of molecular water; rather, both surfaces show a high affinity for adventitious carbon contaminants. Results of isobaric and isothermic experimentsmore » are compared, and the strengths and potential drawbacks of each method are discussed. We also provide critical evaluations of the effects of the hot filament of the ion pressure gauge on the reactivity of gas-phase species, the peak fitting procedure on the quantitative analysis of spectra, and rigorous accounting of carbon contamination on data analysis and interpretation. Lastly, this work underscores the importance of considering experimental design and data analysis protocols during APXPS experiments with water vapor in order to minimize misinterpretations arising from these factors.« less

Stability of Phosphonic Self Assembled Monolayers (SAMs) on Cobalt Chromium (Co-Cr) Alloy under Oxidative conditions

PubMed Central

Bhure, Rahul; Abdel-Fattah, Tarek M.; Bonner, Carl; Hall, Felicia; Mahapatro, Anil

2011-01-01

Cobalt Chromium (Co-Cr) alloys has been widely used in the biomedical arena for cardiovascular, orthopedic and dental applications. Surface modification of the alloy allows us to tailor the interfacial properties to address critical challenges of Co-Cr alloy in medical applications. Self assembled monolayers (SAMs) of Octadecylphosphonic acid (ODPA) have been used to form thin films on the oxide layer of the Co-Cr alloy surface by solution deposition technique. The SAMs formed were investigated for their stability to oxidative conditions of ambient laboratory environment over periods of 1, 3, 7 and 14 days. The samples were then characterized for their stability using X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and Contact Angle Measurements. Detailed high energy XPS elemental scans confirmed the presence of the phosphonic monolayer after oxidative exposure which suggested that the SAMs were firmly attached to the oxide layer of Co-Cr alloy. AFM images gave topographical data of the surface and showed islands of SAMs on Co-Cr alloy surface, before and after SAM formation and also over the duration of the oxidative exposure. Contact angle measurements confirmed the hydrophobicity of the surface over 14 days. Thus the SAMs were found to be stable for the duration of the study. These SAMs could be subsequently tailored by modifying the terminal functional groups and could be used for various potential biomedical applications such as drug delivery, biocompatibility and tissue integration PMID:21603056

Efficacy of electrolysed oxidizing water in inactivating Vibrio parahaemolyticus on kitchen cutting boards and food contact surfaces.

PubMed

Chiu, T-H; Duan, J; Liu, C; Su, Y-C

2006-12-01

To determine the efficacy of electrolysed oxidizing (EO) water in inactivating Vibrio parahaemolyticus on kitchen cutting boards and food contact surfaces. Cutting boards (bamboo, wood and plastic) and food contact surfaces (stainless steel and glazed ceramic tile) were inoculated with V. parahaemolyticus. Viable cells of V. parahaemolyticus were detected on all cutting boards and food contact surfaces after 10 and 30 min, respectively, at room temperatures. Soaking inoculated food contact surfaces and cutting boards in distilled water for 1 and 3 min, respectively, resulted in various reductions of V. parahaemolyticus, but failed to remove the organism completely from surfaces. However, the treatment of EO water [pH 2.7, chlorine 40 ppm, oxidation-reduction potential 1151 mV] for 30, 45, and 60 s, completely inactivated V. parahaemolyticus on stainless steel, ceramic tile, and plastic cutting boards, respectively. EO water could be used as a disinfecting agent for inactivating V. parahaemolyticus on plastic and wood cutting boards and food contact surfaces. Rinsing the food contact surfaces with EO water or soaking cutting boards in EO water for up to 5 min could be a simple strategy to reduce cross-contamination of V. parahaemolyticus during food preparation.

X-PEEM, XPS and ToF-SIMS characterisation of xanthate induced chalcopyrite flotation: Effect of pulp potential

NASA Astrophysics Data System (ADS)

Kalegowda, Yogesh; Chan, Yuet-Loy; Wei, Der-Hsin; Harmer, Sarah L.

2015-05-01

Synchrotron-based X-ray photoemission electron microscopy (X-PEEM), X-ray photo-electron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and ultraviolet visible spectroscopy were used to characterize the flotation behaviour of chalcopyrite with xanthate at different processing conditions. The flotation recovery of chalcopyrite decreased from 97% under oxidative conditions (Eh ~ 385 mV SHE, pH 4) to 41% at a reductive potential of - 100 mV SHE (at pH 9). X-PEEM images constructed from the metal L3 absorption edges were used to produce near-edge X-ray absorption fine structure (NEXAFS) spectra from regions of interest, allowing the variability in mineral surface chemistry of each mineral particle to be analysed, and the effect of pulp potential (Eh) on the flotation of chalcopyrite to be determined. XPS, ToF-SIMS and NEXAFS analyses of chalcopyrite particles at oxidative conditions show that the surface was mildly oxidised and covered with adsorbed molecular CuEX. The Cu 2p XPS and Cu L2,3 NEXAFS spectra were dominated by CuI species attributed to bulk chalcopyrite and adsorbed CuEX. At a reductive potential of - 100 mV SHE, an increase in concentration of CuI and FeIII oxides and hydroxides was observed. X-PEEM analysis was able to show the presence of a low percentage of CuII oxides (CuO or Cu(OH)2) with predominantly CuI oxide (Cu2O) which is not evident in Cu 2p XPS spectra.

Bacterial Phosphating of Mild (Unalloyed) Steel

PubMed Central

Volkland, Hans-Peter; Harms, Hauke; Müller, Beat; Repphun, Gernot; Wanner, Oskar; Zehnder, Alexander J. B.

2000-01-01

Mild (unalloyed) steel electrodes were incubated in phosphate-buffered cultures of aerobic, biofilm-forming Rhodococcus sp. strain C125 and Pseudomonas putida mt2. A resulting surface reaction leading to the formation of a corrosion-inhibiting vivianite layer was accompanied by a characteristic electrochemical potential (E) curve. First, E increased slightly due to the interaction of phosphate with the iron oxides covering the steel surface. Subsequently, E decreased rapidly and after 1 day reached −510 mV, the potential of free iron, indicating the removal of the iron oxides. At this point, only scattered patches of bacteria covered the surface. A surface reaction, in which iron was released and vivianite precipitated, started. E remained at −510 mV for about 2 days, during which the vivianite layer grew steadily. Thereafter, E increased markedly to the initial value, and the release of iron stopped. Changes in E and formation of vivianite were results of bacterial activity, with oxygen consumption by the biofilm being the driving force. These findings indicate that biofilms may protect steel surfaces and might be used as an alternative method to combat corrosion. PMID:11010888

An atomic charge model for graphene oxide for exploring its bioadhesive properties in explicit water.

PubMed

Stauffer, D; Dragneva, N; Floriano, W B; Mawhinney, R C; Fanchini, G; French, S; Rubel, O

2014-07-28

Graphene Oxide (GO) has been shown to exhibit properties that are useful in applications such as biomedical imaging, biological sensors, and drug delivery. The binding properties of biomolecules at the surface of GO can provide insight into the potential biocompatibility of GO. Here we assess the intrinsic affinity of amino acids to GO by simulating their adsorption onto a GO surface. The simulation is done using Amber03 force-field molecular dynamics in explicit water. The emphasis is placed on developing an atomic charge model for GO. The adsorption energies are computed using atomic charges obtained from an ab initio electrostatic potential based method. The charges reported here are suitable for simulating peptide adsorption to GO.

Controlled surface oxidation of multi-layered graphene anode to increase hole injection efficiency in organic electronic devices

NASA Astrophysics Data System (ADS)

Han, Tae-Hee; Kwon, Sung-Joo; Seo, Hong-Kyu; Lee, Tae-Woo

2016-03-01

Ultraviolet ozone (UVO) surface treatment of graphene changes its sp2-hybridized carbons to sp3-bonded carbons, and introduces oxygen-containing components. Oxidized graphene has a finite energy band gap, so UVO modification of the surface of a four-layered graphene anode increases its surface ionization potential up to ∼5.2 eV and improves the hole injection efficiency (η) in organic electronic devices by reducing the energy barrier between the graphene anode and overlying organic layers. By controlling the conditions of the UVO treatment, the electrical properties of the graphene can be tuned to improve η. This controlled surface modification of the graphene will provide a way to achieve efficient and stable flexible displays and solid-state lighting.

The Redox Potentials of n-type Colloidal Semiconductor Nanocrystals

NASA Astrophysics Data System (ADS)

Carroll, Gerard Michael

This thesis presents investigations for two related fields of semiconductor electrochemistry: redox potential determination of colloidal semiconductor nanocrystals, and mechanistic analysis of photoelectrochemical water oxidation with electrocatalyst modified mesostructured hematite photoanodes. Adapting electrochemical techniques to colloidal semiconductor nanocrystals (SC NC) is a long-standing challenge for this class of materials. Subject to a variety of complications, standard voltammetric techniques are not as straight forward for SC NCs as they are for small molecules. As a result, researchers have developed creative ways to side step these complications by coupling electrochemistry with NC spectroscopy. Chapter 1 discusses the fundamental electronic and spectroscopic properties of SC NCs at different redox states. We present a brief review of some of the notable studies employing SC NC spectroelectrochemistry that provide the theoretical and experimental context for the following chapters. Chapter 2 presents an investigation on NC redox potentials of photochemically reduced colloidal ZnO NCs using a solvated redox-indicator method. In the one electron limit, conduction band electrons show evidence of quantum confinement, but at higher electron concentrations, the NC Fermi-level becomes dependent on the electron density across all NC sizes. Chapter 3 outlines a poteniometric method for monitoring the NC redox potentials in situ. NC redox potentials for ZnO and CdSe are measured, and as predicted from these measurements, spontaneous electron transfer from CdSe to ZnO is demonstrated. Chapter 4 details the impact of the surface of CdSe NCs on the NC redox potentials. We find that the ratio of Cd2+:Se2- on the surface of CdSe NCs changes both the NC band edge potentials, as well as the maximum electron density achievable by photochemical reduction. These changes are proposed to arise from interfacial dipoles when CdSe has a Se2-rich surface. Chapters 5 and 6 examine the mechanistic pathways of solar water oxidation on Co-Pi modified alpha-Fe2O3 photoanodes. A rate constant analysis of water oxidation and electron-hole recombination paired with the identification of surface-morphology-dependent current-voltage characteristics reveal new insights into the role of the semiconductor/electrocatalyst interface on the overall solar water oxidation efficiency. These findings reconcile disparate observations from previous studies.

Titanium dental implant surfaces obtained by anodic spark deposition - From the past to the future.

PubMed

Kaluđerović, Milena R; Schreckenbach, Joachim P; Graf, Hans-Ludwig

2016-12-01

Commercial titanium-based dental implants are obtained applying various methods such as machining, acid etching, anodization, plasma spraying, grit blasting or combination techniques yielding materials with smooth or micro-roughened surfaces. Those techniques are used to optimize the surface properties and to maximize biocompatibility and bioactivity with bone tissue. Present review is focused on the material surfaces obtained by anodic spark deposition (ASD). From the early 1980s till present, the results of numerous studies have shown that anodically oxidized surfaces with different dopants express a positive effect on osteoblasts behavior in vitro and osseointegration in vivo. Those surfaces demonstrated a high biocompatibility and rapid osseointegration in clinical application. This paper provides an overview of the preparation of implant surfaces by employing ASD process. Moreover, reviewed are clinically used ASD implant surfaces (Ticer, TiUnite, Osstem, etc.). The electrolyte variations in ASD process and their influence on surface properties are given herein. Using different electrolytes, anode voltages and temperatures, the above fabrication process can yield various surface morphologies from smooth to rough, porous surfaces. Furthermore, ASD enables thickening of oxide layers and enrichment with different dopands from used electrolyte, which hinder release of potentially toxic titanium ions in surrounding tissue. Particularly exciting results were achieved by calcium and phosphorus doping of the oxide layer (Ticer, ZL Microdent; TiUnite, Nobel Biocare Holding AB) which significantly increased the osteocompatibility. Ticer, a dental implant with anodically oxidized surface and the first among similar materials employed in clinical practice, was found to promote fast osteoblast cell differentiation and mineralization processes. Moreover, Ticer accelerate the integration with the bone, increase the bone/implant contact and improve primary and secondary stability of the implants. Additionally, potential innovations in this field such as fabrication of nanotubes on the implant surfaces as well as novel approaches (e.g. coating with proteins, nanostructured topography; combining implant body and surface derived from titanium and zirconia) are elaborated in this review. Besides, biochemical aspects on implant surface cell/tissue interaction are summarized. From the clinical point of view implant surfaces fabricated by ASD technology possess fast and improved osseointegration, high healing rates and long term prognosis. Copyright © 2016 Elsevier B.V. All rights reserved.

Covalent surface modification of gallium arsenide photocathodes for water splitting in highly acidic electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garner, Logan E.; Steirer, K. Xerxes; Young, James L.

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Resultsmore » indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m -2) illumination resulting from the covalently bound surface dipole. Furthermore, X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm -2 within -0.5 V of the reversible hydrogen electrode.« less

Covalent surface modification of gallium arsenide photocathodes for water splitting in highly acidic electrolyte

DOE PAGES

Garner, Logan E.; Steirer, K. Xerxes; Young, James L.; ...

2016-12-12

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Resultsmore » indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m -2) illumination resulting from the covalently bound surface dipole. Furthermore, X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm -2 within -0.5 V of the reversible hydrogen electrode.« less

Enargite oxidation: A review

NASA Astrophysics Data System (ADS)

Lattanzi, Pierfranco; Da Pelo, Stefania; Musu, Elodia; Atzei, Davide; Elsener, Bernhard; Fantauzzi, Marzia; Rossi, Antonella

2008-01-01

Enargite, Cu 3AsS 4, is common in some deposit types, e.g. porphyry systems and high sulphidation epithermal deposits. It is of environmental concern as a potential source of arsenic. In this communication, we review the current knowledge of enargite oxidation, based on the existing literature and our own original data. Explicit descriptions of enargite oxidation in natural environments are scarce. The most common oxidized alteration mineral of enargite is probably scorodite, FeAsO 4.2H 2O, with iron provided most likely by pyrite, a phase almost ubiquitously associated with enargite. Other secondary minerals after enargite include arsenates such as chenevixite, Cu 2Fe 2(AsO 4) 2(OH) 4.H 2O, and ceruleite, Cu 2Al 7(AsO 4) 4.11.5H 2O, and sulphates such as brochantite, Cu 4(SO 4)(OH) 6, and posnjakite, Cu 4(SO 4)(OH) 6·H 2O. Detailed studies of enargite field alteration at Furtei, Sardinia, suggest that most alteration occurs through dissolution, as testified by the appearance of etch pits at the surface of enargite crystals. However, apparent replacement by scorodite and cuprian melanterite was observed. Bulk oxidation of enargite in air is a very slow process. However, X-ray photoelectron spectroscopy (XPS) reveals subtle surface changes. From synchrotron-based XPS it was suggested that surface As atoms react very fast, presumably by forming bonds with oxygen. Conventional XPS shows the formation, on aged samples, of a nanometer-size alteration layer with an appreciably distinct composition with respect to the bulk. Mechanical activation considerably increases enargite reactivity. In laboratory experiments at acidic to neutral pH, enargite oxidation/dissolution is slow, although it is accelerated by the presence of ferric iron and/or bacteria such as Acidithiobacillus ferrooxidans and Sulfolobus BC. In the presence of sulphuric acid and ferric iron, the reaction involves dissolution of Cu and formation of native sulphur, subsequently partly oxidized to sulphate. At alkaline pH, the reactivity of enargite is apparently slightly greater. XPS spectra of surfaces conditioned at pH 11 have been interpreted as evidence of formation of a number of surface species, including cupric oxide and arsenic oxide. Treatment with hypochlorite solutions at pH 12.5 quickly produces a coating of cupric oxide. Electrochemical oxidation of enargite typically involves low current densities, confirming that the oxidation process is slow. Important surface changes occur only at high applied potentials, e.g. + 0.74 V vs. SHE. It is confirmed that, at acidic pH, the dominant process is Cu dissolution, accompanied (at + 0.56 V vs. SHE, pH = 1) by formation of native sulphur. At alkaline pH, a number of surface products have been suggested, including copper and arsenic oxides, and copper arsenates. XPS studies of the reacted surfaces demonstrate the evolution of Cu from the monovalent to the divalent state, the formation of As-O bonds, and the oxidation of sulphur to polysulphide, sulphite and eventually sulphate. In most natural and quasi-natural (mining) situations, it is expected that enargite reactivity will be slow. Moreover, it is likely that the release of arsenic will be further slowed down by at least temporary trapping in secondary phases. Therefore, an adequate management of exposed surfaces and wastes should minimize the environmental impact of enargite-bearing deposits. In spite of an increasing body of data, there are several gaps in our knowledge of enargite oxidation. The exact nature of most mechanisms and products remains poorly constrained, and there is a lack of quantitative data on the dependence on parameters such as pH and dissolved oxygen.

Volume Ice Radiolysis in the Outer Solar System

NASA Technical Reports Server (NTRS)

Cooper, John F.; Cooper, Paul D.

2006-01-01

The primary energy flux of charged particle components of the heliospheric and magnetospheric environments of the solar system is primarily carried by highly penetrating energetic particles. Although laboratory experiments on production of organics and oxidants typically only address effects on very thin surface layers, energy deposition occurs on surfaces of icy bodies of the outer solar system to meters in depth. Time scales for significant radiolytic deposition vary from thousands of years at millimeter depths on Europa to billions of years in the meters-deep regolith of Kuiper Belt Objects. Radioisotope decay (e.g., K-40) also contributes to volume radiolysis as the only energy source at much greater depths. Radiolytic oxygen is a potential resource for life within Europa and a partial source of oxygen for Saturn's magnetosphere and Titan's upper atmosphere. Interactions of very high energy cosmic rays with ices at Titan's surface may provide one of the few sources of oxidants in that highly reducing environment. The red colors of low-inclination classical Kuiper Belt Objects at 40-50 AU, and Centaur objects originating from this same population, may arise from volume radiolysis of deep ice layers below more refractory radiation crusts eroded away by surface sputtering and micrometeoroid impacts. A variety of techniques are potentially available to measure volume radiolysis products and have been proposed for study as part of the new Space Physics of Life initiative at NASA Goddard Space Flight Center. The technique of Electron Paramagnetic Resonance (EPR) has been used in medical studies to measure oxidant production in irradiated human tissue for cancer treatment. Other potential techniques include optical absorption spectroscopy and standard wet chemical analysis. These and other potential techniques are briefly reviewed for applicability to problems in solar system ice radiolysis and astrobiology.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Masuda, Takuya; PRESTO, Japan Science and Technology Agency; Yoshikawa, Hideki

In situ electrochemical X-ray photoelectron spectroscopy (XPS) apparatus, which allows XPS at solid/liquid interfaces under potential control, was constructed utilizing a microcell with an ultra-thin Si membrane, which separates vacuum and a solution. Hard X-rays from a synchrotron source penetrate into the Si membrane surface exposed to the solution. Electrons emitted at the Si/solution interface can pass through the membrane and be analyzed by an analyzer placed in vacuum. Its operation was demonstrated for potential-induced Si oxide growth in water. Effect of potential and time on the thickness of Si and Si oxide layers was quantitatively determined at sub-nanometer resolution.

The effects of interfacial potential on antimicrobial propensity of ZnO nanoparticle

PubMed Central

Arakha, Manoranjan; Saleem, Mohammed; Mallick, Bairagi C.; Jha, Suman

2015-01-01

The work investigates the role of interfacial potential in defining antimicrobial propensity of ZnO nanoparticle (ZnONP) against different Gram positive and Gram negative bacteria. ZnONPs with positive and negative surface potential are tested against different bacteria with varying surface potentials, ranging −14.7 to −23.6 mV. Chemically synthesized ZnONPs with positive surface potential show very high antimicrobial propensity with minimum inhibitory concentration of 50 and 100 μg/mL for Gram negative and positive bacterium, respectively. On other hand, ZnONPs of the same size but with negative surface potential show insignificant antimicrobial propensity against the studied bacteria. Unlike the positively charged nanoparticles, neither Zn2+ ion nor negatively charged ZnONP shows any significant inhibition in growth or morphology of the bacterium. Potential neutralization and colony forming unit studies together proved adverse effect of the resultant nano-bacterial interfacial potential on bacterial viability. Thus, ZnONP with positive surface potential upon interaction with negative surface potential of bacterial membrane enhances production of the reactive oxygen species and exerts mechanical stress on the membrane, resulting in the membrane depolarization. Our results show that the antimicrobial propensity of metal oxide nanoparticle mainly depends upon the interfacial potential, the potential resulting upon interaction of nanoparticle surface with bacterial membrane. PMID:25873247

Enhanced H2O2 Production at Reductive Potentials from Oxidized Boron-Doped Ultrananocrystalline Diamond Electrodes.

PubMed

Thostenson, James O; Ngaboyamahina, Edgard; Sellgren, Katelyn L; Hawkins, Brian T; Piascik, Jeffrey R; Klem, Ethan J D; Parker, Charles B; Deshusses, Marc A; Stoner, Brian R; Glass, Jeffrey T

2017-05-17

This work investigates the surface chemistry of H 2 O 2 generation on a boron-doped ultrananocrystalline diamond (BD-UNCD) electrode. It is motivated by the need to efficiently disinfect liquid waste in resource constrained environments with limited electrical power. X-ray photoelectron spectroscopy was used to identify functional groups on the BD-UNCD electrode surfaces while the electrochemical potentials of generation for these functional groups were determined via cyclic voltammetry, chronocoulometry, and chronoamperometry. A colorimetric technique was employed to determine the concentration and current efficiency of H 2 O 2 produced at different potentials. Results showed that preanodization of an as-grown BD-UNCD electrode can enhance the production of H 2 O 2 in a strong acidic environment (pH 0.5) at reductive potentials. It is proposed that the electrogeneration of functional groups at oxidative potentials during preanodization allows for an increased current density during the successive electrolysis at reductive potentials that correlates to an enhanced production of H 2 O 2 . Through potential cycling methods, and by optimizing the applied potentials and duty cycle, the functional groups can be stabilized allowing continuous production of H 2 O 2 more efficiently compared to static potential methods.

A Study on Factors Affecting the Degradation of Magnesium and a Magnesium-Yttrium Alloy for Biomedical Applications

PubMed Central

Johnson, Ian; Liu, Huinan

2013-01-01

Controlling degradation of magnesium or its alloys in physiological saline solutions is essential for their potential applications in clinically viable implants. Rapid degradation of magnesium-based materials reduces the mechanical properties of implants prematurely and severely increases alkalinity of the local environment. Therefore, the objective of this study is to investigate the effects of three interactive factors on magnesium degradation, specifically, the addition of yttrium to form a magnesium-yttrium alloy versus pure magnesium, the metallic versus oxide surfaces, and the presence versus absence of physiological salt ions in the immersion solution. In the immersion solution of phosphate buffered saline (PBS), the magnesium-yttrium alloy with metallic surface degraded the slowest, followed by pure magnesium with metallic or oxide surfaces, and the magnesium-yttrium alloy with oxide surface degraded the fastest. However, in deionized (DI) water, the degradation rate showed a different trend. Specifically, pure magnesium with metallic or oxide surfaces degraded the slowest, followed by the magnesium-yttrium alloy with oxide surface, and the magnesium-yttrium alloy with metallic surface degraded the fastest. Interestingly, only magnesium-yttrium alloy with metallic surface degraded slower in PBS than in DI water, while all the other samples degraded faster in PBS than in DI water. Clearly, the results showed that the alloy composition, presence or absence of surface oxide layer, and presence or absence of physiological salt ions in the immersion solution all influenced the degradation rate and mode. Moreover, these three factors showed statistically significant interactions. This study revealed the complex interrelationships among these factors and their respective contributions to degradation for the first time. The results of this study not only improved our understanding of magnesium degradation in physiological environment, but also presented the key factors to consider in order to satisfy the degradation requirements for next-generation biodegradable implants and devices. PMID:23799028

High temperature microelectrophoresis studies of the solid oxide/water interface

NASA Astrophysics Data System (ADS)

Fedkin, Mark Valentinovich

Metal oxides are abundant components of geo-environmental systems and are widely used materials in industry. Many practical applications of oxide materials require the knowledge of their surface properties at both ambient and elevated temperatures. Due to substantial technical challenges associated with experimental studies of solid/water interfaces at elevated temperatures, consistent data on adsorption, surface charge, and zeta potential for most oxide materials are limited to temperatures less than 100°C. A high temperature microelectrophoresis technique, developed in this study, made it possible to extend the zeta potential measurements at the solid oxide/water interface to 200°C. The design of the high temperature electrophoresis cell allowed for the visual microscopic observation of the electrophoretic movement of suspended particles through pressure-tight sapphire windows. The electrophoretic mobilities of metal oxide particles suspended in aqueous solutions were measured in a DC electric field as a function of pH, ionic strength, and temperature. The experimental procedure and methods for evaluation of the main experimental parameters (electrophoretic mobility, electric field strength, high temperature pH, and cell constant) have been developed. Zeta potentials were calculated from the experimental data using O'Brien and White's (1978) numerical solution for electrophoretic mobility equation. Zeta potentials and isoelectric points (IEP) of the metal oxide/aqueous solution interface were experimentally determined for ZrO2, TiO 2(rutile), and alphaAl2O3 at 25, 120, and 200°C. The background solutions used for the preparation of suspensions were pure H2O, NaCl(aq) (10-4--10-2 mol.kg-1), and SrCl2 (10-4 mol.kg, for TiO2). For all studied materials, the IEPs were found to regularly decrease with increasing temperature, which agrees with available theoretical predictions. Thermodynamic functions, including Gibbs energy, enthalpy, and heat capacity, were estimated for the H +/OH- adsorption from the experimental IEP data using the 1-pK model of the oxide/water interface. The experimental information obtained in this study combined with data from potentiometric titration and other experimental methods form the basis for future theoretical studies of the electrical double layer at the oxide/water interface.

An oxidized liquid metal-based microfluidic platform for tunable electronic device applications.

PubMed

Li, Guangyong; Parmar, Mitesh; Lee, Dong-Weon

2015-02-07

Easy movement of oxidized Galinstan in microfluidic channels is a promising way for the wide application of the non-toxic liquid metal. In this paper, two different surface modification techniques (physical and chemical) are reported, which dramatically improve the non-wetting characteristics of oxidized Galinstan in the microfluidic channel. In the physical technique, normal paper textures are transferred to the inner wall of polydimethylsiloxane (PDMS) channels and four types of nanoparticles are then coated on the surface of the wall for further improvement of the non-wetting characteristics. Highest advancing angle of 167° and receding angle of 151° are achieved on the paper-textured PDMS with titanium oxide (TiO2) nanoparticles. In the chemical technique, three types of inorganic acids are employed to generate dual-scale structures on the PDMS surface. The inner wall surface treated with sulfuric acid (H2SO4) shows the highest contact angle of 167° and a low hysteresis of ~14° in the dynamic measurement. Creating, transporting, separating and merging of oxidized Galinstan droplets are successfully demonstrated in the fabricated PDMS microfluidic channels. After optimization of these modification techniques, the potential application of tunable capacitors and electronic filters is realized by using liquid metal-based microfluidic devices.

Development of graphene oxide/poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) thin film-based electrochemical surface plasmon resonance immunosensor for detection of human immunoglobulin G

NASA Astrophysics Data System (ADS)

Pothipor, Chammari; Lertvachirapaiboon, Chutiparn; Shinbo, Kazunari; Kato, Keizo; Kaneko, Futao; Ounnunkad, Kontad; Baba, Akira

2018-02-01

An electrochemically synthesized graphene oxide (GO)/poly(3,4-ethylenedioxythiophene) (PEDOT)/poly(styrene sulfonate) (PSS) thin film-based electrochemical surface plasmon resonance (EC-SPR) sensor chip was developed and employed for the detection of human immunoglobulin G (IgG). GO introduced the carboxylic group on the film surface, which also allowed electrochemical control, for the immobilization of the anti-IgG antibody via covalent bonding through amide coupling reaction. The SPR sensitivity of the detection was improved under the control by applying an electrochemical potential, by which the sensitivity was increased by the increment in applied potential. Among the open-circuit and different applied potentials in the range of -1.0 to 0.50 V, the EC-SPR immunosensor at an applied potential of 0.50 V exhibited the highest sensitivity of 6.08 × 10-3 mL µg-1 cm-2 and linearity in the human IgG concentration range of 1.0 to 10 µg mL-1 with a relatively low detection limit of 0.35 µg mL-1. The proposed sensor chip is promising for immunosensing at the physiological level.

An ab initio study of Cu-based delafossites as an alternative to nickel oxide in photocathodes: effects of Mg-doping and surface electronic features.

PubMed

Schiavo, Eduardo; Latouche, Camille; Barone, Vincenzo; Crescenzi, Orlando; Muñoz-García, Ana B; Pavone, Michele

2018-05-23

CuMO2 delafossites (M = Al, Ga, and Cr) are p-type semiconductor oxides that have been recently proposed as the electrode in p-type dye-sensitized solar cells (p-DSSC) which is an alternative to the standard, low-performing nickel oxide. To assess this potential application of delafossites, we report here a DFT-based investigation of the structural and electronic properties of CuAlO2, CuGaO2 and CuCrO2. In particular, we address the role of Mg doping to obtain the p-type semiconducting character: the substitution of an M3+ cation with Mg2+ is easier with Ga than with Al and Cr, and, in all cases, the hole introduced by Mg2+ leads to the formation of Cu2+ species. Moreover, we address surface electronic features in order to characterize the most exposed delafossite surface termination and, more importantly, to predict the valence band maximum energy value, which determines the p-DSSC open circuit potential. From analysis of all our results, CuGaO2 emerges as the most promising system that can boost the development of new photocathodes for p-DSSCs.

Evaluating the oxidative, photothermal and electrical stability of colloidal nanocrystal solids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Law, Matt

2016-02-16

IV-VI quantum dot (QD) solids are a novel class of granular electronic materials with great technological potential (e.g., in photodetectors, field-effect transistors (FETs), and solar cells), but their oxidative and thermal instability present a barrier to practical applications [1]. Poor stability is a fundamental issue facing many nanoscale materials due to high surface area and surface energy. Basic studies are needed to elucidate the most important mechanisms of degradation and develop robust countermeasures if QD materials are to become technologically important. This project determined the degradation mechanisms of IV-VI QD solids (primarily PbSe and PbS) and introduced new chemical strategiesmore » to drastically improve their performance, stability, and operating lifetimes [2-5]. Our approach was based on (1) detailed testing of QD thin film materials (principally FETs and solar cells) as a function of oxidative and thermal stress, and (2) the use of organic and inorganic approaches to link the QDs into strongly electronically coupled, high-mobility films, prevent their oxidation, and eliminate internal degrees of freedom that lead to film instability and degradation in response to electrical and thermal stress. Stability against oxidation and thermal degradation was the major focus of this project. We have evaluated the stability of QD thin films and interfaces at temperatures less than 100°C (the regime most relevant to solar and transistor applications). Low-temperature oxidation and sintering of QD films have been investigated using optical absorption spectroscopy, Fourier transform infrared spectroscopy (FTIR), current-voltage scanning of transistors and solar cells, X-ray photoelectron spectroscopy, and scanning Kelvin probe microscopy (SKPM). SKPM was used to map the potential profiles of operating QD FETs and solar cells as a function of bias and illumination, which provides detailed information on how the work functions, potential drops and electric field within these devices determine device operation, and set the stage for future studies targeted at understanding and preventing device failure. We pursued two strategies to fabricate QD films with stable electrical characteristics: (1) the use of robust molecular surface ligands [2], and (2) “matrix engineering,” i.e., infilling the QD solid with metal oxide or metal sulfide matrices by low-temperature atomic layer deposition (ALD) to passivate surface states, prevent oxidation, lock the QDs into position, inhibit diffusion, and tune the height and width of the inter-QD potential barriers that govern charge transport [5,6]. Poor stability is a common feature of nanoscale electronic materials, yet stability is all too rarely the focus of basic research. Fundamental studies are therefore needed to elucidate the most important mechanisms of degradation and develop simple yet effective countermeasures. By revealing both how QD solids degrade in response to environmental stresses (oxidative, photothermal, and electric) and how to prevent this degradation, the project has greatly improved our ability to develop stable, high-performance QD materials for real-world applications.« less

A Method to Manipulate Surface Tension of a Liquid Metal via Surface Oxidation and Reduction

PubMed Central

Dickey, Michael D.

2016-01-01

Controlling interfacial tension is an effective method for manipulating the shape, position, and flow of fluids at sub-millimeter length scales, where interfacial tension is a dominant force. A variety of methods exist for controlling the interfacial tension of aqueous and organic liquids on this scale; however, these techniques have limited utility for liquid metals due to their large interfacial tension. Liquid metals can form soft, stretchable, and shape-reconfigurable components in electronic and electromagnetic devices. Although it is possible to manipulate these fluids via mechanical methods (e.g., pumping), electrical methods are easier to miniaturize, control, and implement. However, most electrical techniques have their own constraints: electrowetting-on-dielectric requires large (kV) potentials for modest actuation, electrocapillarity can affect relatively small changes in the interfacial tension, and continuous electrowetting is limited to plugs of the liquid metal in capillaries. Here, we present a method for actuating gallium and gallium-based liquid metal alloys via an electrochemical surface reaction. Controlling the electrochemical potential on the surface of the liquid metal in electrolyte rapidly and reversibly changes the interfacial tension by over two orders of magnitude (~500 mN/m to near zero). Furthermore, this method requires only a very modest potential (< 1 V) applied relative to a counter electrode. The resulting change in tension is due primarily to the electrochemical deposition of a surface oxide layer, which acts as a surfactant; removal of the oxide increases the interfacial tension, and vice versa. This technique can be applied in a wide variety of electrolytes and is independent of the substrate on which it rests. PMID:26863045

Chemical Functionalization of Graphene Family Members

NASA Astrophysics Data System (ADS)

Vacchi, Isabella Anna; Ménard-Moyon, Cécilia; Bianco, Alberto

2017-01-01

Thanks to their outstanding physicochemical properties, graphene and its derivatives are interesting nanomaterials with a high potential in several fields. Graphene, graphene oxide, and reduced graphene oxide, however, differ partially in their characteristics due to their diverse surface composition. Those differences influence the chemical reactivity of these materials. In the following chapter the reactivity and main functionalization reactions performed on graphene, graphene oxide, and reduced graphene oxide are discussed. A part is also dedicated to the main analytical techniques used for characterization of these materials. Functionalization of graphene and its derivatives is highly important to modulate their characteristics and design graphene-based conjugates with novel properties. Functionalization can be covalent by forming strong and stable bonds with the graphene surface, or non-covalent via π-π, electrostatic, hydrophobic, and/or van der Waals interactions. Both types of functionalization are currently exploited.

Direct k-space mapping of the electronic structure in an oxide-oxide interface.

PubMed

Berner, G; Sing, M; Fujiwara, H; Yasui, A; Saitoh, Y; Yamasaki, A; Nishitani, Y; Sekiyama, A; Pavlenko, N; Kopp, T; Richter, C; Mannhart, J; Suga, S; Claessen, R

2013-06-14

The interface between LaAlO(3) and SrTiO(3) hosts a two-dimensional electron system of itinerant carriers, although both oxides are band insulators. Interface ferromagnetism coexisting with superconductivity has been found and attributed to local moments. Experimentally, it has been established that Ti 3d electrons are confined to the interface. Using soft x-ray angle-resolved resonant photoelectron spectroscopy we have directly mapped the interface states in k space. Our data demonstrate a charge dichotomy. A mobile fraction contributes to Fermi surface sheets, whereas a localized portion at higher binding energies is tentatively attributed to electrons trapped by O vacancies in the SrTiO(3). While photovoltage effects in the polar LaAlO(3) layers cannot be excluded, the apparent absence of surface-related Fermi surface sheets could also be fully reconciled in a recently proposed electronic reconstruction picture where the built-in potential in the LaAlO(3) is compensated by surface O vacancies serving also as a charge reservoir.

Lactoferrin modified graphene oxide iron oxide nanocomposite for glioma-targeted drug delivery.

PubMed

Song, Meng-Meng; Xu, Huai-Liang; Liang, Jun-Xing; Xiang, Hui-Hui; Liu, Rui; Shen, Yu-Xian

2017-08-01

Targeting delivery of drugs in a specific manner represents a potential powerful technology in gliomas. Herein, we prepared a multifunctional targeted delivery system based on graphene oxide (GO) that contains a molecular bio-targeting ligand and superparamagnetic iron oxide nanoparticles on the surface of GO for magnetic targeting. Superparamagnetic Fe 3 O 4 nanoparticles was loaded on the surface of GO via chemical precipitation method to form GO@Fe 3 O 4 nanocomposites. Lactoferrin (Lf), an iron-transporting serum glycoprotein that binds to receptors overexpressed at the surface of glioma cells and vascular endothelial cell of the blood brain barrier, was chosen as the targeted ligand to construct the targeted delivery system Lf@GO@Fe 3 O 4 through EDC/NHS chemistry. With the confirmation of TEM, DLS and VSM, the resulting Lf@GO@Fe 3 O 4 had a size distribution of 200-1000nm and exhibited a superparamagnetic behavior. The nano delivery system had a high loading capacity and exhibited a pH-dependent release behavior. Compared with free DOX and DOX@GO@Fe 3 O 4 , Lf@GO@Fe 3 O 4 @DOX displayed greater intracellular delivery efficiency and stronger cytotoxicity against C6 glioma cells. The results demonstrated the potential utility of Lf conjugated GO@Fe 3 O 4 nanocomposites for therapeutic application in the treatment of gliomas. Copyright © 2017. Published by Elsevier B.V.

Potential-specific structure at the hematite-electrolyte interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

McBriarty, Martin E.; Stubbs, Joanne; Eng, Peter

The atomic-scale structure of interfaces between metal oxides and aqueous electrolytes controls their catalytic, geochemical, and corrosion behavior. Measurements that probe these interfaces in situ provide important details of ion and solvent arrangements, but atomically precise structural models do not exist for common oxide-electrolyte interfaces far from equilibrium. Using a novel cell, we measured the structure of the hematite (a-Fe 2O 3) (110more » $$\\bar{2}$$)-electrolyte interface under controlled electrochemical bias using synchrotron crystal truncation rod X ray scattering. At increasingly cathodic potentials, charge-compensating protonation of surface oxygen groups increases the coverage of specifically bound water while adjacent water layers displace outwardly and became disordered. Returning to open circuit potential leaves the surface in a persistent metastable protonation state. The flux of current and ions at applied potential is thus regulated by a unique interfacial electrolyte environment, suggesting that electrical double layer models should be adapted to the dynamically changing interfacial structure far from equilibrium.« less

Single-layered graphene oxide nanosheet/polyaniline hybrids fabricated through direct molecular exfoliation.

PubMed

Chen, Guan-Liang; Shau, Shi-Min; Juang, Tzong-Yuan; Lee, Rong-Ho; Chen, Chih-Ping; Suen, Shing-Yi; Jeng, Ru-Jong

2011-12-06

In this study, we used direct molecular exfoliation for the rapid, facile, large-scale fabrication of single-layered graphene oxide nanosheets (GOSs). Using macromolecular polyaniline (PANI) as a layered space enlarger, we readily and rapidly synthesized individual GOSs at room temperature through the in situ polymerization of aniline on the 2D GOS platform. The chemically modified GOS platelets formed unique 2D-layered GOS/PANI hybrids, with the PANI nanorods embedded between the GO interlayers and extended over the GO surface. X-ray diffraction revealed that intergallery expansion occurred in the GO basal spacing after the PANI nanorods had anchored and grown onto the surface of the GO layer. Transparent folding GOSs were, therefore, observed in transmission electron microscopy images. GOS/PANI nanohybrids possessing high conductivities and large work functions have the potential for application as electrode materials in optoelectronic devices. Our dispersion/exfoliation methodology is a facile means of preparing individual GOS platelets with high throughput, potentially expanding the applicability of nanographene oxide materials. © 2011 American Chemical Society

Characterization of a Self-Assembled Monolayer of 1-Thio-β-D-Glucose with Electrochemical Surface Enhanced Raman Spectroscopy Using a Nanoparticle Modified Gold Electrode.

PubMed

Smith, Scott R; Seenath, Ryan; Kulak, Monika R; Lipkowski, Jacek

2015-09-15

Preparation of a nanoparticle modified gold substrate designed for characterization of hydrophilic self-assembled monolayers (SAMs) of 1-thio-β-D-glucose (TG) with electrochemical surface-enhanced Raman spectroscopy (EC-SERS) is presented. Citrate stabilized gold nanoparticles were deposited on a polycrystalline gold electrode and subjected to an electrochemical desorption procedure to completely remove all traces of adsorbed citrate. Complete desorption of citrate was confirmed by recording cyclic voltammetry curves and SERS spectra. The citrate-free nanoparticle modified gold electrode was then incubated in a 1 mg mL(-1) aqueous solution of TG for 16 h prior to being characterized by EC-SERS. The SERS spectra confirmed that at potentials more negative than -0.10 V vs SCE thioglucose forms a monolayer in which the majority of the molecules preserve their lactol ring structure and only a small fraction of molecules appear to be oxidized. At potentials more positive than -0.10 V, the oxidation of TG molecules becomes prominent, and at potentials more positive than 0.20 V vs SCE, the monolayer of TG consists chiefly of oxidized product. The SERS spectra collected in the double layer region suggest the SAM of TG is well hydrated and hence can be used for hydrophilic modifications of a gold surface.

A Study of the Mechanism of the Hydrogen Evolution Reaction on Nickel by Surface Interrogation Scanning Electrochemical Microscopy.

PubMed

Liang, Zhenxing; Ahn, Hyun S; Bard, Allen J

2017-04-05

The hydrogen evolution reaction (HER) on Ni in alkaline media was investigated by scanning electrochemical microscopy under two operating modes. First, the substrate generation/tip collection mode was employed to extract the "true" cathodic current associated with the HER from the total current in the polarization curve. Compared to metallic Ni, the electrocatalytic activity of the HER is improved in the presence of the low-valence-state oxide of Ni. This result is in agreement with a previous claim that the dissociative adsorption of water can be enhanced at the Ni/Ni oxide interface. Second, the surface-interrogation scanning electrochemical microscopy (SI-SECM) mode was used to directly measure the coverage of the adsorbed hydrogen on Ni at given potentials. Simulation indicates that the hydrogen coverage follows a Frumkin isotherm with respect to the applied potential. On the basis of the combined analysis of the Tafel slope and surface hydrogen coverage, the rate-determining step is suggested to be the adsorption of hydrogen (Volmer step) in the investigated potential window.

Oxidative degradation of nalidixic acid by nano-magnetite via Fe2+/O2-mediated reactions.

PubMed

Ardo, Sandy G; Nélieu, Sylvie; Ona-Nguema, Georges; Delarue, Ghislaine; Brest, Jessica; Pironin, Elsa; Morin, Guillaume

2015-04-07

Organic pollution has become a critical issue worldwide due to the increasing input and persistence of organic compounds in the environment. Iron minerals are potentially able to degrade efficiently organic pollutants sorbed to their surfaces via oxidative or reductive transformation processes. Here, we explored the oxidative capacity of nano-magnetite (Fe3O4) having ∼ 12 nm particle size, to promote heterogeneous Fenton-like reactions for the removal of nalidixic acid (NAL), a recalcitrant quinolone antibacterial agent. Results show that NAL was adsorbed at the surface of magnetite and was efficiently degraded under oxic conditions. Nearly 60% of this organic contaminant was eliminated after 30 min exposure to air bubbling in solution in the presence of an excess of nano-magnetite. X-ray diffraction (XRD) and Fe K-edge X-ray absorption spectroscopy (XANES and EXAFS) showed a partial oxidation of magnetite to maghemite during the reaction, and four byproducts of NAL were identified by liquid chromatography-mass spectroscopy (UHPLC-MS/MS). We also provide evidence that hydroxyl radicals (HO(•)) were involved in the oxidative degradation of NAL, as indicated by the quenching of the degradation reaction in the presence of ethanol. This study points out the promising potentialities of mixed valence iron oxides for the treatment of soils and wastewater contaminated by organic pollutants.

In Situ Scanning Tunneling Microscopy Topography Changes of Gold (111) in Aqueous Sulfuric Acid Produced by Electrochemical Surface Oxidation and Reduction and Relaxation Phenomena

NASA Astrophysics Data System (ADS)

Pasquale, M. A.; Nieto, F. J. Rodríguez; Arvia, A. J.

The electrochemical formation and reduction of O-layers on gold (111) films in 1 m sulfuric acid under different potentiodynamic routines are investigated utilizing in situ scanning tunneling microscopy. The surface dynamics is interpreted considering the anodic and cathodic reaction pathways recently proposed complemented with concurrent relaxation phenomena occurring after gold (111) lattice mild disruption (one gold atom deep) and moderate disruption (several atoms deep). The dynamics of both oxidized and reduced gold topographies depends on the potentiodynamic routine utilized to form OH/O surface species. The topography resulting from a mild oxidative disruption is dominated by quasi-2D holes and hillocks of the order of 5 nm, involving about 500-600 gold atoms each, and their coalescence. A cooperative turnover process at the O-layer, in which the anion ad-layer and interfacial water play a key role, determines the oxidized surface topography. The reduction of these O-layers results in gold clusters, their features depending on the applied potential routine. A moderate oxidative disruption produces a surface topography of hillocks and holes several gold atoms high and deep, respectively. The subsequent reduction leads to a spinodal gold pattern. Concurrent coalescence appears to be the result of an Ostwald ripening that involves the surface diffusion of both gold atoms and clusters. These processes produce an increase in surface roughness and an incipient gold faceting. The dynamics of different topographies can be qualitatively explained employing the arguments from colloidal science theory. For 1.1 V ≤ E ≅ Epzc weak electrostatic repulsions favor gold atom/cluster coalescence, whereas for E < Epzc the attenuated electrostatic repulsions among gold surfaces stabilize small clusters over the substrate producing string-like patterns.

Secondary electron emission influenced by oxidation on the aluminum surface: the roles of the chemisorbed oxygen and the oxide layer

NASA Astrophysics Data System (ADS)

Li, Jiangtao; Hoekstra, Bart; Wang, Zhen-Bin; Qiu, Jie; Pu, Yi-Kang

2018-04-01

A relationship between the apparent secondary electron yield ({γ }{{se}}) and the oxygen coverage/oxide layer thickness on an aluminum cathode is obtained in an experiment under a controlled environment. The apparent secondary electron yield ({γ }{{se}}) is deduced from the breakdown voltage between two parallel plate electrodes in a 360 mTorr argon environment using a simple Townsend breakdown model with the assumption that the variation of the apparent secondary electron yield is dominated by the variation of the argon ion induced processes. The oxygen coverage/oxide layer thickness on the aluminum cathode is measured by a semi in situ x-ray photoemission spectroscopy equipment which is directly attached to the discharge chamber. It is found that three phases exist: (1) in the monomonolayer regime, as the oxygen coverage increases from 0 to 0.3, {γ }{{se}} decreases by nearly 40 % , (2) as the oxygen coverage increases from 0.3 to 1, {γ }{{se}} keeps nearly constant, (3) as the oxide layer thickness increases from about 0.3 nm to about 1.1 nm, {γ }{{se}} increases by 150 % . We propose that, in the submonolayer regime, the chemisorbed oxygen on the aluminum surface causes the decrease of {γ }{{se}} by creating a local potential barrier, which reduces the Auger neutralization rate and the energy gained by the Auger electrons. In the multilayer regime, as the oxide layer grows in thickness, there are three proposed mechanisms which cause the increase of {γ }{{se}}: (1) the work function decreases; (2) resonance neutralization and Auger de-excitation may exist. This is served as another channel for secondary electron production; (3) the kinetic energy of Auger electrons is increased on average, leading to a higher probability for electrons to overcome the surface potential barrier.

Separating nano graphene oxide from the residual strong-acid filtrate of the modified Hummers method with alkaline solution

NASA Astrophysics Data System (ADS)

Hu, Xuebing; Yu, Yun; Wang, Yongqing; Zhou, Jianer; Song, Lixin

2015-02-01

In the modified Hummers method for preparing graphene oxide, the yellow slurry can be obtained. After filtering through a quantitative filter paper, the strong-acid filtrate containing the unprecipitated nano graphene oxide was gained. The corresponding filtrate was added gradually with an alkaline (NaOH or KOH) solution at room temperature. The unprecipitated nano graphene oxide could undergo fast aggregation when the pH value of the filtrate was about 1.7 and formed the stable floccules. X-ray diffraction analysis shows the dominant peak of the floccules is about 11°, which accords to the peak of graphene oxide. Spectra of X-ray photoelectron spectroscopy confirm the presence in the floccules of an abundance of oxygen functional groups and the purified graphene oxide floccules can be obtained. Atomic force microscopy measurement shows the graphene oxide floccules consists of sheet-like objects, mostly containing only a few layers (about 5 layers). Zeta potential analysis demonstrates the surface charge of the graphene oxide is pH-sensitive and its isoelectric point is ∼1.7. The flocculation mechanism of graphene oxide ascribes to the acid-base interaction with the surface functional groups of the carbon layers.

Effect of different alloyed layers on the high temperature oxidation behavior of newly developed Ti 2AlNb-based alloys

NASA Astrophysics Data System (ADS)

Wu, Hongyan; Zhang, Pingze; Zhao, Haofeng; Wang, Ling; Xie, Aigen

2011-01-01

The application of titanium aluminide orthorhombic alloys (O-phase alloys) as potential materials in aircraft and jet engines was limited by their poor oxidation resistance at high temperature. The Ti 2AlNb-based alloys were chromised (Cr), chromium-tungstened (Cr-W) and nickel-chromised (Ni-Cr) by the double glow plasma surface alloying process to improve their high temperature oxidation resistance. The discontinuous oxidative behavior of Cr, Cr-W and Ni-Cr alloyed layers on Ti 2AlNb-based alloy at 1093 K was explored in this study. After exposing at 1093 K, the TiO 2 layer was formed on the bare alloy and accompanied by the occurrence of crack, which promoted oxidation rate. The oxidation behavior of Ti 2AlNb-based alloys was improved by surface alloying due to the formation of protective Al 2O 3 scale or continuous and dense NiCr 2O 4 film. The Ni-Cr alloyed layer presented the best high-temperature oxidation resistance among three alloyed layers.

Energy of Supported Metal Catalysts: From Single Atoms to Large Metal Nanoparticles

DOE PAGES

James, Trevor E.; Hemmingson, Stephanie L.; Campbell, Charles T.

2015-08-14

It is known that many catalysts consist of late transition metal nanoparticles dispersed across oxide supports. The chemical potential of the metal atoms in these particles correlate with their catalytic activity and long-term thermal stability. This chemical potential versus particle size across the full size range between the single isolated atom and bulklike limits is reported here for the first time for any metal on any oxide. The chemical potential of Cu atoms on CeO 2(111) surfaces, determined by single crystal adsorption calorimetry of gaseous Cu atoms onto slightly reduced CeO 2(111) at 100 and 300 K is shown tomore » decrease dramatically with increasing Cu cluster size. The Cu chemical potential is ~110 kJ/mol higher for isolated Cu adatoms on stoichometric terrace sites than for Cu in nanoparticles exceeding 2.5 nm diameter, where it reaches the bulk Cu(solid) limit. In Cu dimers, Cu’s chemical potential is ~57 kJ/mol lower at step edges than on stoichiometric terrace sites. Since Cu avoids oxygen vacancies, these monomer and dimer results are not strongly influenced by the 2.5% oxygen vacancies present on this CeO 2 surface and are thus considered representative of stoichiometric CeO 2(111) surfaces.« less

Toxicity Assessment of Silica Coated Iron Oxide Nanoparticles and Biocompatibility Improvement by Surface Engineering

PubMed Central

Malvindi, Maria Ada; De Matteis, Valeria; Galeone, Antonio; Brunetti, Virgilio; Anyfantis, George C.; Athanassiou, Athanassia; Cingolani, Roberto; Pompa, Pier Paolo

2014-01-01

We have studied in vitro toxicity of iron oxide nanoparticles (NPs) coated with a thin silica shell (Fe3O4/SiO2 NPs) on A549 and HeLa cells. We compared bare and surface passivated Fe3O4/SiO2 NPs to evaluate the effects of the coating on the particle stability and toxicity. NPs cytotoxicity was investigated by cell viability, membrane integrity, mitochondrial membrane potential (MMP), reactive oxygen species (ROS) assays, and their genotoxicity by comet assay. Our results show that NPs surface passivation reduces the oxidative stress and alteration of iron homeostasis and, consequently, the overall toxicity, despite bare and passivated NPs show similar cell internalization efficiency. We found that the higher toxicity of bare NPs is due to their stronger in-situ degradation, with larger intracellular release of iron ions, as compared to surface passivated NPs. Our results indicate that surface engineering of Fe3O4/SiO2 NPs plays a key role in improving particles stability in biological environments reducing both cytotoxic and genotoxic effects. PMID:24465736

Electrochemical characterization of gelatinized starch dispersions: voltammetry and electrochemical impedance spectroscopy on platinum surface.

PubMed

Hernandez-Jaimes, C; Lobato-Calleros, C; Sosa, E; Bello-Pérez, L A; Vernon-Carter, E J; Alvarez-Ramirez, J

2015-06-25

The electrochemical properties of gelatinized starch dispersions (GSD; 5% w/w) from different botanical sources were studied using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests over a platinum surface. The phenomenological modelling of EIS data using equivalent circuits indicated that after gelatinization the electrical resistance was determined mainly by the resistance of insoluble material (i.e., ghosts). Sonication of the GSD disrupted the ghost microstructure, and produced an increase in electrical conductivity by reducing the resistance of the insoluble material. The CV data showed three oxidation peaks at potentials where glucose solutions displayed oxidation waves. It is postulated that hydrolysis at the bulk and electrocatalyzed oxidation on the Pt-surface are reactions involved in the starch transformation. Starches peak intensity increased with the amylose content, suggesting that the amylose-rich matrix played an important role in the charge transfer in the electrolytic system. Copyright © 2015 Elsevier Ltd. All rights reserved.

Fabricating Ohmic contact on Nb-doped SrTiO{sub 3} surface in nanoscale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Yuhang; National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics, Chinese Academy of Engineering Physics, Mianyang, Sichuan 621999; Shi, Xiaolan

2016-05-09

Fabricating reliable nano-Ohmic contact on wide gap semiconductors is an important yet difficult step in oxide nanoelectronics. We fabricated Ohmic contact on the n-type wide gap oxide Nb-doped SrTiO{sub 3} in nanoscale by mechanically scratching the surface using an atomic force microscopy tip. Although contacted to high work function metal, the scratched area exhibits nearly linear IV behavior with low contact resistance, which maintains for hours in vacuum. In contrast, the unscratched area shows Fowler–Nordheim tunneling dominated Schottky rectifying behavior with high contact resistance. It was found that the Ohmic conductivity in the scratched area was drastically suppressed by oxygenmore » gas indicating the oxygen vacancy origin of the Ohmic behavior. The surface oxygen vacancy induced barrier width reduction was proposed to explain the phenomena. The nanoscale approach is also applicable to macroscopic devices and has potential application in all-oxide devices.« less

Surface oxidation under ambient air--not only a fast and economical method to identify double bond positions in unsaturated lipids but also a reminder of proper lipid processing.

PubMed

Zhou, Ying; Park, Hyejung; Kim, Philseok; Jiang, Yan; Costello, Catherine E

2014-06-17

A simple, fast approach elucidated carbon-carbon double bond positions in unsaturated lipids. Lipids were deposited onto various surfaces and the products from their oxidation in ambient air were observed by electrospray ionization (ESI) mass spectrometry (MS). The most common oxidative products, aldehydes, were detected as transformations at the cleaved double bond positions. Ozonides and carboxylic acids were generated in certain lipids. Investigations of the conditions controlling the appearance of these products indicated that the surface oxidation depends on light and ambient air. Since the lipid oxidation was slower in a high concentration of ozone, singlet oxygen appeared to be a parallel oxidant for unsaturated lipids. The 3-hydroxyl group in the sphingoid base of sulfatides offered some protection from oxidation for the Δ4,5-double bond, slowing its oxidation rate relative to that of the isolated double bond in the N-linked fatty acyl chain. Direct sampling by thin-layer chromatography (TLC)-ESI-MS provides a powerful approach to elucidate detailed structural information on biological samples. Co-localization of the starting lipids and their oxidation products after TLC separation allowed assignment of the native unsaturation sites. Phosphatidylserine and N,N-dimethyl phosphatidylethanolamine isomers in a bovine brain total lipid extract were distinguished on the basis of their oxidation products. Meanwhile, the findings reported herein reveal a potential pitfall in the assignment of structures to lipids extracted from TLC plates because of artifactual oxidation after the plate development.

Surface electrical properties of stainless steel fibres: An AFM-based study

NASA Astrophysics Data System (ADS)

Yin, Jun; D'Haese, Cécile; Nysten, Bernard

2015-03-01

Atomic force microscopy (AFM) electrical modes were used to study the surface electrical properties of stainless steel fibres. The surface electrical conductivity was studied by current sensing AFM and I-V spectroscopy. Kelvin probe force microscopy was used to measure the surface contact potential. The oxide film, known as passivation layer, covering the fibre surface gives rise to the observation of an apparently semiconducting behaviour. The passivation layer generally exhibits a p-type semiconducting behaviour, which is attributed to the predominant formation of chromium oxide on the surface of the stainless steel fibres. At the nanoscale, different behaviours are observed from points to points, which may be attributed to local variations of the chemical composition and/or thickness of the passivation layer. I-V curves are well fitted with an electron tunnelling model, indicating that electron tunnelling may be the predominant mechanism for electron transport.

Hip Dislocation Increases Roughness of Oxidized Zirconium Femoral Heads in Total Hip Arthroplasty: An Analysis of 59 Retrievals

PubMed Central

Moussa, Mohamed E.; Esposito, Christina I.; Elpers, Marcella E.; Wright, Timothy M.; Padgett, Douglas E.

2014-01-01

The aims of this study were to assess damage on the surface of retrieved oxidized zirconium metal (OxZr) femoral heads, to measure surface roughness of scratches, and to evaluate the extent of surface effacement using scanning electron microscopy (SEM). Ceramic zirconia-toughened alumina (ZTA) heads were analyzed for comparison. OxZr femoral heads explanted for recurrent dislocation had the most severe damage (p<0.001). The median surface roughness of damaged OxZr femoral heads was 1.49μm, compared to 0.084μm for damaged ZTA heads and 0.052μm for undamaged OxZr (p<0.001). This may be of clinical concern because increased surface roughness has the potential to increase the wear of polyethylene liners articulating against these OxZr heads in THA. PMID:25443362

Mechanical writing of n-type conductive layers on the SrTiO3 surface in nanoscale

PubMed Central

Wang, Yuhang; Zhao, Kehan; Shi, Xiaolan; Li, Geng; Xie, Guanlin; Lai, Xubo; Ni, Jun; Zhang, Liuwan

2015-01-01

The fabrication and control of the conductive surface and interface on insulating SrTiO3 bulk provide a pathway for oxide electronics. The controllable manipulation of local doping concentration in semiconductors is an important step for nano-electronics. Here we show that conductive patterns can be written on bare SrTiO3 surface by controllable doping in nanoscale using the mechanical interactions of atomic force microscopy tip without applying external electric field. The conductivity of the layer is n-type, oxygen sensitive, and can be effectively tuned by the gate voltage. Hence, our findings have potential applications in oxide nano-circuits and oxygen sensors. PMID:26042679

Exploring a potential energy surface by machine learning for characterizing atomic transport

NASA Astrophysics Data System (ADS)

Kanamori, Kenta; Toyoura, Kazuaki; Honda, Junya; Hattori, Kazuki; Seko, Atsuto; Karasuyama, Masayuki; Shitara, Kazuki; Shiga, Motoki; Kuwabara, Akihide; Takeuchi, Ichiro

2018-03-01

We propose a machine-learning method for evaluating the potential barrier governing atomic transport based on the preferential selection of dominant points for atomic transport. The proposed method generates numerous random samples of the entire potential energy surface (PES) from a probabilistic Gaussian process model of the PES, which enables defining the likelihood of the dominant points. The robustness and efficiency of the method are demonstrated on a dozen model cases for proton diffusion in oxides, in comparison with a conventional nudge elastic band method.

Transpassive Dissolution of Copper and Rapid Formation of Brilliant Colored Copper Oxide Films

NASA Astrophysics Data System (ADS)

Fredj, Narjes; Burleigh, T. David; New Mexico Tech Team

2014-03-01

This investigation describes an electrochemical technique for growing adhesive copper oxide films on copper with attractive colors ranging from gold-brown to pearl with intermediate colors from red violet to gold green. The technique consists of anodically dissolving copper at transpassive potentials in hot sodium hydroxide, and then depositing brilliant color films of Cu2O onto the surface of copper after the anodic potential has been turned off. The color of the copper oxide film depends on the temperature, the anodic potential, the time t1 of polarization, and the time t2, which is the time of immersion after potential has been turned off. The brilliant colored films were characterized using glancing angle x-ray diffraction, and the film was found to be primarily Cu2O. Cyclic voltammetry, chronopotentiometry, scanning electron microscopy, and x-ray photoelectron spectroscopy were also used to characterize these films.

High manganese concentrations in rocks at Gale crater, Mars

USGS Publications Warehouse

Lanza, Nina L.; Fischer, Woodward W.; Wiens, Roger C.; Grotzinger, John P.; Ollila, Ann M.; Anderson, Ryan B.; Clark, Benton C.; Gellert, Ralf; Mangold, Nicolas; Maurice, Sylvestre; Le Mouélic, Stéphane; Nachon, Marion; Schmidt, Mariek E.; Berger, Jeffrey; Clegg, Samuel M.; Forni, Olivier; Hardgrove, Craig; Melikechi, Noureddine; Newsom, Horton E.; Sautter, Violaine

2014-01-01

The surface of Mars has long been considered a relatively oxidizing environment, an idea supported by the abundance of ferric iron phases observed there. However, compared to iron, manganese is sensitive only to high redox potential oxidants, and when concentrated in rocks, it provides a more specific redox indicator of aqueous environments. Observations from the ChemCam instrument on the Curiosity rover indicate abundances of manganese in and on some rock targets that are 1–2 orders of magnitude higher than previously observed on Mars, suggesting the presence of an as-yet unidentified manganese-rich phase. These results show that the Martian surface has at some point in time hosted much more highly oxidizing conditions than has previously been recognized.

Sorption of carbamazepine by commercial graphene oxides: a comparative study with granular activated carbon and multiwalled carbon nanotubes.

PubMed

Cai, Nan; Larese-Casanova, Philip

2014-07-15

Graphene nanosheet materials represent a potentially new high surface area sorbent for the treatment of endocrine disrupting compounds (EDCs) in water. However, sorption behavior has been reported only for laboratory graphene prepared by a laborious and hazardous graphite exfoliation process. A careful examination of commercially available, clean, high-volume produced graphene materials should reveal whether they are appropriate for sorbent technologies and which physicochemical properties most influence sorption performance. In this study, three commercially available graphene oxide powders of various particle sizes, specific surface areas, and surface chemistries were evaluated for their sorption performance using carbamazepine and nine other EDCs and were compared to that of conventional granular activated carbon (GAC) and multi-walled carbon nanotubes (MWCNTs). Sorption kinetics of carbamazepine on graphene oxide powders was rapid and reversible with alcohol washing, consistent with π-π interactions. The various sorption extents as described by Freundlich isotherms were best explained by available surface area, and only the highest surface area graphene oxide (771 m(2)/g) out-performed GAC and MWCNTs. Increasing pH caused more negative surface charge, a twofold decrease in sorption of anionic ibuprofen, a onefold increase in sorption of cationic atenolol, and no change for neutral carbamazepine, highlighting the role of electrostatic interactions. Copyright © 2014 Elsevier Inc. All rights reserved.

Corrosion, ion release and Mott-Schottky probe of chromium oxide coatings in saline solution with potential for orthopaedic implant applications

NASA Astrophysics Data System (ADS)

Ogwu, A. A.; Oje, A. M.; Kavanagh, J.

2016-04-01

We report our investigation on chromium oxide thin film coatings that show a negligible ion release during electrochemical corrosion testing in saline solution. The chemical constituents of the films prepared by reactive magnetron sputtering were identified to be predominantly Cr2O3 based on Raman spectroscopy anti-symmetric stretching vibration modes for CrIII-O and other peaks and an FTIR spectroscopy E u vibrational mode at 409 cm-1. X-ray photoelectron spectroscopy, multiplet fitting for 2P 3/2 and 2P 1/2 states also confirmed the predominantly Cr2O3 stoichiometry in the films. The prepared chromium oxide coatings showed superior pitting corrosion resistance compared to the native chromium oxide films on bare uncoated stainless steel when tested under open circuit potential, potentiodynamic polarisation and cyclic voltammetry in saline solution. The chromium ion released into solution during the corrosion testing of stainless steel substrates coated with chromium oxide coatings was found to be negligibly small based on atomic absorption spectroscopy measurements. Our Mott-Schottky analysis investigation showed that the negligibly small ion release from the chromium oxide coated steel substrates is most likely due to a much lower defect density on the surface of the deposited coatings compared to the native oxide layer on the uncoated steel substrates. This opens up the opportunity for using chromium oxide surface coatings in hip, knee and other orthopaedic implants where possible metal ion release in vivo still poses a great challenge.

Surface Characterization of an Organized Titanium Dioxide Layer

NASA Astrophysics Data System (ADS)

Curtis, Travis

Soft lithographic printing techniques can be used to control the surface morphology of titanium dioxide layers on length scales of several hundred nanometers. Controlling surface morphology and volumetric organization of titanium dioxide electrodes can potentially be used in dye-sensitized solar cell devices. This thesis explores how layer-by-layer replication can lead to well defined, dimensionally controlled volumes and details how these control mechanisms influence surface characteristics of the semiconducting oxide.

Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol.

PubMed

Liu, Chang; Ma, Qingxin; Liu, Yongchun; Ma, Jinzhu; He, Hong

2012-02-07

Sulfate is one of the most important aerosols in the atmosphere. A new sulfate formation pathway via synergistic reactions between SO(2) and NO(2) on mineral oxides was proposed. The heterogeneous reactions of SO(2) and NO(2) on CaO, α-Fe(2)O(3), ZnO, MgO, α-Al(2)O(3), TiO(2), and SiO(2) were investigated by in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) at ambient temperature. Formation of sulfate from adsorbed SO(2) was promoted by the coexisting NO(2), while surface N(2)O(4) was observed as the crucial oxidant for the oxidation of surface sulfite. This process was significantly promoted by the presence of O(2). The synergistic effect between SO(2) and NO(2) was not observed on other mineral particles (such as CaCO(3) and CaSO(4)) probably due to the lack of the surface reactive oxygen sites. The synergistic reaction between SO(2) and NO(2) on mineral oxides resulted in the formation of internal mixtures of sulfate, nitrate, and mineral oxides. The change of mixture state will affect the physicochemical properties of atmospheric particles and therefore further influence their environmental and climate effects.

Damage free Ar ion plasma surface treatment on In{sub 0.53}Ga{sub 0.47}As-on-silicon metal-oxide-semiconductor device

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koh, Donghyi; Shin, Seung Heon; Ahn, Jaehyun

2015-11-02

In this paper, we investigated the effect of in-situ Ar ion plasma surface pre-treatment in order to improve the interface properties of In{sub 0.53}Ga{sub 0.47}As for high-κ top-gate oxide deposition. X-ray photoelectron spectroscopy (XPS) and metal-oxide-semiconductor capacitors (MOSCAPs) demonstrate that Ar ion treatment removes the native oxide on In{sub 0.53}Ga{sub 0.47}As. The XPS spectra of Ar treated In{sub 0.53}Ga{sub 0.47}As show a decrease in the AsO{sub x} and GaO{sub x} signal intensities, and the MOSCAPs show higher accumulation capacitance (C{sub acc}), along with reduced frequency dispersion. In addition, Ar treatment is found to suppress the interface trap density (D{sub it}),more » which thereby led to a reduction in the threshold voltage (V{sub th}) degradation during constant voltage stress and relaxation. These results outline the potential of surface treatment for III-V channel metal-oxide-semiconductor devices and application to non-planar device process.« less

Accelerated cell-surface interlocking on plasma polymer-modified porous ceramics.

PubMed

Rebl, Henrike; Finke, Birgit; Schmidt, Jürgen; Mohamad, Heba S; Ihrke, Roland; Helm, Christiane A; Nebe, J Barbara

2016-12-01

Excellent osseointegration of permanent implants is crucial for the long lasting success of the implantation. To improve the osseointegrative potential, bio-inert titanium alloy surfaces (Ti6Al4V) are modified by plasma chemical oxidation (PCO®) of the titanium-oxide layer to a non-stoichiometric, amorphous calcium phosphate layer. The native titanium-oxide film measuring only a few nanometers is converted by PCO® to a thick porous calcium phosphate layer of about 10μm. In a second step the PCO surface is combined with a cell adhesive plasma-polymerized allylamine (PPAAm) nano film (5 and 50nm). Independent of the PPAAm coating homogeneity, the human osteoblast-like MG-63 cells show a remarkable increase in cell size and well-developed filopodia. Analyses of the actin cytoskeleton reveal that the cells mold to the pore shape of the PPAAm-covered PCO, thereby establishing a strong attachment to the surface. Interestingly, we could demonstrate that even though our untreated PCO shows excellent hydrophilicity, this alone is not sufficient to facilitate fast cell spreading, but the positive surface charges mediated by PPAAm. This multilayer composite material guarantees enhanced interlocking of the cells with the porous surface. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of sterilisation method on surface topography and in-vitro cell behaviour of electrostatically spun scaffolds.

PubMed

Andrews, Kirstie D; Hunt, John A; Black, Richard A

2007-02-01

Electrostatic spinning is a potentially significant technique for scaffold production within the field of tissue engineering; however, the effect of sterilisation upon these structures is not known. This research investigated the extent of any topographical alteration to electrostatically spun scaffolds post-production through sterilisation, and examined any subsequent effect on contacting cells. Scaffolds made from Tecoflex SG-80A polyurethane were sterilised using ethylene oxide and UV-ozone. Scaffold topography was characterized in terms of inter-fibre separation (ifs), fibre diameter (f.dia) and surface roughness. Cell culture was performed over 7 days with both mouse L929 and human embryonic lung fibroblasts, the results of which were assessed using SEM, image analysis and confocal microscopy. Sterilisation by UV-ozone and ethylene oxide decreased ifs and increased f.dia; surface roughness was decreased by UV-ozone but increased by ethylene oxide. Possible mechanisms to explain these observations are discussed, namely photo-oxidative degradation in the case of UV-ozone and process-induced changes in surface roughness. UV-ozone sterilised scaffolds showed greater cell coverage than those treated with ethylene oxide, but lower coverage than all the controls. Changes in cell attachment and morphology were thought to be due to the changes in topography brought about by the sterilisation process. We conclude that surface modification by sterilisation could prove to be a useful tool at the final stage of scaffold production to enhance cell contact, phenotype or function.

Influence of microorganisms on the oxidation state distribution of multivalent actinides under anoxic conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reed, Donald Timothy; Borkowski, Marian; Lucchini, Jean - Francois

2010-12-10

The fate and potential mobility of multivalent actinides in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium, uranium and neptunium are the near-surface multivalent contaminants of concern and are also key contaminants for the deep geologic disposal of nuclear waste. Their mobility is highly dependent on their redox distribution at their contamination source as well as along their potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity.more » Under anoxic conditions, indirect and direct bioreduction mechanisms exist that promote the prevalence of lower-valent species for multivalent actinides. Oxidation-state-specific biosorption is also an important consideration for long-term migration and can influence oxidation state distribution. Results of ongoing studies to explore and establish the oxidation-state specific interactions of soil bacteria (metal reducers and sulfate reducers) as well as halo-tolerant bacteria and Archaea for uranium, neptunium and plutonium will be presented. Enzymatic reduction is a key process in the bioreduction of plutonium and uranium, but co-enzymatic processes predominate in neptunium systems. Strong sorptive interactions can occur for most actinide oxidation states but are likely a factor in the stabilization of lower-valent species when more than one oxidation state can persist under anaerobic microbiologically-active conditions. These results for microbiologically active systems are interpreted in the context of their overall importance in defining the potential migration of multivalent actinides in the subsurface.« less

Air-stable electrical conduction in oxidized poly[2-methoxy-5-(2-ethylhexyloxy)-p-phenylene vinylene] thin films

NASA Astrophysics Data System (ADS)

Hossein-Babaei, F.; Shabani, P.; Azadinia, M.

2013-11-01

Oxidation-caused electroluminescence and electrical conduction deteriorations in poly[2-methoxy-5-(2-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV) have prevented the material from being used in applications requiring air exposure. Here, we report air-stable electrical conduction in oxidized MEH-PPV layers produced by room temperature annealing of MEH-PPV thin films in air. Oxidized layers exhibit lower, but stable, conductivities. As the process is irreversible, the final conductivity is retained in vacuum, inert gas, hydrogen, and oxygen. The oxidation rates recorded at different conditions for layers of varied thickness and electrode configuration are described by a surface oxidation model. Potentials of the oxidized MEH-PPV layers in sensor technology are demonstrated.

Osteoconductive phosphoserine-modified poly(ε-lysine) dendrons: synthesis, titanium oxide surface functionalization and response of osteoblast-like cell lines

PubMed Central

Meikle, S. T.; Bianchi, G.; Olivier, G.; Santin, M.

2013-01-01

The lack of direct bonding between the surface of an implant and the mineralized bony tissue is among the main causes of aseptic loosening in titanium-based implants. Surface etching and ceramic coatings have led to improved osteointegration, but their clinical performance is still limited either by partial bonding or by coating delamination. In this work, a solid-phase synthesis method has been optimized to produce poly(ε-lysine) dendrons, the outermost branching generation of which is functionalized by phosphoserine (PS), a known catalyst of the biomineralization process. The dendrons were deposited onto etched titanium oxide surfaces as a near-to-monolayer film able to induce the formation of a homogeneous calcium phosphate phase in a simulated body fluid over 3 days. The dendron films also stimulated MG63 and SAOS-2 osteoblast-like cells to proliferate at a rate significantly higher than etched titanium, with SAOS-2 also showing a higher degree of differentiation over 14 days. PS-tethered dendron films were not affected by various sterilization methods and UV treatment appeared to improve the cell substrate potential of these films, thus suggesting their potential as a surface functionalization method for bone implants. PMID:23193106

Colour changes by laser irradiation of reddish building limestones

NASA Astrophysics Data System (ADS)

Grossi, C. M.; Benavente, D.

2016-10-01

We have used X-ray photoelectron spectroscopy (XPS) as a novel method to investigate the causes of colour changes in a reddish limestone under irradiation by a Q-switched Nd:YAG 1064 nm laser. We irradiated clean dry and wet surfaces of Pidramuelle Roja, a building stone frequently used in the Asturian heritage, at fluences ranging from 0.12 to 1.47 J cm-2. We measured the colour coordinates and undertook XPS analysis of the state of oxidation of iron both before and after irradiation. Visible colour changes and potential aesthetic damage occurred on dry surfaces from a fluence of 0.31 J cm-2, with the stone showing a greening effect and very intense darkening. The colour change on dry surfaces was considerably higher than on wet surfaces, which at the highest fluence (1.47 J cm-2) was also above the human visual detection threshold. The use of XPS demonstrated that the change in colour (chroma and hue) is associated with a reduction in the iron oxidation state on dry surfaces during laser irradiation. This points out to a potential routinary use of XPS to analyse causes of colour changes during laser cleaning in other types of coloured building stones.

Investigation of Silica-Supported Vanadium Oxide Catalysts by High-Field 51 V Magic-Angle Spinning NMR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jaegers, Nicholas R.; Wan, Chuan; Hu, Mary Y.

Supported V2O5/SiO2 catalysts were studied using solid state 51V MAS NMR at a sample spinning rate of 36 kHz and at a magnetic field of 19.975 T for a better understanding of the coordination of the vanadium oxide as a function of environmental conditions . Structural transformations of the supported vanadium oxide species between the catalyst in the dehydrated state and hydrated state under an ambient environment were revisited to examine the degree of oligomerization and the effect of water. The experimental results indicate the existence of a single dehydrated surface vanadium oxide species that resonates at -675 ppm andmore » two vanadium oxide species under ambient conditions that resonate at -566 and -610 ppm, respectively. No detectable structural difference was found as a function of vanadium oxide loading on SiO2 (3% V2O5/SiO2 and 8% V2O5/SiO2). Quantum chemistry simulations of the 51V NMR chemical shifts on predicted surface structures were used as an aide in understanding potential surface vanadium oxide species on the silica support. The results suggest the formation of isolated surface VO4 units for the dehydrated catalysts with the possibility of dimer and cyclic trimer presence. The absence of bridging V-O-V vibrations (~200-300 cm-1) in the Raman spectra [Gao et al. J. Phys. Chem. B 1998, 102, 10842-10852], however, indicates that the isolated surface VO4 sites are the dominant dehydrated surface vanadia species on silica. Upon exposure to water, hydrolysis of the bridging V-O-Si bonds is most likely responsible for the decreased electron shielding experienced by vanadium. No indicators for the presence of hydrated decavanadate clusters or hydrated vanadia gels previously proposed in the literature were detected in this study.« less

Covalent Surface Modification of Gallium Arsenide Photocathodes for Water Splitting in Highly Acidic Electrolyte.

PubMed

Garner, Logan E; Steirer, K Xerxes; Young, James L; Anderson, Nicholas C; Miller, Elisa M; Tinkham, Jonathan S; Deutsch, Todd G; Sellinger, Alan; Turner, John A; Neale, Nathan R

2017-02-22

Efficient water splitting using light as the only energy input requires stable semiconductor electrodes with favorable energetics for the water-oxidation and proton-reduction reactions. Strategies to tune electrode potentials using molecular dipoles adsorbed to the semiconductor surface have been pursued for decades but are often based on weak interactions and quickly react to desorb the molecule under conditions relevant to sustained photoelectrolysis. Here, we show that covalent attachment of fluorinated, aromatic molecules to p-GaAs(1 0 0) surfaces can be employed to tune the photocurrent onset potentials of p-GaAs(1 0 0) photocathodes and reduce the external energy required for water splitting. Results indicate that initial photocurrent onset potentials can be shifted by nearly 150 mV in pH -0.5 electrolyte under 1 Sun (1000 W m -2 ) illumination resulting from the covalently bound surface dipole. Though X-ray photoelectron spectroscopy analysis reveals that the covalent molecular dipole attachment is not robust under extended 50 h photoelectrolysis, the modified surface delays arsenic oxide formation that results in a p-GaAs(1 0 0) photoelectrode operating at a sustained photocurrent density of -20.5 mA cm -2 within -0.5 V of the reversible hydrogen electrode. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization and growth analysis of two types of thin films formed on copper surfaces: An inorganic chromium containing film and an organic film formed via reduction of diazonium ions

NASA Astrophysics Data System (ADS)

Hurley, Belinda Louise

Surface enhanced Raman scattering was used to observe interactions of dilute CrVI solutions with silver and copper surfaces in situ. Using silver as a model surface, CrIII was observed at the near monolayer level, and the spectra were compared to those from CrIII oxyhydroxide species and CrIII/Cr VI mixed oxide. Similar experiments were conducted with copper surfaces and 785 nm excitation. Upon exposure of a copper surface to CrVI solution, the characteristic copper oxide Raman bands disappeared, and a Cr III band increased in intensity over a period of ˜20 hours. The intensity of the CrIII band on copper became self limiting after the formation of several CrIII monolayers, as supported by chronoamperometry experiments. This CrIII spectrum was stable after CrVI was removed from the solution provided the potential remained negative of -200 mV vs. Ag/AgCl. The results support the conclusion that CrVI is reductively adsorbed to copper at the near neutral pH and open circuit potentials expected for Cu/Al alloys in field applications. The CrIII film is stable and strongly inhibits oxygen reduction at the treated copper surface. Copper surfaces and polished Aluminum Alloy 2024 T3 substrates were derivatized at open circuit potential with arenediazonium salts in both aprotic and aqueous media. Raman spectroscopy confirmed the presence of a derivatized film on the substrates before and after exposure to boiling water and sonication in acetone. Preliminary experiments to test these films for corrosion inhibition proved unsuccessful. Aluminum and copper substrates were prepared and used for x-ray photoelectron spectroscopy (XPS) analysis of the derivatization results. In the copper experiments, one surface was native oxide copper, predominantly in the form of Cu2O, and one surface was predominantly Cu 0. Results of the XPS analysis indicate the presence of a Cu-O-C linkage and possibly a Cu-C covalent bond between the aryl ring and the copper substrate. XPS results also indicate the formation of multilayers on both types of copper surfaces with different percentages of azo coupling within the multilayers on the two surfaces. These easily prepared, covalently bonded organic films could be used for applications currently fulfilled with self-absorbed monolayers and Langmuir Blodgett films.

Photoactivity of N-doped ZnO nanoparticles in oxidative and reductive reactions

NASA Astrophysics Data System (ADS)

Oliveira, Jéssica A.; Nogueira, André E.; Gonçalves, Maria C. P.; Paris, Elaine C.; Ribeiro, Caue; Poirier, Gael Y.; Giraldi, Tania R.

2018-03-01

N-doped ZnO is a prospective material for photocatalytic reactions. However, only oxidative paths are well investigated in the literature. This paper describes a comparative study about ZnO and ZnO:N potential for oxidative and reductive reactions, probed by rhodamine B dye photodegradation and CO2 photoreduction. The materials were prepared by the polymeric precursor method, using urea as a nitrogen source, and different heat treatments were used to observe their effects on surface decontamination, crystallinity, particle sizes and shapes, and photocatalytic performance. ZnO and ZnO:N presented a wurtzite crystalline structure and nanometric-scale particles. Samples submitted to higher temperatures showed lower specific surface areas, but higher crystallinity and lower contents of species adsorbed on their surfaces. On the other hand, the photocatalysts annealed in shorter times presented smaller crystallite sizes and lower crystallinity. These factors influenced the photoactivity in both conditions, i.e., oxidation and reduction reactions, under the ultraviolet and visible light, indicating that structural factors influenced the adequate charge separation and consequent photocatalytic activity since the as-synthesized samples were versatile photocatalysts in both redox reactions.

Graphene sheets modified with polyindole for electro-chemical detection of dopamine.

PubMed

Kumar, Ashish; Prakash, Rajiv

2014-03-01

Oxidized polyindole is coated over graphene surface by in-situ chemical oxidation method in dilute hydrochloric acid solution. Morphology of graphene modified with oxidized polyindole is investigated by scanning electron microscope. The interaction of graphene to polyindole is observed by Raman spectroscopy. The introduction of carboxylate functionality is observed in graphene due to pyrolysis. The association of this functionality with indole monomer and their interactive behaviour led to formation of uniform polyindole over graphene surface in presence of oxidizing agent. Our chemical synthesis results not only formation of uniform polymer thin layer over the graphene sheets but also enhances various properties and processibility of the graphene. Negative surface charge on the composite material is observed at acidic pH, which shows potential for accumulation of positively charged species in the solution. Further it is explored for electro-catalytic and sensing applications and shows cation permselective behavior of dopamine hydrochloride. It is demonstrated by differential pulse voltammetric technique in dopamine concentration range from 10 microM to 1 mM (in presence of 1 mM ascorbic acid).

Electrocatalytic behaviour of surface confined pentanethio cobalt (II) binuclear phthalocyanines towards the oxidation of 4-chlorophenol

NASA Astrophysics Data System (ADS)

Makinde, Zainab O.; Louzada, Marcel; Mashazi, Philani; Nyokong, Tebello; Khene, Samson

2017-12-01

Cobalt binuclear phthalocyanine (CoBiPc) bearing pentanethio substituents at the peripheral positions were synthesized. The immobilization of the synthesized cobalt phthalocyanines on gold electrode was achieved using self-assembled monolayer method (SAM). X-ray photoelectron spectroscopy (XPS) and Kelvin Probe (KP) techniques were used to characterise the formation of monomeric and binuclear phthalocyanine SAMs on the gold surface. The phthalocyanine SAMs on gold electrodes were investigated for electrocatalytic oxidation of 4-chlorophenol. The electrocatalytic properties of tetra- and octa- pentanethio substituted cobalt binuclear phthalocyanine (CoBiPc) are compared with their tetra- and octa-pentanethio substituted phthalocyanine (CoPc). The SAMs modified gold electrode surfaces showed a peak current enhancement and stability and reduction in electrocatalytic potentials compared to the bare or unmodified electrodes towards the detection of the 4-chlorophenol. The SAMs of cobalt binuclear phthalocyanines exhibited more enhanced electrocatalytic properties in terms of stability, detection peak current and reduction of the electrocatalytic over potential.

Hierarchical nano-on-micro copper with enhanced catalytic activity towards electro-oxidation of hydrazine

NASA Astrophysics Data System (ADS)

Yan, Xiaodong; Liu, Yuan; Scheel, Kyle R.; Li, Yong; Yu, Yunhua; Yang, Xiaoping; Peng, Zhonghua

2018-03-01

The electrochemical properties of catalyst materials are highly dependent on the materials structure and architecture. Herein, nano-on-micro Cu electrodes are fabricated by growing Cu microcrystals on Ni foam substrate, followed by introducing Cu nanocrystals onto the surface of the Cu microcrystals. The introduction of Cu nanocrystals onto the surface of Cu microcrystals is shown to dramatically increase the electrochemically active surface area and thus significantly enhances the catalytic activity of the catalyst electrode towards electro-oxidation of hydrazine. The onset potential (-1.04 V vs. Ag/AgCl) of the nano-on-micro Cu electrode is lower than those of the reported Cu-based catalysts under similar testing conditions, and a current density of 16 mA·cm-2, which is 2 times that of the microsized Cu electrode, is achieved at a potential of -0.95 V vs. Ag/AgCl. Moreover, the nano-on-micro Cu electrode demonstrates good long-term stability.

Effectiveness of acidic oxidative potential water in preventing bacterial infection in islet transplantation.

PubMed

Miyamoto, M; Inoue, K; Gu, Y; Hoki, M; Haji, S; Ohyanagi, H

1999-01-01

At a number of points in the current procedures of islet isolation and islet culture after the harvesting of donor pancreata, microorganisms could potentially infect the islet preparation. Furthermore, the use of islets from multiple donors can compound the risks of contamination of individual recipients. Acidic oxidative potential water (also termed electrolyzed strong acid solution, function water, or acqua oxidation water), which was developed in Japan, is a strong acid formed on the anode in the electrolysis of water containing a small amount of sodium chloride. It has these physical properties: pH, from 2.3 to 2.7; oxidative-reduction potential, from 1,000 to 1,100 mV; dissolved chlorine, from 30 to 40 ppm; and dissolved oxygen, from 10 to 30 ppm. Because of these properties, acidic oxidative potential water has strong bactericidal effects on all bacteria including methicillin-resistant Staphylococcus aureus (MRSA), viruses including HIV, HBV, HCV, CMV, and fungi as a result of the action of the active oxygen and active chlorine that it contains. We conducted this study to evaluate the effect of acidic oxidative potential water irrigation on bacterial contamination on the harvesting of porcine pancreata from slaughterhouses for islet xenotransplantation by counting the number of pancreatic surface bacteria using the Dip-slide method, and on the results of islet culture; and to evaluate the direct effect on isolated islets when it is used to prevent bacterial contamination by the static incubation test and by morphological examination. Direct irrigation of the pancreas by acidic oxidative potential water was found to be very effective in preventing bacterial contamination, but direct irrigation of isolated islets slightly decreased their viability and function.

Integration of graphene onto silicon through electrochemical reduction of graphene oxide layers in non-aqueous medium

NASA Astrophysics Data System (ADS)

Marrani, Andrea Giacomo; Coico, Anna Chiara; Giacco, Daniela; Zanoni, Robertino; Scaramuzzo, Francesca Anna; Schrebler, Ricardo; Dini, Danilo; Bonomo, Matteo; Dalchiele, Enrique A.

2018-07-01

Wafer-scale integration of reduced graphene oxide with H-terminated Si(1 1 1) surfaces has been accomplished by electrochemical reduction of a thin film of graphene oxide deposited onto Si by drop casting. Two reduction methods have been assayed and carried out in an acetonitrile solution. The initial deposit was subjected either to potential cycling in a 0.1 M TBAPF6/CH3CN solution at scan rates values of 20 mV s-1 and 50 mV s-1, or to a potentiostatic polarization at Eλ,c = -3 V for 450 s. The resulting interface has been characterized in its surface composition, morphology and electrochemical behavior by X-ray photoelectron spectroscopy, Raman spectroscopy, atomic force microscopy and electrochemical measurements. The results evidence that few-layer graphene deposits on H-Si(1 1 1) were obtained after reduction, and use of organic instead of aqueous medium led to a very limited surface oxidation of the Si substrate and a very low oxygen-to-carbon ratio. The described approach is fast, simple, economic, scalable and straightforward, as one reduction cycle is already effective in promoting the establishment of a graphene-Si interface. It avoids thermal treatments at high temperatures, use of aggressive chemicals and the presence of metal contaminants, and enables preservation of Si(1 1 1) surface from oxidation.

Pretreatment-dependent surface chemistry of wood nanocellulose for pH-sensitive hydrogels.

PubMed

Chinga-Carrasco, Gary; Syverud, Kristin

2014-09-01

Nanocellulose from wood is a promising material with potential in various technological areas. Within biomedical applications, nanocellulose has been proposed as a suitable nano-material for wound dressings. This is based on the capability of the material to self-assemble into 3D micro-porous structures, which among others have an excellent capacity of maintaining a moist environment. In addition, the surface chemistry of nanocellulose is suitable for various applications. First, OH-groups are abundant in nanocellulose materials, making the material strongly hydrophilic. Second, the surface chemistry can be modified, introducing aldehyde and carboxyl groups, which have major potential for surface functionalization. In this study, we demonstrate the production of nanocellulose with tailor-made surface chemistry, by pre-treating the raw cellulose fibres with carboxymethylation and periodate oxidation. The pre-treatments yielded a highly nanofibrillated material, with significant amounts of aldehyde and carboxyl groups. Importantly, the poly-anionic surface of the oxidized nanocellulose opens up for novel applications, i.e. micro-porous materials with pH-responsive characteristics. This is due to the swelling capacity of the 3D micro-porous structures, which have ionisable functional groups. In this study, we demonstrated that nanocellulose gels have a significantly higher swelling degree in neutral and alkaline conditions, compared to an acid environment (pH 3). Such a capability can potentially be applied in chronic wounds for controlled and intelligent release of antibacterial components into biofilms. © The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Pretreatment-dependent surface chemistry of wood nanocellulose for pH-sensitive hydrogels

PubMed Central

Syverud, Kristin

2014-01-01

Nanocellulose from wood is a promising material with potential in various technological areas. Within biomedical applications, nanocellulose has been proposed as a suitable nano-material for wound dressings. This is based on the capability of the material to self-assemble into 3D micro-porous structures, which among others have an excellent capacity of maintaining a moist environment. In addition, the surface chemistry of nanocellulose is suitable for various applications. First, OH-groups are abundant in nanocellulose materials, making the material strongly hydrophilic. Second, the surface chemistry can be modified, introducing aldehyde and carboxyl groups, which have major potential for surface functionalization. In this study, we demonstrate the production of nanocellulose with tailor-made surface chemistry, by pre-treating the raw cellulose fibres with carboxymethylation and periodate oxidation. The pre-treatments yielded a highly nanofibrillated material, with significant amounts of aldehyde and carboxyl groups. Importantly, the poly-anionic surface of the oxidized nanocellulose opens up for novel applications, i.e. micro-porous materials with pH-responsive characteristics. This is due to the swelling capacity of the 3D micro-porous structures, which have ionisable functional groups. In this study, we demonstrated that nanocellulose gels have a significantly higher swelling degree in neutral and alkaline conditions, compared to an acid environment (pH 3). Such a capability can potentially be applied in chronic wounds for controlled and intelligent release of antibacterial components into biofilms. PMID:24713295

Assessment of strontium oxide functionalized graphene nanoflakes for enhanced photocatalytic activity: A density functional theory approach

NASA Astrophysics Data System (ADS)

Divya, A.; Mathavan, T.; Asath, R. Mohamed; Archana, J.; Hayakawa, Y.; Benial, A. Milton Franklin

2016-05-01

A series of strontium oxide functionalized graphene nanoflakes were designed and their optoelectronic properties were studied for enhanced photocatalytic activity. The efficiency of designed molecules was studied using various parameters such as HOMO-LUMO energy gap, light harvesting efficiency and exciton binding energy. The computed results show that by increasing the degree of functionalization of strontium oxide leads to lowering the band gap of hydrogen terminated graphene nanoflakes. Furthermore, the study explores the role of strontium oxide functionalization in Frontier Molecular Orbitals, ionization potential, electron affinity, exciton binding energy and light harvesting efficiency of designed molecules. The infrared and Raman spectra were simulated for pure and SrO functionalized graphene nanoflakes. The electron rich and electron deficient regions which are favorable for electrophilic and nucleophilic attacks respectively were analyzed using molecular electrostatic potential surface analysis.

The potential of cashew gum functionalization as building blocks for layer-by-layer films.

PubMed

Leite, Álvaro J; Costa, Rui R; Costa, Ana M S; Maciel, Jeanny S; Costa, José F G; de Paula, Regina C M; Mano, João F

2017-10-15

Cashew gum (CG), an exudate polysaccharide from Anacardium occidentale trees, was carboxymethylated (CGCm) and oxidized (CGO). These derivatives were characterized by FTIR and zeta potential measurements confirming the success of carboxymethylation and oxidation reactions. Nanostructured multilayered films were then produced through layer-by-layer (LbL) assembly in conjugation with chitosan via electrostatic interactions or Schiff bases covalent bonds. The films were analyzed by QCM-D and AFM. CG functionalization increased the film thickness, with the highest thickness being achieved for the lowest oxidation degree. The roughest surface was obtained for the CGO with the highest oxidation degree due to the predominance of covalent Schiff bases. This work shows that nanostructured films can be assembled and stabilized by covalent bonds in alternative to the conventional electrostatic ones. Moreover, the functionalization of CG can increase its feasibility in multilayers films, widening its potential in biomedical, food industry, or environmental applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Minimizing analyte electrolysis in electrospray ionization mass spectrometry using a redox buffer coated emitter electrode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peintler-Krivan, Emese; Van Berkel, Gary J; Kertesz, Vilmos

2010-01-01

An emitter electrode with an electroactive poly(pyrrole) (PPy) polymer film coating was constructed for use in electrospray ionization mass spectrometry (ESI-MS). The PPy film acted as a surface-attached redox buffer limiting the interfacial potential of the emitter electrode. While extensive oxidation of selected analytes (reserpine and amodiaquine) was observed in positive ion mode ESI using a bare metal (gold) emitter electrode, the oxidation was suppressed for these same analytes when using the PPy-coated electrode. A semi-quantitative relationship between the rate of oxidation observed and the interfacial potential of the emitter electrode was shown. The redox buffer capacity, and therefore themore » lifetime of the redox buffering effect, correlated with the oxidation potential of the analyte and with the magnitude of the film charge capacity. Online reduction of the PPy polymer layer using negative ion mode ESI between analyte injections was shown to successfully restore the redox buffering capacity of the polymer film to its initial state.« less

Influence of Pb 2+ ions in the H 2 oxidation on Pt catalyzed hydrogen diffusion anodes in sulfuric acid: presence of oscillatory phenomena

NASA Astrophysics Data System (ADS)

Expósito, E.; Sánchez-Sánchez, C. M.; Solla-Gullón, J.; Montiel, V.

The influence of Pb 2+ ions in sulfuric acid medium on the behavior of a platinum catalyzed hydrogen diffusion electrode (HDE) in a filter press reactor has been studied. A voltammetric study of the H 2 oxidation reaction on a polyoriented platinum electrode and a platinum rotating disk electrode (RDE) in presence of lead ions in solution has also been carried out. Potential oscillations were found in galvanostatic experiments of H 2 oxidation using a HDE catalyzed with platinum when Pb 2+ ions are present in solution. This oscillatory phenomenon was also observed when hydrogen oxidation was carried out in presence of Pb 2+ ions using a platinum RDE. The oscillatory behavior observed has been attributed to an adsorption-oxidation-desorption process of lead on the platinum surface. Due to the low solubility of Pb 2+ in sulfuric acid, at high values of coverage, lead is oxidised to insoluble lead sulfate that blocks the Pt surface. The coupling of the dissolution of lead sulfate and the Pb electrochemical adsorption-oxidation processes cause the oscillatory phenomenon.

Nanosecond-Pulsed DBD Plasma-Generated Reactive Oxygen Species Trigger Immunogenic Cell Death in A549 Lung Carcinoma Cells through Intracellular Oxidative Stress

PubMed Central

Lin, Abraham; Truong, Billy; Patel, Sohil; Kaushik, Nagendra; Choi, Eun Ha; Fridman, Gregory; Fridman, Alexander; Miller, Vandana

2017-01-01

A novel application for non-thermal plasma is the induction of immunogenic cancer cell death for cancer immunotherapy. Cells undergoing immunogenic death emit danger signals which facilitate anti-tumor immune responses. Although pathways leading to immunogenic cell death are not fully understood; oxidative stress is considered to be part of the underlying mechanism. Here; we studied the interaction between dielectric barrier discharge plasma and cancer cells for oxidative stress-mediated immunogenic cell death. We assessed changes to the intracellular oxidative environment after plasma treatment and correlated it to emission of two danger signals: surface-exposed calreticulin and secreted adenosine triphosphate. Plasma-generated reactive oxygen and charged species were recognized as the major effectors of immunogenic cell death. Chemical attenuators of intracellular reactive oxygen species successfully abrogated oxidative stress following plasma treatment and modulated the emission of surface-exposed calreticulin. Secreted danger signals from cells undergoing immunogenic death enhanced the anti-tumor activity of macrophages. This study demonstrated that plasma triggers immunogenic cell death through oxidative stress pathways and highlights its potential development for cancer immunotherapy. PMID:28467380

Enhanced H2O2 Production at Reductive Potentials from Oxidized Boron-Doped Ultrananocrystalline Diamond Electrodes

PubMed Central

2017-01-01

This work investigates the surface chemistry of H2O2 generation on a boron-doped ultrananocrystalline diamond (BD-UNCD) electrode. It is motivated by the need to efficiently disinfect liquid waste in resource constrained environments with limited electrical power. X-ray photoelectron spectroscopy was used to identify functional groups on the BD-UNCD electrode surfaces while the electrochemical potentials of generation for these functional groups were determined via cyclic voltammetry, chronocoulometry, and chronoamperometry. A colorimetric technique was employed to determine the concentration and current efficiency of H2O2 produced at different potentials. Results showed that preanodization of an as-grown BD-UNCD electrode can enhance the production of H2O2 in a strong acidic environment (pH 0.5) at reductive potentials. It is proposed that the electrogeneration of functional groups at oxidative potentials during preanodization allows for an increased current density during the successive electrolysis at reductive potentials that correlates to an enhanced production of H2O2. Through potential cycling methods, and by optimizing the applied potentials and duty cycle, the functional groups can be stabilized allowing continuous production of H2O2 more efficiently compared to static potential methods. PMID:28471651

Exposing high-energy surfaces by rapid-anneal solid phase epitaxy

DOE PAGES

Wang, Y.; Song, Y.; Peng, R.; ...

2017-08-08

The functional design of nanoscale transition metal oxide heterostructures depends critically on the growth of atomically flat epitaxial thin films. Much of the time, improved functionality is expected for heterostructures and surfaces with orientations that do not have the lowest surface free energy. For example, crystal faces with a high surface free energy, such as rutile (001) planes, frequently exhibit higher catalytic activities but are correspondingly harder to synthesize due to energy-lowering faceting transitions. We propose a broadly applicable rapid-anneal solid phase epitaxial synthesis approach for the creation of atomically flat, high surface free energy oxide heterostructures. We also demonstratemore » its efficacy via the synthesis of atomically flat, epitaxial RuO 2(001) films with a superior oxygen evolution activity, quantified by their lower onset potential and higher current density, relative to that of more common RuO 2(110) films.« less

Preparation of ordered mesoporous and macroporous thermoplastic polyurethane surfaces for potential medical applications.

PubMed

Chennell, Philip; Feschet-Chassot, Emmanuelle; Sautou, Valérie; Mailhot-Jensen, Bénédicte

2018-05-01

Thermoplastic polyurethanes are widely used in medical devices. In order to limit some of their shortfalls, like microbial attachment, surfaces modifications can be required. In this work, a two-step replication method was used to create ordered macroporous and mesoporous thermoplastic polyurethane surfaces using anodic aluminum oxide as master template. The intermediate mould materials that were tested were polystyrene and a polyacrylate resin with inorganic filler. All obtained surfaces were characterized by scanning electron microscopy. The initial anodic aluminum oxide surfaces possessed macro or mesopores, function of anodization conditions. The intermediate mould structure correctly replicated the pattern, but the polystyrene surface structures (pillars) were less resistant than the polyacrylate resin ones. The thermoplastic polyurethane pattern possessed macropores or mesopores of about 130 nm or 46 nm diameter and of about 300 nm or 99 nm interpore distances, respectively, in accordance with the initial pattern. Thermoplastic polyurethanes pore depth was however less than initial anodic aluminum oxide pore depth, linked to an incomplete replication during intermediate mould preparation (60 to 90% depth replication). The correct replication of the original pattern confirms that this novel fabrication method is a promising route for surface patterning of thermoplastic polyurethanes that could be used for medical applications.

Heterogeneous oxidation of SO2 by O3-aged black carbon and its dithiothreitol oxidative potential.

PubMed

Xu, Weiwei; Li, Qian; Shang, Jing; Liu, Jia; Feng, Xiang; Zhu, Tong

2015-10-01

Ozone (O3) is an important atmospheric oxidant. Black carbon (BC) particles released into the atmosphere undergo an aging process via O3 oxidation. O3-aged BC particles may change their uptake ability toward trace reducing gases such as SO2 in the atmosphere, leading to different environmental and health effects. In this paper, the heterogeneous reaction process between O3-aged BC and SO2 was explored via in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Combined with ion chromatography (IC), DRIFTS was used to qualitatively and quantitatively analyze the sulfate product. The results showed that O3-aged BC had stronger SO2 oxidation ability than fresh BC, and the reactive species/sites generated on the surface had an important role in the oxidation of SO2. Relative humidity or 254nm UV (ultraviolet) light illumination enhanced the oxidation uptake of SO2 on O3-aged BC. The oxidation potentials of the BC particles were detected via dithiothreitol (DTT) assay. The DTT activity over BC was decreased in the process of SO2 reduction, with the consumption of oxidative active sites. Copyright © 2015. Published by Elsevier B.V.

Water Photo-oxidation Initiated by Surface-Bound Organic Chromophores.

PubMed

Eberhart, Michael S; Wang, Degao; Sampaio, Renato N; Marquard, Seth L; Shan, Bing; Brennaman, M Kyle; Meyer, Gerald J; Dares, Christopher; Meyer, Thomas J

2017-11-15

Organic chromophores can be synthesized by established methods and offer an opportunity to expand overall solar spectrum utilization for dye-sensitized photoelectrosynthesis cells. However, there are complications in the use of organic chromophores arising from the instability of their oxidized forms, the inability of their oxidized forms to activate a water oxidation catalyst, or the absence of a sufficiently reducing excited state for electron injection into appropriate semiconductors. Three new triarylamine donor-acceptor organic dyes have been investigated here for visible-light-driven water oxidation. They offer highly oxidizing potentials (>1 V vs NHE in aqueous solution) that are sufficient to drive a water oxidation catalyst and excited-state potentials (∼-1.2 V vs NHE) sufficient to inject into TiO 2 . The oxidized form of one of the chromophores is sufficiently stable to exhibit reversible electrochemistry in aqueous solution. The chromophores also have favorable photophysics. Visible-light-driven oxygen production by an organic chromophore for up to 1 h of operation has been demonstrated with reasonable faradaic efficiencies for measured O 2 production. The properties of organic chromophores necessary for successfully driving water oxidation in a light-driven system are explored along with strategies for improving device performance.

Erratum to ;Coastal water column ammonium and nitrite oxidation are decoupled in summer;

NASA Astrophysics Data System (ADS)

Heiss, Elise M.; Fulweiler, Robinson W.

2017-07-01

Water column nitrification is a key process in the nitrogen cycle as it links reduced and oxidized forms of nitrogen and also provides the substrate (nitrate) needed for reactive nitrogen removal by denitrification. We measured potential water column ammonium and nitrite oxidation rates at four sites along an estuary to continental shelf gradient over two summers. In most cases, nitrite oxidation rates outpaced ammonium oxidation rates. Overall, ammonium and nitrite oxidation rates were higher outside of the estuary, and this trend was primarily driven by higher oxidation rates in deeper waters. Additionally, both ammonium and nitrite oxidation rates were impacted by different in situ variables. Ammonium oxidation rates throughout the water column as a whole were most positively correlated to depth and salinity and negatively correlated to dissolved oxygen, light, and temperature. In contrast, nitrite oxidation rates throughout the water column were negatively correlated with temperature, light and pH. Multivariate regression analysis revealed that surface (<20 m) ammonium oxidation rates were most strongly predicted by substrate (NH4+), salinity, and light, while deep (>20 m) rates were regulated by temperature, light, and [H+] (i.e. pH). In addition, surface (<20 m) nitrite oxidation rates were best explained by [H+] alone, while [H+], temperature, and dissolved oxygen all played a role in predicting deep (>20 m) nitrite oxidation rates. These results support the growing body of evidence that ammonium oxidation and nitrite oxidation are not always coupled, should be measured separately, and are influenced by different environmental conditions.

Fungal oxidative dissolution of the Mn(II)-bearing mineral rhodochrosite and the role of metabolites in manganese oxide formation.

PubMed

Tang, Yuanzhi; Zeiner, Carolyn A; Santelli, Cara M; Hansel, Colleen M

2013-04-01

Microbially mediated oxidation of Mn(II) to Mn(III/IV) oxides influences the cycling of metals and remineralization of carbon. Despite the prevalence of Mn(II)-bearing minerals in nature, little is known regarding the ability of microbes to oxidize mineral-hosted Mn(II). Here, we explored oxidation of the Mn(II)-bearing mineral rhodochrosite (MnCO3 ) and characteristics of ensuing Mn oxides by six Mn(II)-oxidizing Ascomycete fungi. All fungal species substantially enhanced rhodochrosite dissolution and surface modification. Mineral-hosted Mn(II) was oxidized resulting in formation of Mn(III/IV) oxides that were all similar to δ-MnO2 but varied in morphology and distribution in relation to cellular structures and the MnCO3 surface. For four fungi, Mn(II) oxidation occurred along hyphae, likely mediated by cell wall-associated proteins. For two species, Mn(II) oxidation occurred via reaction with fungal-derived superoxide produced at hyphal tips. This pathway ultimately resulted in structurally unique Mn oxide clusters formed at substantial distances from any cellular structure. Taken together, findings for these two fungi strongly point to a role for fungal-derived organic molecules in Mn(III) complexation and Mn oxide templation. Overall, this study illustrates the importance of fungi in rhodochrosite dissolution, extends the relevance of biogenic superoxide-based Mn(II) oxidation and highlights the potential role of mycogenic exudates in directing mineral precipitation. © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

Role of alloying elements in adhesive transfer and friction of copper-base alloys

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1978-01-01

Sliding friction experiments were conducted in a vacuum with binary-copper alloy riders sliding against a conventional bearing-steel surface with normal residual oxides present. The binary alloys contained 1 atomic percent of various alloying elements. Auger spectroscopy analysis was used to monitor the adhesive transfer of the copper alloys to the bearing-steel surface. A relation was found to exist between adhesive transfer and the reaction potential and free energy of formation of the alloying element in the copper. The more chemically active the element and the more stable its oxide, the greater was the adhesive transfer and wear of the copper alloy. Transfer occurred in all the alloys except copper-gold after relatively few (25) passes across the steel surface.

Formula of an ideal carbon nanomaterial supercapacitor

NASA Astrophysics Data System (ADS)

Samuilova, Larissa; Frenkel, Alexander; Samuilov, Vladimir

2014-03-01

Supercapacitors exhibit great potential as high-performance energy sources for a large variety of potential applications, ranging from consumer electronics through wearable optoelectronics to hybrid electric vehicles. We focuse on carbon nanomaterials, especially carbon nanotube films, 3-D graphene, graphene oxide due to their high specific surface area, excellent electrical and mechanical properties. We have developed a simple approach to lower the equivalent series resistance by fabricating electrodes of arbitrary thickness using carbon nanotube films and reduced graphene oxide based composites. Besides of the problem of increasing of the capacitance, the minimization of the loss tangent (dissipation factor) is marginal for the future development of the supercapacitors. This means, not only a very well developed surface area of the electrodes, but the role of the good quality of the porous separator and the electrolyte are important. We address these factors as well.

Double layer effects in electrocatalysis: The oxygen reduction reaction and ethanol oxidation reaction on Au(111), Pt(111) and Ir(111) in alkaline media containing Na and Li cations

DOE PAGES

Lopes, Pietro P.; Strmcnik, Dusan; Jirkovsky, Jakub S.; ...

2015-09-28

Oxygen reduction and ethanol oxidation reactions were studied on Au(111), Pt(111) and Ir(111) in alkaline solutions containing sodium and/or lithium cations. By keeping the same (111) surface orientation and exploring oxophilicity trends and non-covalent interactions between OH ad and alkali metal cations (AMC n+), we were able to gain deep insights into the multiple roles that OH ad plays in these important electrocatalytic reactions. Cyclic voltammetry experiments revealed that OH ad formation initiates at distinct electrode potentials, governed by the oxophilicity of the specific metal surface, with further OH ad adlayer stabilization by non-covalent alkali-cation interactions and affecting the formationmore » of a “true oxide” layer at higher electrode potentials. Although OH ad is a simple spectator for the ORR, it promotes the ethanol oxidation reaction (EOR) at lower potentials and act as spectator at high OHad coverages. By changing the alkali metal cation at the interface (Li +) on more oxophilic surfaces, it was possible to promote the EOR even more, relative to Na +, without changing the product distribution for the reaction. This cation effect suggests that OH ad—Li +(H 2O) x clusters can stabilize the ethoxide adlayer, thus improving the EOR activity. Finally, our results indicate the importance of the entire electrochemical interface in determining the electrocatalytic activity during reaction.« less

Relating the Chemical Composition of Dissolved Organic Matter Draining Permafrost Soils to its Photochemical Degradation in Arctic Surface Waters.

NASA Astrophysics Data System (ADS)

Ward, C.; Cory, R. M.

2015-12-01

Thawing permafrost soils are expected to shift the chemical composition of DOM exported to and degraded in arctic surface waters. While DOM photo-degradation is an important component of the freshwater C cycle in the Arctic, the molecular controls on DOM photo-degradation remain poorly understood, making it difficult to predict how shifting chemical composition may alter DOM photo-degradation in arctic surface waters. To address this knowledge gap, we quantified the susceptibility of DOM draining the shallow organic mat and the deeper permafrost layer to complete photo-oxidation to CO₂ and partial photo-oxidation to compounds that remain in the DOM pool, and investigated changes in DOM chemical composition following sunlight exposure. DOM leached from the organic mat contained higher molecular weight, more oxidized and unsaturated aromatic species compared to permafrost DOM. Despite significant differences in initial chemical composition, permafrost and organic mat DOM had similar susceptibilities to complete photo-oxidation to CO₂. Concurrent losses of carboxyl moieties and shifts in chemical composition during photo-degradation indicated that carboxyl-rich tannin-like compounds in both DOM sources were likely photo-decarboxylated to CO₂. Permafrost DOM had a higher susceptibility to partial photo-oxidation compared to organic mat DOM, potentially due to a lower abundance of phenolic compounds that act as "antioxidants" and slow the oxidation of DOM. These results demonstrated how chemical composition controls the photo-degradation of DOM in arctic surface waters, and that DOM photo-degradation will likely remain an important component of the freshwater C budget in the Arctic with increased export of permafrost DOM to surface waters.

Mineralogical, crystallographic and morphological characteristics of natural kaolins from the Ivory Coast (West Africa)

NASA Astrophysics Data System (ADS)

Sei, J.; Morato, F.; Kra, G.; Staunton, S.; Quiquampoix, H.; Jumas, J. C.; Olivier-Fourcade, J.

2006-10-01

Thirteen clay samples from four deposits in the Ivory Coast (West Africa) were studied using X-ray diffraction, thermogravimetric analysis and chemical analysis. Mineralogical, crystallographic and morphological characteristics of these samples are given. Kaolinite is the principal mineral but other minerals are present in small quantities: illite, quartz, anatase and iron oxides (oxides and oxyhydroxides). The crystallographic, morphological and surface characteristics are influenced by the presence of these impurities. In particular, the presence of iron oxides was associated with reduced structural ordering and thermal stability of kaolinite and increased specific surface area. These clays could be used in the ceramics industry to make tiles and bricks, and also in agronomy as supports for chemical fertilizers or for environmental protection by immobilising potentially toxic waste products.

Electrochemical studies of Copper, Tantalum and Tantalum Nitride surfaces in aqueous solutions for applications in chemical-mechanical and electrochemical-mechanical planarization

NASA Astrophysics Data System (ADS)

Sulyma, Christopher Michael

This report will investigate fundamental properties of materials involved in integrated circuit (IC) manufacturing. Individual materials (one at a time) are studied in different electrochemical environmental solutions to better understand the kinetics associated with the polishing process. Each system tries to simulate a real CMP environment in order to compare our findings with what is currently used in industry. To accomplish this, a variety of techniques are used. The voltage pulse modulation technique is useful for electrochemical processing of metal and alloy surfaces by utilizing faradaic reactions like electrodeposition and electrodissolution. A theoretical framework is presented in chapter 4 to facilitate quantitative analysis of experimental data (current transients) obtained in this approach. A typical application of this analysis is demonstrated for an experimental system involving electrochemical removal of copper surface layers, a relatively new process for abrasive-free electrochemical mechanical planarization of copper lines used in the fabrication of integrated circuits. Voltage pulse modulated electrodissolution of Cu in the absence of mechanical polishing is activated in an acidic solution of oxalic acid and hydrogen peroxide. The current generated by each applied voltage step shows a sharp spike, followed by a double-exponential decay, and eventually attains the rectangular shape of the potential pulses. For the second system in chapter 5, open-circuit potential measurements, cyclic voltammetry and Fourier transform impedance spectroscopy have been used to study pH dependent surface reactions of Cu and Ta rotating disc electrodes (RDEs) in aqueous solutions of succinic acid (SA, a complexing agent), hydrogen peroxide (an oxidizer), and ammonium dodecyl sulfate (ADS, a corrosion inhibitor for Cu). The surface chemistries of these systems are relevant for the development of a single-slurry approach to chemical mechanical planarization (CMP) of Cu lines and Ta barriers in the fabrication of semiconductor devices. It is shown that in non-alkaline solutions of H2O2, the SA-promoted surface complexes of Cu and Ta can potentially support chemically enhanced material removal in low-pressure CMP of surface topographies overlying fragile low-k dielectrics. ADS can suppress Cu dissolution without significantly affecting the surface chemistry of Ta. Chapter 6 discusses anodic corrosion of Ta, which is examined as a possible route to voltage induced removal of Ta for potential applications in electrochemical mechanical planarization (ECMP) of diffusion barriers. This strategy involves electro-oxidation of Ta in the presence of NO3- anions to form mechanically weak surface oxide films, followed by removal of the oxide layers by moderate mechanical abrasion. This NO3 - system is compared with a reference solution of Br -. In both electrolytes, the voltammetric currents of anodic oxidation exhibit oscillatory behaviors in the initial cycles of slow (5 mV s-1) voltage scans. The frequencies of these current oscillations are show signature attributes of localized pitting or general surface corrosion caused by Br- or NO3 -, respectively. Scanning electron microscopy, cyclic voltammetry, polarization resistance measurements, and time resolved Fourier transform impedance spectroscopy provide additional details about these corrosion mechanism. Apart from their relevance in the context of ECMP, the results also address certain fundamental aspects of pitting and general corrosions. The general protocols necessary to combine and analyze the results of D.C. and A.C. electrochemical measurements involving such valve metal corrosion systems are discussed in detail. In chapter 7 potassium salts of certain oxyanions (nitrate, sulfate and phosphate in particular) are shown to serve as effective surface-modifying agents in chemically enhanced, low-pressure chemical mechanical planarization (CMP) of Ta and TaN barrier layers for interconnect structures. The surface reactions that form the basis of this CMP strategy are investigated here in detail using the electrochemical techniques of cyclic voltammetry, open circuit potential analysis, polarization resistance measurements, and Fourier transform impedance spectroscopy. The results suggest that forming structurally weak oxide layers on the CMP samples is a key to achieving the goal of chemically controlled CMP of Ta/TaN at low down-pressures. (Abstract shortened by UMI.)

Partial oxidation (“aging”) and surface modification decrease the toxicity of nano-sized zero valent iron     

EPA Science Inventory

Zero-valent iron (nZVI) is a redox-active nanomaterial used for in situ remediation of contaminated groundwater. To assess the effect of “aging” and surface modification on its potential neurotoxicity, cultured rodent microglia and neurons were exposed to fresh nZVI, “aged” (>11...

Enhanced Adsorption of Selenium Ions from Aqueous Solution Using Iron Oxide Impregnated Carbon Nanotubes

PubMed Central

Bakather, Omer Y.; Khraisheh, Majeda; Nasser, Mustafa S.

2017-01-01

The aim of this research was to investigate the potential of raw and iron oxide impregnated carbon nanotubes (CNTs) as adsorbents for the removal of selenium (Se) ions from wastewater. The original and modified CNTs with different loadings of Fe2O3 nanoparticles were characterized using high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), X-ray diffractometer (XRD), Brunauer, Emmett, and Teller (BET) surface area analyzer, thermogravimetric analysis (TGA), zeta potential, and energy dispersive X-ray spectroscopy (EDS). The adsorption parameters of the selenium ions from water using raw CNTs and iron oxide impregnated carbon nanotubes (CNT-Fe2O3) were optimized. Total removal of 1 ppm Se ions from water was achieved when 25 mg of CNTs impregnated with 20 wt.% of iron oxide nanoparticles is used. Freundlich and Langmuir isotherm models were used to study the nature of the adsorption process. Pseudo-first and pseudo-second-order models were employed to study the kinetics of selenium ions adsorption onto the surface of iron oxide impregnated CNTs. Maximum adsorption capacity of the Fe2O3 impregnated CNTs, predicted by Langmuir isotherm model, was found to be 111 mg/g. This new finding might revolutionize the adsorption treatment process and application by introducing a new type of nanoadsorbent that has super adsorption capacity towards Se ions. PMID:28555093

Activity–stability relationship in the surface electrochemistry of the oxygen evolution reaction

DOE PAGES

Chang, Seo Hyoung; Connell, Justin G.; Danilovic, Nemanja; ...

2014-07-25

Understanding the functional links between the stability and reactivity of oxide materials during the oxygen evolution reaction (OER) is one key to enabling a vibrant hydrogen economy capable of competing with fossil fuel-based technologies. In this work, by focusing on the surface chemistry of monometallic Ru oxide in acidic and alkaline environments, we found that the kinetics of the OER are almost entirely controlled by the stability of the Ru surface atoms. The same activity–stability relationship was found for more complex, polycrystalline and single-crystalline SrRuO 3 thin films in alkaline solutions. We propose that the electrochemical transformation of either watermore » (acidic solutions) or hydroxyl ions (alkaline solutions) to di-oxygen molecules takes place at defect sites that are inherently present on every electrode surface. During the OER, surface defects are also created by the corrosion of the Ru ions. The dissolution is triggered by the potential-dependent change in the valence state ( n) of Ru: from stable but inactive Ru 4+ to unstable but active Ru n>4+. We conclude that if the oxide is stable then it is completely inactive for the OER. As a result, a practical consequence is that the best materials for the OER should balance stability and activity in such a way that the dissolution rate of the oxide is neither too fast nor too slow.« less

Atomic-scale electrochemistry on the surface of a manganite

DOE PAGES

Vasudevan, Rama K.; Tselev, Alexander; Baddorf, Arthur P.; ...

2015-04-09

The doped manganese oxides (manganites) have been widely studied for their colossal magnetoresistive effects, for potential applications in oxide spintronics, electroforming in resistive switching devices, and are materials of choice as cathodes in modern solid oxide fuel cells. However, little experimental knowledge of the dynamics of the surfaces of perovskite manganites at the atomic scale exists. Here, through in-situ scanning tunnelling microscopy (STM), we demonstrate atomic resolution on samples of La 0.625Ca 0.375MnO 3 grown on (001) SrTiO 3 by pulsed laser deposition (PLD). Furthermore, by applying triangular DC waveforms of increasing amplitude to the STM tip, and measuring themore » tunnelling current, we demonstrate the ability to both perform and monitor surface electrochemical processes at the atomic level, including, for the first time in a manganite, formation of single and multiple oxygen vacancies, disruption of the overlying manganite layers, and removal and deposition of individual atomic units or clusters. Our work paves the way for better understanding of surface oxygen reactions in these systems.« less

Effect of temperature on the passivation behavior of steel rebar

NASA Astrophysics Data System (ADS)

Chen, Shan-meng; Cao, Bei; Wu, Yin-shun; Ma, Ke

2014-05-01

Steel rebar normally forms an oxide or rusty skin before it is embedded into concrete and the passivation properties of this skin will be heavily influenced by temperature. To study the effect of temperature on the passivation properties of steel rebar under different surface conditions, we conducted scanning electron microscopy (SEM) observations and electrochemical measurements, such as measurements of the free corrosion potential and polarization curves of HPB235 steel rebar. These measurements identified three kinds of surfaces: polished, oxide skin, and rusty skin. Our results show that the passivation properties of all the surface types decrease with the increase of temperature. Temperature has the greatest effect on the rusty-skin rebar and least effect on the polished steel rebar, because of cracks and crevices on the mill scale on the steel rebar's surface. The rusty-skin rebar exhibits the highest corrosion rate because crevice corrosion can accelerate the corrosion of the steel rebar, particularly at high temperature. The results also indicate that the threshold temperatures of passivation for the oxide-skin rebar and the rusty-skin rebar are 37°C and 20°C, respectively.

Analytical drain current model for symmetric dual-gate amorphous indium gallium zinc oxide thin-film transistors

NASA Astrophysics Data System (ADS)

Qin, Ting; Liao, Congwei; Huang, Shengxiang; Yu, Tianbao; Deng, Lianwen

2018-01-01

An analytical drain current model based on the surface potential is proposed for amorphous indium gallium zinc oxide (a-InGaZnO) thin-film transistors (TFTs) with a synchronized symmetric dual-gate (DG) structure. Solving the electric field, surface potential (φS), and central potential (φ0) of the InGaZnO film using the Poisson equation with the Gaussian method and Lambert function is demonstrated in detail. The compact analytical model of current-voltage behavior, which consists of drift and diffusion components, is investigated by regional integration, and voltage-dependent effective mobility is taken into account. Comparison results demonstrate that the calculation results obtained using the derived models match well with the simulation results obtained using a technology computer-aided design (TCAD) tool. Furthermore, the proposed model is incorporated into SPICE simulations using Verilog-A to verify the feasibility of using DG InGaZnO TFTs for high-performance circuit designs.

Enhancement in ion adsorption rate and desalination efficiency in a capacitive deionization cell through improved electric field distribution using electrodes composed of activated carbon cloth coated with zinc oxide nanorods.

PubMed

Laxman, Karthik; Myint, Myo Tay Zar; Bourdoucen, Hadj; Dutta, Joydeep

2014-07-09

Electrodes composed of activated carbon cloth (ACC) coated with zinc oxide (ZnO) nanorods are compared with plain ACC electrodes, with respect to their desalination efficiency of a 17 mM NaCl solution at different applied potentials. Polarization of the ZnO nanorods increased the penetration depth and strength of the electric field between the electrodes, leading to an increase in the capacitance and charge efficiency at reduced input charge ratios. Uniform distribution of the electric field lines between two electrodes coated with ZnO nanorods led to faster ion adsorption rates, reduced the electrode saturation time, and increased the average desalination efficiency by ∼45% for all applied potentials. The electrodes were characterized for active surface area, capacitance from cyclic voltammetry, theoretical assessment of surface area utilization, and the magnitude of electric field force acting on an ion of unit charge for each potential.

Electricity from Coal Combustion: Improving the hydrophobicity of oxidized coals

NASA Astrophysics Data System (ADS)

Seehra, Mohindar; Singh, Vivek

2011-03-01

To reduce pollution and improve efficiency, undesirable mineral impurities in coals are usually removed in coal preparation plants prior to combustion first by crushing and grinding coals followed by gravity separation using surfactant aided water flotation. However certain coals in the US are not amendable to this process because of their poor flotation characteristics resulting in a major loss of an energy resource. This problem has been linked to surface oxidation of mined coals which make these coals hydrophilic. In this project, we are investigating the surface and water flotation properties of the eight Argonne Premium (AP) coals using x-ray diffraction, IR spectroscopy and zeta potential measurements. The role of the surface functional groups, (phenolic -OH and carboxylic -COOH), produced as a result of chemisorptions of O2 on coals in determining their flotation behavior is being explored. The isoelectric point (IEP) in zeta potential measurements of good vs. poor floaters is being examined in order to improved the hydrophobicity of poor floating coals (e.g. Illinois #6). Results from XRD and IR will be presented along with recent findings from zeta potential measurements, and use of additives to improve hydrophobicity. Supported by USDOE/CAST, Contract #DE-FC26-05NT42457.

Enhanced Fe2O3 Reducibility via Surface Modification with Pd: Characterizing the Synergy within Pd/Fe Catalysts for Hydrodeoxygenation Reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hensley, Alyssa; Hong, Yongchun; Zhang, Renqin

2014-10-03

The synergistic catalysis in the hydrodeoxygenation of phenolic compounds over a Pd/Fe bimetallic surface has been well established. However, the nature of this synergy is still in part a mystery. In this work, we used a combined experimental and theoretical approach to understand a potential function of the surface Pd in the reduction of Pd/Fe2O3. This function of Pd was investigated via the comparison of the reduction properties as well as other physicochemical properties of samples synthesized by the reduction of Fe2O3 nanoparticles with and without surface Pd. Temperature-programmed reduction studies demonstrated the remarkable facilitation of reduction by addition ofmore » Pd, evidenced by a 150 degrees C shift toward lower temperature of the reduction peak of Fe3+. From X-ray photoelectron spectroscopy and theoretical calculation results, the interaction between Pd and the Fe2O3 surface occurs through the exchange of electrons with both the surface Fe and O atoms. This bonding between the Pd and surface oxide elements causes the Pd to partially donate electrons to the oxide surface, making the surface electrons more delocalized. This electron delocalization stabilizes the reduced oxide surfaces, as suggested by the TPR results and theoretical prediction. Therefore, the stabilization of the reduced Fe surface as well as the facilitated water formation by introduction of Pd is expected to significantly contribute to the Pd-Fe synergy in hydrodeoxygenation catalysis.« less

Microbial nitrogen transformation potential in surface run-off leachate from a tropical landfill

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mangimbulude, Jubhar C.; Straalen, Nico M. van; Roeling, Wilfred F.M., E-mail: wilfred.roling@falw.vu.nl

2012-01-15

Highlights: Black-Right-Pointing-Pointer Microbial nitrogen transformations can alleviate toxic ammonium discharge. Black-Right-Pointing-Pointer Aerobic ammonium oxidation was rate-limiting in Indonesian landfill leachate. Black-Right-Pointing-Pointer Organic nitrogen ammonification was most dominant. Black-Right-Pointing-Pointer Anaerobic nitrate reduction and ammonium oxidation potential were also high. Black-Right-Pointing-Pointer A two-stage aerobic-anaerobic nitrogen removal system needs to be implemented. - Abstract: Ammonium is one of the major toxic compounds and a critical long-term pollutant in landfill leachate. Leachate from the Jatibarang landfill in Semarang, Indonesia, contains ammonium in concentrations ranging from 376 to 929 mg N L{sup -1}. The objective of this study was to determine seasonal variation in themore » potential for organic nitrogen ammonification, aerobic nitrification, anaerobic nitrate reduction and anaerobic ammonium oxidation (anammox) at this landfilling site. Seasonal samples from leachate collection treatment ponds were used as an inoculum to feed synthetic media to determine potential rates of nitrogen transformations. Aerobic ammonium oxidation potential (<0.06 mg N L{sup -1} h{sup -1}) was more than a hundred times lower than the anaerobic nitrogen transformation processes and organic nitrogen ammonification, which were of the same order of magnitude. Anaerobic nitrate oxidation did not proceed beyond nitrite; isolates grown with nitrate as electron acceptor did not degrade nitrite further. Effects of season were only observed for aerobic nitrification and anammox, and were relatively minor: rates were up to three times higher in the dry season. To completely remove the excess ammonium from the leachate, we propose a two-stage treatment system to be implemented. Aeration in the first leachate pond would strongly contribute to aerobic ammonium oxidation to nitrate by providing the currently missing oxygen in the anaerobic leachate and allowing for the growth of ammonium oxidisers. In the second pond the remaining ammonium and produced nitrate can be converted by a combination of nitrate reduction to nitrite and anammox. Such optimization of microbial nitrogen transformations can contribute to alleviating the ammonium discharge to surface water draining the landfill.« less

Development of Multifunctional Nanoparticles for Cancer Therapy Applications

NASA Astrophysics Data System (ADS)

Huth, Christopher

The focus of this thesis is the functionalization and tailoring of nanoparticle surfaces to perform specific objectives in a biological environment. The nanoparticles examined include carbon nanotubes (CNTs), superparamagnetic iron oxide nanoparticles and superparamagnetic iron oxide nanocomposites. The unique nanomaterials have been developed to address continued issues in cancer therapy, including cancer diagnosis and efficient drug delivery. CNT surfaces were modified by plasma polymerization, providing functional groups for conjugation. Luminescent amine labeled quantum dots were fixed to the surface of the CNTs to aid in cancer diagnosis by in vivo imaging. Mice, injected with the quantum dot functionalized carbon nanotubes, were imaged displaying the in vivo imaging capability. In addition, the drug loading and drug release capabilities were examined by incorporating the drug paclitaxel into PLGA-coated CNTs, which showed much higher cytotoxicity to PC-3MM2 human prostate carcinoma cells compared to CNTs without paclitaxel. Paclitaxel was loaded at 112.5 microg/mg of PLGA-coated CNTs. Iron oxide nanocomposites were functionalized with quantum dots for diagnosis applications. Because the nanocomposites contain iron oxide, the nanoparticle provides the opportunity for magnetic hyperthermia, creating a unique material for diagnosis and therapy. Mice, injected with the quantum dot functionalized iron oxide nanocomposites, were imaged displaying the in vivo imaging capability. The magnetic hyperthermic property of the quantum dot functionalized nanocomposites was observed with the attainment of temperatures above 50°C during exposure to an alternating magnetic field. Thermoresponsive nanoparticles were prepared by immobilizing a 2 - 3 nm thick phospholipid layer on the surface of superparamagnetic Fe3O 4 nanoparticles via high affinity avidin/biotin interactions. Morphological and physicochemical surface properties were assessed using TEM, confocal laser scanning microscopy, differential scanning calorimetry, and ATR-FTIR. The zeta potential of Fe3O4 colloids in phosphate buffered saline (PBS) decreased from -23.6 to -5.0 mV as a consequence of phospholipid immobilization. Hyperthermia-relevant temperatures greater than 40°C were achieved within 10--15 min using a 7-mT magnetic field alternating at a frequency of 1MHz. Loading of the surface-associated phospholipid layer with the hydrophobic dye dansylcadaverine was accomplished at an efficiency of 479 ng/mg Fe3O4. Release of this drug surrogate was temperature-dependent, resulting in a 2.5-fold greater release rate when nanoparticles were exposed to temperatures above the experimentally determined melting temperature of 39.7°C. In vitro cytotoxicity studies by release of the cytotoxic drug, doxorubicin, from the thermoresponsive nanoparticles was lastly intended. However, colloidal stability became an issue, prompting a thorough review of nanoparticle stabilization. Factors affecting stabilization, including dispersant, the nanoparticle, and the thermoresponsive coating, were characterized by dynamic light scattering and zeta potential. PBS was compared to two dispersants containing lower ionic concentrations, HBSS and HEPES, using the original iron oxide nanoparticles compared to an iron oxide nanocomposite. The nanocomposite in the HEPES buffer displayed the greatest stability with a zeta potential of -30.47 mV and particle size of 155.4 nm. Stabilization of the immobilized phospholipid bilayer was examined with and without incorporation of the cationic lipid stearylamine. Zeta potential (33.6 mV) and size (315 nm) data indicate that stearylamine incorporated DPPC coated nanoparticles provide better stability.

Titanium oxide as substrate for neural cell growth.

PubMed

Carballo-Vila, Mónica; Moreno-Burriel, Berta; Chinarro, Eva; Jurado, José R; Casañ-Pastor, Nieves; Collazos-Castro, Jorge E

2009-07-01

Titanium oxide has antiinflammatory activity and tunable electrochemical behavior that make it an attractive material for the fabrication of implantable devices. The most stable composition is TiO2 and occurs mainly in three polymorphs, namely, anatase, rutile, and brookite, which differ in its crystallochemical properties. Here, we report the preparation of rutile surfaces that permit good adherence and axonal growth of cultured rat cerebral cortex neurons. Rutile disks were obtained by sinterization of TiO2 powders of commercial origin or precipitated from hydrolysis of Ti(IV)-isopropoxide. Commercial powders sintered at 1300-1600 degrees C produced rutile surfaces with abnormal grain growth, probably because of impurities of the powders. Neurons cultured on those surfaces survived in variable numbers and showed fewer neurites than on control materials. On the other hand, rutile sintered from precipitated powders had less contaminants and more homogenous grain growth. By adjusting the thermal treatment it was possible to obtain surfaces performing well as substrate for neuron survival for at least 10 days. Some surfaces permitted normal axonal elongation, whereas dendrite growth was generally impaired. These findings support the potential use of titanium oxide in neuroprostheses and other devices demanding materials with enhanced properties in terms of biocompatibility and axon growth promotion.

Interlocked by nanoscale sculpturing: pure aluminum copper contacts (Conference Presentation)

NASA Astrophysics Data System (ADS)

Gerngross-Baytekin, Melike; Gerngross, Mark Daniel; Carstensen, Jürgen; Adelung, Rainer

2017-06-01

Connecting metals reliable with different corrosion potential is a well-known challenge. An extreme example are copper aluminum contacts. Galvanic corrosion occurs if the two different metals are in contact with each other and an electrolyte, the aluminum becomes susceptible to corrosion under current flow. Usually, antioxidant pastes containing metals are employed but create difficulties e.g. for fatigue resistant power electronic connections. The recently described process of nanoscale sculpturing [1] offers an alternative. Usually, if the surface of metals like aluminium are prepared they are just arbitrary cuts through the bulk. There is no optimization of the surface grain structure towards stability at all. Neither the crystalline facets in the grains are in their most stable orientation nor is the protective oxide shell the most stable one. The nanoscale sculpturing approach is carving out the most stable grains and planes by chemical or electrochemical treatment. The decisive trick is that the chemistry is targeting towards the instable oxide and not the metal. Aluminium sample surfaces including alloys like AA575 exhibit afterwards single crystalline surface facets covered with nanoscale stable oxide films. Galvanically deposited copper forms extremely reliable interlocked connections on top, even allowing for soldering on top of their surface.

Methanol oxidation reaction on core-shell structured Ruthenium-Palladium nanoparticles: Relationship between structure and electrochemical behavior

NASA Astrophysics Data System (ADS)

Kübler, Markus; Jurzinsky, Tilman; Ziegenbalg, Dirk; Cremers, Carsten

2018-01-01

In this work the relationship between structural composition and electrochemical characteristics of Palladium(Pd)-Ruthenium(Ru) nanoparticles during alkaline methanol oxidation reaction is investigated. The comparative study of a standard alloyed and a precisely Ru-core-Pd-shell structured catalyst allows for a distinct investigation of the electronic effect and the bifunctional mechanism. Core-shell catalysts benefit from a strong electronic effect and an efficient Pd utilization. It is found that core-shell nanoparticles are highly active towards methanol oxidation reaction for potentials ≥0.6 V, whereas alloyed catalysts show higher current outputs in the lower potential range. However, differential electrochemical mass spectrometry (DEMS) experiments reveal that the methanol oxidation reaction on core-shell structured catalysts proceeds via the incomplete oxidation pathway yielding formaldehyde, formic acid or methyl formate. Contrary, the alloyed catalyst benefits from the Ru atoms at its surface. Those are found to be responsible for high methanol oxidation activity at lower potentials as well as for complete oxidation of CH3OH to CO2 via the bifunctional mechanism. Based on these findings a new Ru-core-Pd-shell-Ru-terrace catalyst was synthesized, which combines the advantages of the core-shell structure and the alloy. This novel catalyst shows high methanol electrooxidation activity as well as excellent selectivity for the complete oxidation pathway.

Microbial Fe biomineralization in mafic and ultramafic rocks

NASA Astrophysics Data System (ADS)

Templeton, A. S.; Mayhew, L.; McCollom, T.; Trainor, T.

2011-12-01

Fluid-filled microfractures within mafic and ultramafic rocks, such as basalt and peridotite, may be one of the most ubiquitous microbial habitats on the modern and ancient earth. In seafloor and subseafloor systems, one of the dominant energy sources is the oxidation of Fe by numerous potential oxidants under aerobic to anaerobic conditions. In particular, the oxidation of Fe may be directly catalyzed by microbial organisms, or result in the production of molecular hydrogen which can then fuel diverse lithotrophic metabolisms. However, it remains challenging to identify the dominant metabolic activities and unravel the microscale biogeochemical processes occuring within such rock-hosted systems. We are investigating the mechanisms of solid-state Fe-oxidation and biomineralization in basalt, olivine, pyroxenes and basalts, in the presence and absence of microbial organisms that can thrive across the full stability range of water. In this talk we will present synchrotron-based x-ray scattering and spectroscopic analyses of Fe speciation within secondary minerals formed during microbially-mediated vs. abiotic water-rock interactions. Determining the valence state and mineralogy of Fe-bearing phases is critical for determining the water-rock reaction pathways and identifying potential biominerals that may form; therefore, we will highlight new approaches for identifying key Fe transformations within complex geological media. In addition, many of our experimental studies involve the growth of lithotrophic biofilms on well-characterized mineral surfaces in order to determine the chemistry of the microbe-mineral interface during progressive electron-transfer reactions. By coupling x-ray spectroscopy, x-ray diffraction, and electron-microscopy measurements, we will also contrast the evolution of mineral surfaces that undergo microbially-mediated oxidative alteration against minerals surfaces that produce H2 to sustain anaerobic microbial communities.

Electrochemical behavior of lead alloys in sulfuric and phosphoric acid solutions

NASA Astrophysics Data System (ADS)

Paleska, I.; Pruszkowska-Drachal, R.; Kotowski, J.; Dziudzi, A.; Milewski, J. D.; Kopczyk, M.; Czerwiński, A.

The electrochemical behavior of lead, lead-antimony, and lead-calcium-aluminium-tin alloys has been studied in solutions containing various concentrations of sulfuric and phosphoric acids. The dependence of these electrode processes on some experimental conditions (mainly sweep rate and potential range) has been studied. The measurements were performed using a cyclic voltammetry technique. The study and the analysis of the morphology of alloys have been performed using a scanning electron microscope (SEM). Cyclic voltammograms of the lead-antimony alloy electrodes, similarly to pure lead electrode, also show the "anodic excursion" peak under some experimental conditions. Well defined current waves, corresponding to the oxidation and reduction processes of Sb, are observed, if the alloy surface is freshly abraded. The oxidation of antimony starts at potentials at which the formation of PbO takes place. The peak current of Sb oxidation reaction decreases during successive cycles, suggesting that Sb dissolves from the alloy surface during the first CV sweeps. Another explanation for this effect might be the formation of a PbSO 4 selective membrane.

Formation of Oxides in the Interior of Friction Stir Welds

NASA Technical Reports Server (NTRS)

Schneider, Judy; Chen, Po; Nunes, Arthur C., Jr.

2016-01-01

In friction stir welding (FSWing) the actual solid state joining takes place between the faying surfaces which form the weld seam. Thus the seam trace is often investigated for clues when the strength of the weld is reduced. Aluminum and its alloys are known to form a native, protective oxide on the surface. If these native surface oxides are not sufficiently broken up during the FSW process, they are reported to remain in the FSW interior and weaken the bond strength. This type of weld defect has been referred to as a lazy "S", lazy "Z", joint line defect, kissing bond, or residual oxide defect. Usually these defects are mitigated by modification of the process parameters, such as increased tool rotation rate, which causes a finer breakup of the native oxide particles. This study proposes that there may be an alternative mechanism for formation of oxides found within the weld nugget. As the oxidation rate increases at elevated temperatures above 400ºC, it may be possible for enhanced oxidation to occur on the interior surfaces during the FSW process from entrained air entering the seam gap. Normally, FSWs of aluminum alloys are made without a purge gas and it is unknown how process parameters and initial fit up could affect a potential air path into the interior during the processing. In addition, variations in FSW parameters, such as the tool rotation, are known to have a strong influence on the FSW temperature which may affect the oxidation rate if internal surfaces are exposed to entrained air. A series of FSWs were made in 3 different thickness panels of AA2219 (0.95, 1.27 and 1.56 cm) at 2 different weld pitches. As the thickness of the panels increased, there was an increased tendency for a gap to form in advance of the weld tool. If sufficient air is able to enter the workpiece gap prior to consolidation, the weld temperature can increase the oxidation rate on the interior surfaces. These oxidation rates would also be accelerated in areas of localized liquation. Metallographs from the weld panels showed indications of liquation at the grain boundaries. In FSWs of thicker panels, these regions of liquation were found to be heavily oxidized. The quality of the FSWs was evaluated from tensile testing at room temperature. As the panel thickness increased, a slight decrease in tensile strength was observed which was attributed to the presence of oxides. No oxide formation was observed in the thinner workpieces, although there were indications of localized liquation at the grain boundaries. Results from this study will assist in a better understand of the mechanisms of oxide formation in FSW interiors and provide methodology for minimizing their occurrence.

Surface functionalization of copper via oxidative graft polymerization of 2,2'-bithiophene and immobilization of silver nanoparticles for combating biocorrosion.

PubMed

Wan, Dong; Yuan, Shaojun; Neoh, K G; Kang, E T

2010-06-01

An environmentally benign approach to surface modification was developed to impart copper surface with enhanced resistance to corrosion, bacterial adhesion and biocorrosion. Oxidative graft polymerization of 2,2'-bithiophene from the copper surface with self-assembled 2,2'-bithiophene monolayer, and subsequent reduction of silver ions to silver nanoparticles (Ag NPs) on the surface, give rise to a homogeneous bithiophene polymer (PBT) film with densely coupled Ag NPs on the copper surface (Cu-g-PBT-Ag NP surface). The immobilized Ag NPs were found to significantly inhibit bacterial adhesion and enhance the antibacterial properties of the PBT modified copper surface. The corrosion inhibition performance of the functionalized copper substrates was evaluated by Tafel polarization curves and electrochemical impedance spectroscopy. Arising from the chemical affinity of thiols for the noble and coinage metals, the copper surface functionalized with both PBT brushes and Ag NPs also exhibits long-term stability, and is thus potentially useful for combating the combined problems of corrosion and biocorrosion in harsh marine and aquatic environments.

Visualizing different uranium oxidation states during the surface alteration of uraninite and uranium tetrachloride.

PubMed

Grossmann, Kay; Arnold, Thuro; Steudtner, Robin; Weiss, Stefan; Bernhard, Gert

2009-08-01

Low-temperature alteration reactions on uranium phases may lead to the mobilization of uranium and thereby poses a potential threat to humans living close to uranium-contaminated sites. In this study, the surface alteration of uraninite (UO(2)) and uranium tetrachloride (UCl(4)) in air atmosphere was studied by confocal laser scanning microscopy (CLSM) and laser-induced fluorescence spectroscopy using an excitation wavelength of 408 nm. It was found that within minutes the oxidation state on the surface of the uraninite and the uranium tetrachloride changed. During the surface alteration process U(IV) atoms on the uraninite and uranium tetrachloride surface became stepwise oxidized by a one-electron step at first to U(V) and then further to U(VI). These observed changes in the oxidation states of the uraninite surface were microscopically visualized and spectroscopically identified on the basis of their fluorescence emission signal. A fluorescence signal in the wavelength range of 415-475 nm was indicative for metastable uranium(V), and a fluorescence signal in the range of 480-560 nm was identified as uranium(VI). In addition, the oxidation process of tetravalent uranium in aqueous solution at pH 0.3 was visualized by CLSM and U(V) was fluorescence spectroscopically identified. The combination of microscopy and fluorescence spectroscopy provided a very convincing visualization of the brief presence of U(V) as a metastable reaction intermediate and of the simultaneous coexistence of the three states U(IV), U(V), and U(VI). These results have a significant importance for fundamental uranium redox chemistry and should contribute to a better understanding of the geochemical behavior of uranium in nature.

Impact of Interfacial Composition on Lipid and Protein Co-Oxidation in Oil-in-Water Emulsions Containing Mixed Emulisifers.

PubMed

Zhu, Zhenbao; Zhao, Cui; Yi, Jianhua; Liu, Ning; Cao, Yuangang; Decker, Eric A; McClements, David Julian

2018-05-02

The impact of interfacial composition on lipid and protein co-oxidation in oil-in-water emulsions containing a mixture of proteins and surfactants was investigated. The emulsions consisted of 5% v/v walnut oil, 0.5% w/v whey protein isolate (WPI), and 0 to 0.4% w/v Tween 20 (pH 3 and pH 7). The protein surface load, magnitude of the ξ-potential, and mean particle diameter of the emulsions decreased as the Tween 20 concentration was increased, indicating the whey proteins were displaced by this nonionic surfactant. The whey proteins were displaced from the lipid droplet surfaces more readily at pH 3 than at pH 7, which may have been due to differences in the conformation or interactions of the proteins at the droplet surfaces at different pH values. Emulsions stabilized by whey proteins alone had relatively low lipid oxidation rates when incubated in the dark at 45 °C for up to 8 days, as determined by measuring lipid hydroperoxides and 2-thiobarbituric acid-reactive substances (TBARS). Conversely, the whey proteins themselves were rapidly oxidized, as shown by carbonyl formation, intrinsic fluorescence, sulfhydryl group loss, and electrophoresis measurements. Displacement of whey proteins from the interface by Tween 20 reduced protein oxidation but promoted lipid oxidation. These results indicated that the adsorbed proteins were more prone to oxidation than the nonadsorbed proteins, and therefore, they could act as better antioxidants. Protein oxidation was faster, while lipid oxidation was slower at pH 3 than at pH 7, which was attributed to a higher antioxidant activity of whey proteins under acidic conditions. These results highlight the importance of interfacial composition and solution pH on the oxidative stability of emulsions containing mixed emulsifiers.

Mars surface weathering products and spectral analogs: Palagonites and synthetic iron minerals

NASA Technical Reports Server (NTRS)

Golden, D. C.; Ming, D. W.; Morris, R. V.; Lauer, H. V., Jr.

1992-01-01

There are several hypotheses regarding the formation of Martian surface fines. These surface fines are thought to be products of weathering processes occurring on Mars. Four major weathering environments of igneous rocks on Mars have been proposed; (1) impact induced hydrothermal alterations; (2) subpermafrost igneous intrusion; (3) solid-gas surface reactions; and (4) subaerial igneous intrusion over permafrost. Although one or more of these processes may be important on the Martian surface, one factor in common for all these processes is the reaction of solid or molten basalt with water (solid, liquid, or gas). These proposed processes, with the exception of solid-gas surface reactions, are transient processes. The most likely product of transient hydrothermal processes are layer silicates, zeolites, hydrous iron oxides and palagonites. The long-term instability of hydrous clay minerals under present Martian conditions has been predicted; however, the persistence of such minerals due to slow kinetics of dehydration, or entrapment in permafrost, where the activity of water is high, can not be excluded. Anhydrous oxides of iron (e.g., hematite and maghemite) are thought to be stable under present Martian surface conditions. Oxidative weathering of sulfide minerals associated with Martian basalts has been proposed. Weathering of sulfide minerals leads to a potentially acidic permafrost and the formation of Fe(3) oxides and sulfates. Weathering of basalts under acidic conditions may lead to the formation of kaolinite through metastable halloysite and metahalloysite. Kaolinite, if present, is thought to be a thermodynamically stable phase at the Martian surface. Fine materials on Mars are important in that they influence the surface spectral properties; these fines are globally distributed on Mars by the dust storms and this fraction will have the highest surface area which should act as a sink for most of the absorbed volatiles near the surface of Mars. Therefore, the objectives of this study were to: (1) examine the fine fraction mineralogy of several palagonitic materials from Hawaii; and (2) compare spectral properties of palagonites and submicron sized synthetic iron oxides with the spectral properties of the Martian surface.

Quantum chemical study of arsenic (III, V) adsorption on Mn-oxides: implications for arsenic(III) oxidation.

PubMed

Zhu, Mengqiang; Paul, Kristian W; Kubicki, James D; Sparks, Donald L

2009-09-01

Density functional theory (DFT) calculations were used to investigate As(V) and As(III) surface complex structures and reaction energies on both Mn(III) and Mn(IV) sites in an attempt to better understand As(III) oxidation bybirnessite, a layered Mn-dioxide mineral. Edge-sharing dioctahedral Mn(III) and Mn(IV) clusters with different combinations of surface functional groups (>MnOH and >MnOH2) were employed to mimic pH variability. Results show that As(V) adsorption was more thermodynamically favorable than As(III) adsorption on both Mn(III) and Mn(IV) surface sites under simulated acidic pH conditions. Therefore, we propose that As(V) adsorption inhibits As(III) oxidation by blocking adsorption sites. Under simulated acidic pH conditions, Mn(IV) sites exhibited stronger adsorption affinity than Mn(III) sites for both As(III) and As(V). Overall, we hypothesize that Mn(III) sites are less reactive in terms of As(III) oxidation due to their lower affinity for As(III) adsorption, higher potential to be blocked by As(V) complexes, and slower electron transfer rates with adsorbed As(III). Results from this study offer an explanation regarding the experimental observations of Mn(III) accumulation on birnessite and the long residence time of As(III) adsorption complexes on manganite (r-MnOOH) during As(III) oxidation.

Different effect of hydrogelation on anti-fouling and circulation properties of dextran–iron oxide nanoparticles

PubMed Central

Karmali, Priya Prakash; Chao, Ying; Park, Ji-Ho (Joe); Sailor, Michael J.; Ruoslahti, Erkki; Esener, Sadik C.; Simberg, Dmitri

2012-01-01

Premature recognition and clearance of nanoparticulate imaging and therapeutic agents by macrophages in the tissues can dramatically reduce both the nanoparticle half-life and delivery to the diseased tissue. Grafting nanoparticles with hydrogels prevents nanoparticulate recognition by liver and spleen macrophages and greatly prolongs circulation times in vivo. Understanding the mechanisms by which hydrogels achieve this “stealth” effect has implications for the design of long-circulating nanoparticles. Thus, the role of plasma protein absorption in the hydrogel effect is not yet understood. Short-circulating dextran-coated iron oxide nanoparticles could be converted into stealth hydrogel nanoparticles by crosslinking with 1-chloro-2,3-epoxypropane. We show that hydrogelation did not affect the size, shape and zeta potential, but completely prevented the recognition and clearance by liver macrophages in vivo. Hydrogelation decreased the number of hydroxyl groups on the nanoparticle surface and reduced the binding of the anti-dextran antibody. At the same time, hydrogelation did not reduce the absorption of cationic proteins on the nanoparticle surface. Specifically, there was no effect on the binding of kininogen, histidine-rich glycoprotein, and protamine sulfate to the anionic nanoparticle surface. In addition, hydrogelation did not prevent activation of plasma kallikrein on the metal oxide surface. These data suggest that: (a) a stealth hydrogel coating does not mask charge interactions with iron oxide surface and (b) the total blockade of plasma protein absorption is not required for maintaining iron oxide nanoparticles’ long-circulating stealth properties. These data illustrate a novel, clinically promising property of long-circulating stealth nanoparticles. PMID:22243419

Poly(organo phosphazene) nanoparticles surface modified with poly(ethylene oxide).

PubMed

Vandorpe, J; Schacht, E; Stolnik, S; Garnett, M C; Davies, M C; Illum, L; Davis, S S

1996-10-05

The use of biodegradable derivatives of poly(organo phosphazenes) for the preparation of nanoparticles and their surface modification with the novel poly(ethylene oxide) derivative of poly(organo phosphazene) has been assessed using a range of in vitro characterization methods. The nanoparticles were produced by the precipitation solvent evaporation method from the derivative co-substituted with phenylalanine and glycine ethyl ester side groups. A reduction in particle size to less than 200 nm was achieved by an increase in pH of the preparation medium. The formation (and colloidal stability) of these nanoparticles seems to be controlled by two opposite effects: attractive hydrophobic interactions between phenylalanine ester groups and electrostatic repulsions arising from the carboxyl groups formed due to (partial) hydrolysis of the ester bond(s) at the high pH of the preparation medium. The poly[(glycine ethyl ester)phosphazene] derivative containing 5000-Da poly(ethylene oxide) as 5% of the side groups was used for the surface modification of nanoparticles. Adsorbed onto the particles, the polymer produced a thick coating layer of approximately 35 nm. The coated nanoparticles exhibited reduced surface negative potential and improved colloidal stability toward electrolyte-induced flocculation, relative to the uncoated system. However, the steric stabilization provided was less effective than that of a Poloxamine 908 coating. This difference in effectiveness of the steric stabilization might indicate that, although both the stabilizing polymers possess a 5000-Da poly(ethylene oxide) moiety, there is a difference in the arrangements of these poly(ethylene oxide) chains at the particle surface. (c) 1996 John Wiley & Sons, Inc.

The effect of metal (hydr)oxide nano-enabling on intraparticle mass transport of organic contaminants in hybrid granular activated carbon.

PubMed

Garcia, Jose; Markovski, Jasmina; McKay Gifford, J; Apul, Onur; Hristovski, Kiril D

2017-05-15

The overarching goal of this study was to ascertain the changes in intraparticle mass transport rates for organic contaminants resulting from nano-enabled hybridization of commercially available granular activated carbon (GAC). Three different nano-enabled hybrid media were fabricated by in-situ synthesizing titanium dioxide nanoparticles inside the pores of GAC sorbent, characterized, and evaluated for removal of two model organic contaminants under realistic conditions to obtain the intraparticle mass transport (pore and surface diffusion) coefficients. The results validated the two hypotheses that: (H1) the pore diffusion rates of organic contaminants linearly decrease with decrease in cumulative pore volume caused by increase in metal (hydr)oxide nanoparticle content inside the pores of the hybrid GAC sorbent; and (H2) introduction of metal (hydr)oxide nanoparticles initially increases surface diffusivity, but additional loading causes its decrease as the increase in metal (hydr)oxide nanoparticles content continues to reduce the porosity of the GAC sorbent. Nano-enabled hybridization of commercially available GAC with metal (hydr)oxides has the potential to significantly increase the intraparticle mass transport limitations for organic contaminants. Introduction of metal (hydr)oxide nanoparticles inside the pores of a pristine sorbent causes the pore diffusion rates of organic contaminants to decrease as the cumulative pore volume is reduced. In contrast, the introduction of limited amounts of metal (hydr)oxide nanoparticles appears to facilitate the surface diffusion rates of these contaminants. Copyright © 2017 Elsevier B.V. All rights reserved.

Improved method for producing catalytic carbon and the potential for increasing its use in commercial applications

USGS Publications Warehouse

Kruse, C.W.; Lizzio, A.A.; DeBarr, J.A.; Feizoulof, C.A.

1997-01-01

This paper describes an improved method for producing a catalytic carbon, which was first produced in the late 1960s. The new activated carbon (AC) removes and destroys organic pollutants in aqueous solutions. To determine the effects of altering the pore structure and surface chemistry of activated carbons, carbons differing in the amount of functional groups on their surfaces were prepared in three steps: (1) oxidizing AC with boiling nitric acid, (2) washing oxidized AC with water to remove the acid, and (3) heating oxidized AC to temperatures beteween 100 and 925 ??C. The surfaces of the products were characterized by determining the amount of CO2 and CO evolved during temperature-programmed desorption. Depending on the desorption temperature, these modified carbons showed enhanced adsorptive and/or catalytic properties that included (1) carbon molecular sieves for separating oxygen from nitrogen, (2) increased capacity for adsorbing sulfur dioxide, (3) stronger adsorption of p-nitrophenol from water, and (4) catalysis of dehydrochlorination reactions. A dehydrohalogenation catalyst produced by the oxidation/ desorption steps was found to be similar to one prepared in the 1960s by oxidizing AC with air at 500-700 ??C. The dehydrohalogenation catalyst produced by either the old method or the new method involves an oxidized surface that has been exposed to a 500-700 ??C temperature range. This carbon catalyst retains modified adsorptive properties of the AC from which it is produced. It can be used both to adsorb pollutants from liquid or gaseous streams and to convert them to recyclable products.

Electrochemical oxidation of ciprofloxacin in two different processes: the electron transfer process on the anode surface and the indirect oxidation process in bulk solutions.

PubMed

Shen, Bo; Wen, Xianghua; Korshin, Gregory V

2018-05-14

Herein, the rotating disk electrode technique was used for the first time to investigate the effects of mass-transfer limitations and pH on the electrochemical oxidation of CPX, to determine the kinetics of CPX oxidation and to explore intrinsic mechanisms during the electron transfer process. Firstly, cyclic voltammetry revealed that an obvious irreversible CPX oxidation peak was observed within the potential window from 0.70 to 1.30 V at all pHs. Based on the Levich equation, the electrochemical oxidation of CPX in the electron transfer process was found to be controlled by both diffusion and kinetic processes when pH = 2, 5, 7 and 9; the diffusion coefficient of CPX at pH = 2 was calculated to be 1.5 × 10-7 cm2 s-1. Kinetic analysis indicated that the reaction on the electrode surface was adsorption-controlled compared to a diffusion process; the surface concentration of electroactive species was estimated to be 1.15 × 10-9 mol cm-2, the standard rate constant of the surface reaction was calculated to be 1.37 s-1, and CPX oxidation was validated to be a two-electron transfer process. Finally, a possible CPX oxidation pathway during the electron transfer process was proposed. The electrochemical degradation of CPX on a Ti-based anode was also conducted subsequently to investigate the electrochemical oxidation of CPX in the indirect oxidation process in bulk solutions. The effects of pH and current density were determined and compared to related literature results. The oxidation of CPX at different pHs is believed to be the result of a counterbalance between favorable and unfavorable factors, namely electromigration and side reactions of oxygen evolution, respectively. The effects of current density indicated a diffusion- and reaction-controlled process at low currents followed by a reaction-controlled process at high currents. The results presented in this study provide better understanding of the electrochemical oxidation of CPX and would enable the development of new treatment methods based on electrochemistry.

Responsive Surface Methodology Optimizes Extraction Conditions of Industrial by-products, Camellia japonica Seed Cake

PubMed Central

Kim, Jae Kyeom; Lim, Ho-Jeong; Kim, Mi-So; Choi, Soo Jung; Kim, Mi-Jeong; Kim, Cho Rong; Shin, Dong-Hoon; Shin, Eui-Cheol

2016-01-01

Background: The central nervous system is easily damaged by oxidative stress due to high oxygen consumption and poor defensive capacity. Hence, multiple studies have demonstrated that inhibiting oxidative stress-induced damage, through an antioxidant-rich diet, might be a reasonable approach to prevent neurodegenerative disease. Objective: In the present study, response surface methodology was utilized to optimize the extraction for neuro-protective constituents of Camellia japonica byproducts. Materials and Methods: Rat pheochromocytoma cells were used to evaluate protective potential of Camellia japonica byproducts. Results: Optimum conditions were 33.84 min, 75.24%, and 75.82°C for time, ethanol concentration and temperature. Further, we demonstrated that major organic acid contents were significantly impacted by the extraction conditions, which may explain varying magnitude of protective potential between fractions. Conclusions: Given the paucity of information in regards to defatted C. japonica seed cake and their health promoting potential, our results herein provide interesting preliminary data for utilization of this byproduct from oil processing in both academic and industrial applications. SUMMARY Neuro-protective potential of C. japonica seed cake on cell viability was affected by extraction conditionsExtraction conditions effectively influenced on active constituents of C. japonica seed cakeBiological activity of C. japonica seed cake was optimized by the responsive surface methodology. Abbreviations used: GC-MS: Gas chromatography-mass spectrometer, MTT: 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide, PC12 cells: Pheochromocytoma, RSM: Response surface methodology. PMID:27601847

Revisiting the Corrosion of the Aluminum Current Collector in Lithium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Tianyuan; Xu, Gui-Liang; Li, Yan

The corrosion of aluminum current collectors and the oxidation of solvents at a relatively high potential have been widely investigated with an aim to stabilize the electrochemical performance of lithium-ion batteries using such components. The corrosion behavior of aluminum current collectors was revisited using a home-build high-precision electrochemical measurement system, and the impact of electrolyte components and the surface protection layer on aluminum foil was systematically studied. The electrochemical results showed that the corrosion of aluminum foil was triggered by the electrochemical oxidation of solvent molecules, like ethylene carbonate, at a relative high potential. The organic radical cations generated frommore » the electrochemical oxidation are energetically unstable, and readily undergo a deprotonation reaction that generates protons and promote the dissolution of Al3+ from the aluminum foil. This new reaction mechanism can also shed light on the dissolution of transitional metal at high potentials.« less

Revisiting the Corrosion of the Aluminum Current Collector in Lithium-Ion Batteries

DOE PAGES

Ma, Tianyuan; Xu, Gui -Liang; Li, Yan; ...

2017-02-16

The corrosion of aluminum current collectors and the oxidation of solvents at a relatively high potential have been widely investigated with an aim to stabilize the electrochemical performance of lithium-ion batteries using such components. The corrosion behavior of aluminum current collectors was revisited using a home-build high-precision electrochemical measurement system, and the impact of electrolyte components and the surface protection layer on aluminum foil was systematically studied. The electrochemical results showed that the corrosion of aluminum foil was triggered by the electrochemical oxidation of solvent molecules, like ethylene carbonate, at a relative high potential. The organic radical cations generated frommore » the electrochemical oxidation are energetically unstable, and readily undergo a deprotonation reaction that generates protons and promote the dissolution of Al 3+ from the aluminum foil. Finally, this new reaction mechanism can also shed light on the dissolution of transitional metal at high potentials.« less

On the cobalt and cobalt oxide electrodeposition from a glyceline deep eutectic solvent.

PubMed

Sakita, Alan M P; Della Noce, Rodrigo; Fugivara, Cecílio S; Benedetti, Assis V

2016-09-14

The electrodeposition of cobalt and cobalt oxides from a glyceline deep eutectic solvent is reported. Cyclic voltammetry, chronoamperometry, scanning electron microscopy, and Raman spectroscopy are employed to study the Co deposition processes. Surface analysis reveals that metallic cobalt is deposited at potentials less negative than the current peak potential whereas cobalt oxides are detected and electrochemically observed when the deposition is done at more negative potentials. i-t transients are analyzed by applying the Scharifker and Hills (SH) theoretical model. It is concluded that cobalt deposition occurs via a progressive nucleation and growth mechanism for concentrations higher than 0.05 mol L -1 cobalt ions. For concentrations ≤0.025 mol L -1 cobalt ions and low overpotentials, the mechanism changes to instantaneous nucleation. The i m -t m relationships of the SH model are used to determine the values of the kinetic parameters and the cobalt ion diffusion coefficient.

Revisiting the Corrosion of the Aluminum Current Collector in Lithium-Ion Batteries.

PubMed

Ma, Tianyuan; Xu, Gui-Liang; Li, Yan; Wang, Li; He, Xiangming; Zheng, Jianming; Liu, Jun; Engelhard, Mark H; Zapol, Peter; Curtiss, Larry A; Jorne, Jacob; Amine, Khalil; Chen, Zonghai

2017-03-02

The corrosion of aluminum current collectors and the oxidation of solvents at a relatively high potential have been widely investigated with an aim to stabilize the electrochemical performance of lithium-ion batteries using such components. The corrosion behavior of aluminum current collectors was revisited using a home-build high-precision electrochemical measurement system, and the impact of electrolyte components and the surface protection layer on aluminum foil was systematically studied. The electrochemical results showed that the corrosion of aluminum foil was triggered by the electrochemical oxidation of solvent molecules, like ethylene carbonate, at a relative high potential. The organic radical cations generated from the electrochemical oxidation are energetically unstable and readily undergo a deprotonation reaction that generates protons and promotes the dissolution of Al 3+ from the aluminum foil. This new reaction mechanism can also shed light on the dissolution of transitional metal at high potentials.

Revisiting the Corrosion of the Aluminum Current Collector in Lithium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Tianyuan; Xu, Gui -Liang; Li, Yan

The corrosion of aluminum current collectors and the oxidation of solvents at a relatively high potential have been widely investigated with an aim to stabilize the electrochemical performance of lithium-ion batteries using such components. The corrosion behavior of aluminum current collectors was revisited using a home-build high-precision electrochemical measurement system, and the impact of electrolyte components and the surface protection layer on aluminum foil was systematically studied. The electrochemical results showed that the corrosion of aluminum foil was triggered by the electrochemical oxidation of solvent molecules, like ethylene carbonate, at a relative high potential. The organic radical cations generated frommore » the electrochemical oxidation are energetically unstable, and readily undergo a deprotonation reaction that generates protons and promote the dissolution of Al 3+ from the aluminum foil. Finally, this new reaction mechanism can also shed light on the dissolution of transitional metal at high potentials.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Toczydlowska, Diana; Kedra-Krolik, Karolina; Nejbert, Krzysztof

The role of surface electrostatics on the reductive dissolution of iron (III) oxides is poorly understood, despite its importance in controlling the amount of mobilized iron. We report the potentiometric titration of the a; y -Fe2O3 oxides exposed to reductants and complexing ligands (Fe(II), ascorbate, oxalate, malonate). We monitored in situ surface and potentials, the ratio of mobilized ferric to ferrous ions, and periodically analyzed nanoparticle crystal structure using X-ray diffraction. We found that addition of Fe2+ ions produces a response consistent with the iron solubilityactivity curve, whereas the presence of ascorbate significantly decreases the amount of mobilized Fe(III) duemore » to reduction to Fe(II). In addition, XRD analysis proved that y-Fe2O3 particles remain structurally unchanged along the titration pathway despite iron cycling between aqueous and solid reservoirs. Our studies, suggest that the surface redoxactivity of iron oxides is primarily governed by the balance between Fe(III) and Fe(II) ions in aqueous phase, which may be easily altered by complexing and reducing agents.« less

The role of crystallographic texture in achieving low friction zinc oxide nanolaminate films

NASA Astrophysics Data System (ADS)

Mojekwu, Nneoma

Metal oxide nanolaminate films are potential high temperature solid lubricants due to their ability to exhibit significant plasticity when grain size is reduced to the nanometer scale, and defective growth structure is achieved by condensation of oxygen vacancies to form intrinsic stacking faults. This is in contrast to conventional microcrystalline and single crystal oxides that exhibit brittle fracture during loading in a sliding contact. This study emphasizes the additional effect of growth orientation, in particular crystallographic texture, on determining the sliding friction behavior in nanocolumnar grain zinc oxide films grown by atomic layer deposition. It was determined that zinc oxide low (0002) versus higher (101¯3) surface energy crystallographic planes influenced the sliding friction coefficient. Texturing of the (0002) grains resulted in a decreased adhesive component of friction thereby lowering the sliding friction coefficient to ˜0.25, while the friction coefficient doubled to ˜0.5 with increasing contribution of surface (101¯3) grains. In addition, the variation of the x-ray grazing incident angle from 0.5° to 5° was studied to better understand the surface grain orientation as a function of ZnO layer thickness in one versus four bilayer nanolaminates where the under layer (seed layer) was load-bearing Zn(Ti,Zr)O3.

Defect Chemistry of Oxides for Energy Applications.

PubMed

Schweke, Danielle; Mordehovitz, Yuval; Halabi, Mahdi; Shelly, Lee; Hayun, Shmuel

2018-05-31

Oxides are widely used for energy applications, as solid electrolytes in various solid oxide fuel cell devices or as catalysts (often associated with noble metal particles) for numerous reactions involving oxidation or reduction. Defects are the major factors governing the efficiency of a given oxide for the above applications. In this paper, the common defects in oxide systems and external factors influencing the defect concentration and distribution are presented, with special emphasis on ceria (CeO 2 ) based materials. It is shown that the behavior of a variety of oxide systems with respect to properties relevant for energy applications (conductivity and catalytic activity) can be rationalized by general considerations about the type and concentration of defects in the specific system. A new method based on transmission electron microscopy (TEM), recently reported by the authors for mapping space charge defects and measuring space charge potentials, is shown to be of potential importance for understanding conductivity mechanisms in oxides. The influence of defects on gas-surface reactions is exemplified on the interaction of CO 2 and H 2 O with ceria, by correlating between the defect distribution in the material and its adsorption capacity or splitting efficiency. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Propitious Dendritic Cu2O-Pt Nanostructured Anodes for Direct Formic Acid Fuel Cells.

PubMed

El-Nagar, Gumaa A; Mohammad, Ahmad M; El-Deab, Mohamed S; El-Anadouli, Bahgat E

2017-06-14

This study introduces a novel competent dendritic copper oxide-platinum nanocatalyst (nano-Cu 2 O-Pt) immobilized onto a glassy carbon (GC) substrate for formic acid (FA) electro-oxidation (FAO); the prime reaction in the anodic compartment of direct formic acid fuel cells (DFAFCs). Interestingly, the proposed catalyst exhibited an outstanding improvement for FAO compared to the traditional platinum nanoparticles (nano-Pt) modified GC (nano-Pt/GC) catalyst. This was evaluated from steering the reaction mechanism toward the desired direct route producing carbon dioxide (CO 2 ); consistently with mitigating the other undesired indirect pathway producing carbon monoxide (CO); the potential poison deteriorating the catalytic activity of typical Pt-based catalysts. Moreover, the developed catalyst showed a reasonable long-term catalytic stability along with a significant lowering in onset potential of direct FAO that ultimately reduces the polarization and amplifies the fuel cell's voltage. The observed catalytic enhancement was believed to originate bifunctionally; while nano-Pt represented the base for the FA adsorption, nanostructured copper oxide (nano-Cu 2 O) behaved as a catalytic mediator facilitating the charge transfer during FAO and providing the oxygen atmosphere inspiring the poison's (CO) oxidation at relatively lower potential. Surprisingly, moreover, nano-Cu 2 O induced a surface retrieval of nano-Pt active sites by capturing the poisoning CO via "a spillover mechanism" to renovate the Pt surface for the direct FAO. Finally, the catalytic tolerance of the developed catalyst toward halides' poisoning was discussed.

Effect of surface treatment and sterilization processes on the corrosion behavior of NiTi shape memory alloy.

PubMed

Thierry, B; Tabrizian, M; Trepanier, C; Savadogo, O; Yahia, L

2000-09-15

Nickel-titanium (NiTi) alloy derives its biocompatibility and good corrosion resistance from a homogeneous oxide layer mainly composed of TiO(2), with a very low concentration of nickel. In this article, we described the corrosion behavior of NiTi alloys after mechanical polishing, electropolishing, and sterilization processes using cyclic polarization and atomic absorption. As a preparative surface treatment, electropolishing decreased the amount of nickel on the surface and remarkably improved the corrosion behavior of the alloy by increasing the mean breakdown potential value and the reproducibility of the results (0.99 +/- 0.05 V/SCE vs. 0.53 +/- 0. 42). Ethylene oxide and Sterrad(R) sterilization techniques did not modify the corrosion resistance of electropolished NiTi, whereas a steam autoclave and, to a lesser extent, peracetic acid sterilization produced scattered breakdown potential. In comparing the corrosion resistance of common biomaterials, NiTi ranked between 316L stainless steel and Ti6A14V even after sterilization. Electropolished NiTi and 316L stainless-steel alloys released similar amounts of nickel after a few days of immersion in Hank's solution. Measurements by atomic absorption have shown that the amount of released nickel from passive dissolution was below the expected toxic level in the human body. Auger electron spectroscopy analyses indicated surface contamination by Ca and P on NiTi during immersion, but no significant modification in oxide thickness was observed.

Effects of size and surface of zinc oxide and aluminum-doped zinc oxide nanoparticles on cell viability inferred by proteomic analyses.

PubMed

Pan, Chih-Hong; Liu, Wen-Te; Bien, Mauo-Ying; Lin, I-Chan; Hsiao, Ta-Chih; Ma, Chih-Ming; Lai, Ching-Huang; Chen, Mei-Chieh; Chuang, Kai-Jen; Chuang, Hsiao-Chi

2014-01-01

Although the health effects of zinc oxide nanoparticles (ZnONPs) on the respiratory system have been reported, the fate, potential toxicity, and mechanisms in biological cells of these particles, as related to particle size and surface characteristics, have not been well elucidated. To determine the physicochemical properties of ZnONPs that govern cytotoxicity, we investigated the effects of size, electronic properties, zinc concentration, and pH on cell viability using human alveolar-basal epithelial A549 cells as a model. We observed that a 2-hour or longer exposure to ZnONPs induced changes in cell viability. The alteration in cell viability was associated with the zeta potentials and pH values of the ZnONPs. Proteomic profiling of A549 exposed to ZnONPs for 2 and 4 hours was used to determine the biological mechanisms of ZnONP toxicity. p53-pathway activation was the core mechanism regulating cell viability in response to particle size. Activation of the Wnt and TGFβ signaling pathways was also important in the cellular response to ZnONPs of different sizes. The cadherin and Wnt signaling pathways were important cellular mechanisms triggered by surface differences. These results suggested that the size and surface characteristics of ZnONPs might play an important role in their observed cytotoxicity. This approach facilitates the design of more comprehensive systems for the evaluation of nanoparticles.

Effect of anodization on the surface characteristics and electrochemical behaviour of zirconium in artificial saliva.

PubMed

Romonti, Daniela E; Gomez Sanchez, Andrea V; Milošev, Ingrid; Demetrescu, Ioana; Ceré, Silvia

2016-05-01

The paper is focused on elaboration of ZrO2 films on pure zirconium via anodizing in phosphoric acid with and without fluoride at constant potentials of 30 V and 60 V. The structure and composition of the films were investigated using scanning electronic microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The composition of the oxides formed at both potentials can be identified as monoclinic ZrO2. In addition to Zr and O, the layers formed in phosphoric acid contain phosphorus originating from the phosphoric acid. When the phosphoric acid solution contains NaF, fluorine is also incorporated into the oxide layer. The oxides formed at a higher voltage have greater roughness than those formed at 30 V. Anodized samples exhibit smaller current densities during anodic polarization compared to the as-received zirconium covered with native oxide. Copyright © 2016 Elsevier B.V. All rights reserved.

Electronic Interactions of Size-Selected Oxide Clusters on Metallic and Thin Film Oxide Supports

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xue, Meng; Nakayama, Miki; Liu, Ping

The interfacial electronic structure of various size-selected metal oxide nanoclusters (M 3O x; M = Mo, Nb, Ti) on Cu(111) and a thin film of Cu 2O supports were investigated in this paper by a combination of experimental methods and density functional theory (DFT). These systems explore electron transfer at the metal–metal oxide interface which can modify surface structure, metal oxidation states, and catalytic activity. Electron transfer was probed by measurements of surface dipoles derived from coverage dependent work function measurements using two-photon photoemission (2PPE) and metal core level binding energy spectra from X-ray photoelectron spectroscopy (XPS). The measured surfacemore » dipoles are negative for all clusters on Cu(111) and Cu 2O/Cu(111), but those on the Cu 2O surface are much larger in magnitude. In addition, sub-stoichiometric or “reduced” clusters exhibit smaller surface dipoles on both the Cu(111) and Cu 2O surfaces. Negative surface dipoles for clusters on Cu(111) suggest Cu → cluster electron transfer, which is generally supported by DFT-calculated Bader charge distributions. For Cu 2O/Cu(111), calculations of the surface electrostatic potentials show that the charge distributions associated with cluster adsorption structures or distortions at the cluster–Cu 2O–Cu(111) interface are largely responsible for the observed negative surface dipoles. Changes observed in the XPS spectra for the Mo 3d, Nb 3d, and Ti 2p core levels of the clusters on Cu(111) and Cu 2O/Cu(111) are interpreted with help from the calculated Bader charges and cluster adsorption structures, the latter providing information about the presence of inequivalent cation sites. Finally, the results presented in this work illustrate how the combined use of different experimental probes along with theoretical calculations can result in a more realistic picture of cluster–support interactions and bonding.« less

Electronic Interactions of Size-Selected Oxide Clusters on Metallic and Thin Film Oxide Supports

DOE PAGES

Xue, Meng; Nakayama, Miki; Liu, Ping; ...

2017-09-13

The interfacial electronic structure of various size-selected metal oxide nanoclusters (M 3O x; M = Mo, Nb, Ti) on Cu(111) and a thin film of Cu 2O supports were investigated in this paper by a combination of experimental methods and density functional theory (DFT). These systems explore electron transfer at the metal–metal oxide interface which can modify surface structure, metal oxidation states, and catalytic activity. Electron transfer was probed by measurements of surface dipoles derived from coverage dependent work function measurements using two-photon photoemission (2PPE) and metal core level binding energy spectra from X-ray photoelectron spectroscopy (XPS). The measured surfacemore » dipoles are negative for all clusters on Cu(111) and Cu 2O/Cu(111), but those on the Cu 2O surface are much larger in magnitude. In addition, sub-stoichiometric or “reduced” clusters exhibit smaller surface dipoles on both the Cu(111) and Cu 2O surfaces. Negative surface dipoles for clusters on Cu(111) suggest Cu → cluster electron transfer, which is generally supported by DFT-calculated Bader charge distributions. For Cu 2O/Cu(111), calculations of the surface electrostatic potentials show that the charge distributions associated with cluster adsorption structures or distortions at the cluster–Cu 2O–Cu(111) interface are largely responsible for the observed negative surface dipoles. Changes observed in the XPS spectra for the Mo 3d, Nb 3d, and Ti 2p core levels of the clusters on Cu(111) and Cu 2O/Cu(111) are interpreted with help from the calculated Bader charges and cluster adsorption structures, the latter providing information about the presence of inequivalent cation sites. Finally, the results presented in this work illustrate how the combined use of different experimental probes along with theoretical calculations can result in a more realistic picture of cluster–support interactions and bonding.« less

Controlled deposition of size-selected MnO nanoparticle thin films for water splitting applications: reduction of onset potential with particle size

NASA Astrophysics Data System (ADS)

Khojasteh, Malak; Haghighat, Shima; Dawlaty, Jahan M.; Kresin, Vitaly V.

2018-05-01

Emulating water oxidation catalyzed by the oxomanganese clusters in the photosynthetic apparatus of plants has been a long-standing scientific challenge. The use of manganese oxide films has been explored, but while they may be catalytically active on the surface, their poor conductivity hinders their overall performance. We have approached this problem by using manganese oxide nanoparticles with sizes of 4, 6 and 8 nm, produced in a sputter-gas-aggregation source and soft-landed onto conducting electrodes. The mass loading of these catalytic particles was kept constant and corresponded to 45%–80% of a monolayer coverage. Measurements of the water oxidation threshold revealed that the onset potential decreases significantly with decreasing particle size. The final stoichiometry of the catalytically active nanoparticles, after exposure to air, was identified as predominantly MnO. The ability of such a sub-monolayer film to lower the reaction threshold implies that the key role is played by intrinsic size effects, i.e., by changes in the electronic properties and surface fields of the nanoparticles with decreasing size. We anticipate that this work will serve to bridge the knowledge gap between bulk thick film electrocatalysts and natural photosynthetic molecular-cluster complexes.

Toxicity studies of six types of carbon nanoparticles in a chicken-embryo model.

PubMed

Kurantowicz, Natalia; Sawosz, Ewa; Halik, Gabriela; Strojny, Barbara; Hotowy, Anna; Grodzik, Marta; Piast, Radosław; Pasanphan, Wanvimol; Chwalibog, André

2017-01-01

In the present study, the toxicity of six different types of carbon nanoparticles (CNPs) was investigated using a chicken-embryo model. Fertilized chicken eggs were divided into the following treatment groups: placebo, diamond NPs, graphite NPs, pristine graphene, small graphene oxide, large graphene oxide, and reduced graphene oxide. Experimental solutions at a concentration of 500 μg/mL were administrated into the egg albumin. Gross pathology and the rate of survival were examined after 5, 10, 15, and 20 days of incubation. After 20 days of incubation, blood samples were collected and the weight of the body and organs measured. The relative ratio of embryo survival decreased after treatment all treatments except diamond NPs. There was no correlation between the rate of survival and the ζ-potential or the surface charge of the CNPs in solution. Body and organ weight, red blood-cell morphology, blood serum biochemical parameters, and oxidative damage in the liver did not differ among the groups. These results indicate that CNPs can remain in blood circulation without any major side effects, suggesting their potential applicability as vehicles for drug delivery or active compounds per se. However, there is a need for further investigation of their properties, which vary depending on production methods and surface functionalization.

Toxicity studies of six types of carbon nanoparticles in a chicken-embryo model

PubMed Central

Kurantowicz, Natalia; Sawosz, Ewa; Halik, Gabriela; Strojny, Barbara; Hotowy, Anna; Grodzik, Marta; Piast, Radosław; Pasanphan, Wanvimol; Chwalibog, André

2017-01-01

In the present study, the toxicity of six different types of carbon nanoparticles (CNPs) was investigated using a chicken-embryo model. Fertilized chicken eggs were divided into the following treatment groups: placebo, diamond NPs, graphite NPs, pristine graphene, small graphene oxide, large graphene oxide, and reduced graphene oxide. Experimental solutions at a concentration of 500 μg/mL were administrated into the egg albumin. Gross pathology and the rate of survival were examined after 5, 10, 15, and 20 days of incubation. After 20 days of incubation, blood samples were collected and the weight of the body and organs measured. The relative ratio of embryo survival decreased after treatment all treatments except diamond NPs. There was no correlation between the rate of survival and the ζ-potential or the surface charge of the CNPs in solution. Body and organ weight, red blood-cell morphology, blood serum biochemical parameters, and oxidative damage in the liver did not differ among the groups. These results indicate that CNPs can remain in blood circulation without any major side effects, suggesting their potential applicability as vehicles for drug delivery or active compounds per se. However, there is a need for further investigation of their properties, which vary depending on production methods and surface functionalization. PMID:28435265

Control of Alq3 wetting layer thickness via substrate surface functionalization.

PubMed

Tsoi, Shufen; Szeto, Bryan; Fleischauer, Michael D; Veinot, Jonathan G C; Brett, Michael J

2007-06-05

The effects of substrate surface energy and vapor deposition rate on the initial growth of porous columnar tris(8-hydroxyquinoline)aluminum (Alq3) nanostructures were investigated. Alq3 nanostructures thermally evaporated onto as-supplied Si substrates bearing an oxide were observed to form a solid wetting layer, likely caused by an interfacial energy mismatch between the substrate and Alq3. Wetting layer thickness control is important for potential optoelectronic applications. A dramatic decrease in wetting layer thickness was achieved by depositing Alq3 onto alkyltrichlorosilane-derivatized Si/oxide substrates. Similar effects were noted with increasing deposition rates. These two effects enable tailoring of the wetting layer thickness.

Interlaminar fracture in carbon fiber/thermoplastic composites

NASA Technical Reports Server (NTRS)

Hinkley, J. A.; Bascom, W. D.; Allred, R. E.

1990-01-01

The surfaces of commercial carbon fibers are generally chemically cleaned or oxidized and then coated with an oligomeric sizing to optimize their adhesion to epoxy matrix resins. Evidence from fractography, from embedded fiber testing and from fracture energies suggests that these standard treatments are relatively ineffective for thermoplastic matrices. This evidence is reviewed and model thermoplastic composites (polyphenylene oxide/high strain carbon fibers) are used to demonstrate how differences in adhesion can lead to a twofold change in interlaminar fracture toughness. The potential for improved adhesion via plasma modification of fiber surfaces is discussed. Finally, a surprising case of fiber-catalyzed resin degradation is described.

A perspective on the hemolytic activity of chemical and green-synthesized silver and silver oxide nanoparticles

NASA Astrophysics Data System (ADS)

Ashokraja, C.; Sakar, M.; Balakumar, S.

2017-10-01

We report the hemolysis properties of silver and silver oxide nanoparticles (NPs) prepared by chemical and green-synthesis methods. The prepared silver and silver oxide NPs were analyzed using UV-vis spectroscopy to confirm their formation by characterizing their surface plasmon resonance (SPR) and absorption band peaks respectively. The Fourier transmission infrared (FTIR) spectra of the materials showed the characteristic functional groups corresponding to the molecules present in leaf extracts, which is proposed to be acted as reducing and capping agents that are also found on the surface of silver and silver oxide nanoparticles that synthesized via green-synthesis method. Zeta potential analysis revealed the surface charge and stability of the prepared NPs. HRTEM images showed almost spherical shape nanoparticles with an average size of 15.2 and 31.5 nm for wet chemical synthesized silver and silver oxide nanoparticles respectively. In the case of green synthesized silver and silver oxide nanoparticles, it was observed to be 19.4 and 30.4 nm respectively. The order of hemolysis efficacy of the materials is found to be as follows: chemically synthesized Ag2O>  chemically synthesized Ag NPs followed by green-synthesized Ag2O and green-synthesized Ag NPs which showed almost similar hemolysis with respect to concentration. The relatively stable nature of the silver NPs could be attributed to their lower hemolysis efficacy, while the increased lysis properties of silver oxide could be attributed due to reductive/oxidative processes that give rise to the hemolysis through interfacial charge interactions with RBCs.

A study of oxidative stress induced by non-thermal plasma-activated water for bacterial damage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Qian; Ma, Ruonan; Tian, Ying

2013-05-20

Ar/O{sub 2} (2%) cold plasma microjet was used to create plasma-activated water (PAW). The disinfection efficacy of PAW against Staphylococcus aureus showed that PAW can effectively disinfect bacteria. Optical emission spectra and oxidation reduction potential results demonstrated the inactivation is attributed to oxidative stress induced by reactive oxygen species in PAW. Moreover, the results of X-ray photoelectron spectroscopy, atomic absorption spectrometry, and transmission electron microscopy suggested that the chemical state of cell surface, the integrity of cell membrane, as well as the cell internal components and structure were damaged by the oxidative stress.

Preparation of well-distributed titania nanopillar arrays on Ti6Al4V surface by induction heating for enhancing osteogenic differentiation of stem cells

NASA Astrophysics Data System (ADS)

Li, Ning-Bo; Sun, Sheng-Jun; Bai, Han-Ying; Xiao, Gui-Yong; Xu, Wen-Hua; Zhao, Jun-Han; Chen, Xin; Lu, Yu-Peng; Zhang, Yi-Lin

2018-01-01

Great effort has recently been devoted to the preparation of nanoscale surfaces on titanium-based implants to achieve clinically fast osteoinduction and osseointegration, which relies on the unique characteristics of the nanostructure. In this work, we used induction heating treatment (IHT) as a rapid oxidation method to fabricate a porous nanoscale oxide layer on the Ti6Al4V surface for better medical application. Well-distributed vertical nanopillars were yielded by IHT for 20-35 s on the alloy surface. The composition of the oxides contained rutile/anatase TiO2 and a small amount of Al2O3 between the TiO2 grain boundaries (GBs). This technology resulted in a reduction and subsequent increase of surface roughness of 26-32 nm when upregulating the heating time, followed by the successive enhancement of the thickness, wettability and adhesion strength of the oxidation layer to the matrix. The surface hardness also distinctly rose to 554 HV in the IHT-35 s group compared with the 350 HV of bare Ti6Al4V. The massive small-angle GBs in the bare alloy promoted the formation of nanosized oxide crystallites. The grain refinement and deformation texture reduction further improved the mechanical properties of the matrix after IHT. Moreover, in vitro experiments on a mesenchymal stem cell (BMSC) culture derived from human bone marrow for 1-7 days indicated that the nanoscale layers did not cause cytotoxicity, and facilitated cell differentiation in osteoblasts by enhancing the gene and osteogenesis-related protein expressions after 1-3 weeks of culturing. The increase of the IHT time slightly advanced the BMSC proliferation and differentiation, especially during long-term culture. Our findings provide strong evidence that IHT oxidation technology is a novel nanosurface modification technology, which is potentially promising for further clinical development.

The Selective Epitaxy of Silicon at Low Temperatures.

NASA Astrophysics Data System (ADS)

Lou, Jen-Chung

1991-01-01

This dissertation has developed a process for the selective epitaxial growth (SEG) of silicon at low temperatures using a dichlorosilane-hydrogen mixture in a hot-wall low pressure chemical vapor deposition (LPCVD) reactor. Some basic issues concerning the quality of epilayers --substrate preparation, ex-situ and in-situ cleaning, and deposition cycle, have been studied. We find it necessary to use a plasma etch to open epitaxial windows for the SEG of Si. A cycled plasma etch, a thin sacrificial oxide growth, and an oxide etching step can completely remove plasma-etch-induced surface damage and contaminants, which result in high quality epilayers. A practical wafer cleaning step is developed for low temperature Si epitaxial growth. An ex-situ HF vapor treatment can completely remove chemical oxide from the silicon surface and retard the reoxidation of the silicon surface. An in-situ low-concentration DCS cycle can aid in decomposition of surface oxide during a 900 ^circC H_2 prebake step. An HF vapor treatment combined with a low-concentration of DCS cycle consistently achieves defect-free epilayers at 850^circC and lower temperatures. We also show that a BF_sp{2}{+ } or F^+ ion implantation is a potential ex-situ wafer cleaning process for SEG of Si at low temperatures. The mechanism for the formation of surface features on Si epilayers is also discussed. Based on O ^+ ion implantation, we showed that the oxygen incorporation in silicon epilayers suppresses the Si growth rate. Therefore, we attribute the formation of surface features to the local reduction of the Si growth rate due to the dissolution of oxide islands at the epi/substrate interface. Finally, with this developed process for the SEG of silicon, defect-free overgrown epilayers are also obtained. This achievement demonstrates the feasibility for the future silicon-on-oxide (SOI) manufacturing technology.

In situ measurements of dissolved oxygen, pH and redox potential of biocathode microenvironments using microelectrodes.

PubMed

Wang, Zejie; Deng, Huan; Chen, Lihui; Xiao, Yong; Zhao, Feng

2013-03-01

Biofilms are the core component of bioelectrochemical systems (BESs). To understand the polarization effects on biocathode performance of BES, dissolved oxygen concentrations, pHs and oxidation-reduction potentials of biofilm microenvironments were determined in situ. The results showed that lower polarization potentials resulted in the generation of larger currents and higher pH values, as well as the consumption of more oxygen. Oxidation-reduction potentials of biofilms were mainly affected by polarization potentials of the electrode rather than the concentration of dissolved oxygen or pH value, and its changes in the potentials corresponded to the electric field distribution of the electrode surface. The results demonstrated that a sufficient supply of dissolved oxygen and pH control of the biocathode are necessary to obtain optimal performance of BESs; a lower polarization potential endowed microorganisms with a higher electrochemical activity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Effect of processing conditions on microstructural features in Mn–Si sintered steels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oro, Raquel, E-mail: raqueld@chalmers.se; Hryha, Eduard, E-mail: hryha@chalmers.se; Campos, Mónica, E-mail: campos@ing.uc3m.es

2014-09-15

Sintering of steels containing oxidation sensitive elements is possible if such elements are alloyed with others which present lower affinity for oxygen. In this work, a master alloy powder containing Fe–Mn–Si–C, specifically designed to create a liquid phase during sintering, has been used for such purpose. The effect of processing conditions such as sintering temperature and atmosphere was studied with the aim of describing the microstructural evolution as well as the morphology and distribution of oxides in the sintered material, evaluating the potential detrimental effect of such oxides on mechanical properties. Chemical analyses, metallography and fractography studies combined with X-raymore » photoelectron spectroscopy analyses on the fracture surfaces were used to reveal the main mechanism of fracture and their correlation with the chemical composition of the different fracture surfaces. The results indicate that the main mechanism of failure in these steels is brittle fracture in the surrounding of the original master alloy particles due to degradation of grain boundaries by the presence of oxide inclusions. Mn–Si oxide inclusions were observed on intergranular decohesive facets. The use of reducing atmospheres and high sintering temperatures reduces the amount and size of such oxide inclusions. Besides, high heating and cooling rates reduce significantly the final oxygen content in the sintered material. A model for microstructure development and oxide evolution during different stages of sintering is proposed, considering the fact that when the master alloy melts, the liquid formed can dissolve some of the oxides as well as the surface of the surrounding iron base particles. - Highlights: • Oxide distribution in steels containing oxidation-sensitive elements • Mn, Si introduced in a master alloy powder, mixed with a base iron powder • Selective oxidation of Mn and Si on iron grain boundaries • Decohesive fracture caused by degradation of grain boundaries by oxide inclusions • Reducing agents efficient at low temperatures critical for avoiding oxide inclusions.« less

Nutrient Controls on Methane Emissions in a Permafrost Thaw Subarctic Peatland

NASA Astrophysics Data System (ADS)

Kashi, N. N.; Perryman, C. R.; Malhotra, A.; Marek, E. A.; Giesler, R.; Varner, R. K.

2015-12-01

Permafrost peatlands in northern latitudes are large reservoirs of sequestered carbon that are vulnerable to climate change. While peatlands account for a small fraction of total global land surfaces, their potential to release sequestered carbon in response to higher temperatures is of concern. Of particular relevance is the conversion of these carbon stores into methane (CH4), a strong greenhouse gas with a global warming potential 20 times greater than that of CO2 over a 100-year time frame. Here, we explore how key nutrients impact the consumption of CH4 at the Stordalen Mire in Abisko, Sweden, a discontinuous permafrost peatland with expanding thaw over the last century. Peatland CH4 emissions are highly spatially variable due to multiple emission pathways and strong dependence on several environmental factors. Among controls on CH4 emissions, such as temperature and water table depth, primary production of wetland vegetation is also a strong factor in the variability of CH4 emissions. Plant community shifts among permafrost thaw stages subsequently change nutrient cycling and availability, which in turn impacts primary production. Early stages of permafrost thaw are mosaicked with a variety of vascular plants and mosses. We analyzed potential enzymatic activities of chitinase, glucosidase, and phosphatase as proxies for organic nitrogen, carbon, and phosphorus cycling, respectively, in tandem with potential CH4 oxidation rates. In addition, stoichiometric ratios of carbon, nitrogen, and phosphorus concentrations are used to illustrate nutrient limitation controls on CH4 oxidation rates. While CH4 emissions are low throughout initial thaw stages, < 7 CH4 mg m-2 day-1, we found they had the highest rates of potential CH4 oxidation. These permafrost thaw-induced CH4 oxidation rates are 5 and 11 times higher, in the surface and depth of the peat profile respectively, than subsequent aerobic permafrost thaw stages. As CH4 emissions are low in intact permafrost peatlands, these high rates of potential CH4 oxidation indicate the importance of plant communities and the methanotrophic microbes they harbor.

Two orders of magnitude enhancement in oxygen evolution reactivity on amorphous Ba0.5Sr0.5Co0.8Fe0.2O3−δ nanofilms with tunable oxidation state

PubMed Central

Chen, Gao; Zhou, Wei; Guan, Daqin; Sunarso, Jaka; Zhu, Yanping; Hu, Xuefeng; Zhang, Wei; Shao, Zongping

2017-01-01

Perovskite oxides exhibit potential for use as electrocatalysts in the oxygen evolution reaction (OER). However, their low specific surface area is the main obstacle to realizing a high mass-specific activity that is required to be competitive against the state-of-the-art precious metal–based catalysts. We report the enhanced performance of Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) for the OER with intrinsic activity that is significantly higher than that of the benchmark IrO2, and this result was achieved via fabrication of an amorphous BSCF nanofilm on a surface-oxidized nickel substrate by magnetron sputtering. The surface nickel oxide layer of the Ni substrate and the thickness of the BSCF film were further used to tune the intrinsic OER activity and stability of the BSCF catalyst by optimizing the electronic configuration of the transition metal cations in BSCF via the interaction between the nanofilm and the surface nickel oxide, which enables up to 315-fold enhanced mass-specific activity compared to the crystalline BSCF bulk phase. Moreover, the amorphous BSCF–Ni foam anode coupled with the Pt–Ni foam cathode demonstrated an attractive small overpotential of 0.34 V at 10 mA cm−2 for water electrolysis, with a BSCF loading as low as 154.8 μg cm−2. PMID:28691090

Oxidation-Mediated Fingering in Liquid Metals

NASA Astrophysics Data System (ADS)

Eaker, Collin B.; Hight, David C.; O'Regan, John D.; Dickey, Michael D.; Daniels, Karen E.

2017-10-01

We identify and characterize a new class of fingering instabilities in liquid metals; these instabilities are unexpected due to the large interfacial tension of metals. Electrochemical oxidation lowers the effective interfacial tension of a gallium-based liquid metal alloy to values approaching zero, thereby inducing drastic shape changes, including the formation of fractals. The measured fractal dimension (D =1.3 ±0.05 ) places the instability in a different universality class than other fingering instabilities. By characterizing changes in morphology and dynamics as a function of droplet volume and applied electric potential, we identify the three main forces involved in this process: interfacial tension, gravity, and oxidative stress. Importantly, we find that electrochemical oxidation can generate compressive interfacial forces that oppose the tensile forces at a liquid interface. The surface oxide layer ultimately provides a physical and electrochemical barrier that halts the instabilities at larger positive potentials. Controlling the competition between interfacial tension and oxidative (compressive) stresses at the interface is important for the development of reconfigurable electronic, electromagnetic, and optical devices that take advantage of the metallic properties of liquid metals.

Monitoring Tensile Fatigue of Superelastic NiTi Wire in Liquids by Electrochemical Potential

NASA Astrophysics Data System (ADS)

Racek, Jan; Stora, Marc; Šittner, Petr; Heller, Luděk; Kopeček, Jaromir; Petrenec, Martin

2015-06-01

Fatigue of superelastic NiTi wires was investigated by cyclic tension in simulated biofluid. The state of the surface of the fatigued NiTi wire was monitored by following the evolution of the electrochemical open circuit potential (OCP) together with macroscopic stresses and strains. The ceramic TiO2 oxide layer on the NiTi wire surface cannot withstand the large transformation strain and fractures in the first cycle. Based on the analysis of the results of in situ OCP experiments and SEM observation of cracks, it is claimed that the cycled wire surface develops mechanochemical reactions at the NiTi/liquid interface leading to cumulative generation of hydrogen, uptake of the hydrogen by the NiTi matrix, local loss of the matrix strength, crack transfer into the NiTi matrix, accelerated crack growth, and ultimately to the brittle fracture of the wire. Fatigue degradation is thus claimed to originate from the mechanochemical processes occurring at the excessively deforming surface not from the accumulation of defects due to energy dissipative bulk deformation processes. Ironically, combination of the two exciting properties of NiTi—superelasticity due to martensitic transformation and biocompatibility due to the protective TiO2 surface oxide layer—leads to excessive fatigue damage during cyclic mechanical loading in biofluids.

The Effects of Different Wavelength UV Photofunctionalization on Micro-Arc Oxidized Titanium

PubMed Central

Zhou, Lei; Guo, Zehong; Rong, Mingdeng; Liu, Xiangning; Lai, Chunhua; Ding, Xianglong

2013-01-01

Many challenges exist in improving early osseointegration, one of the most critical factors in the long-term clinical success of dental implants. Recently, ultraviolet (UV) light-mediated photofunctionalization of titanium as a new potential surface treatment has aroused great interest. This study examines the bioactivity of titanium surfaces treated with UV light of different wavelengths and the underlying associated mechanism. Micro-arc oxidation (MAO) titanium samples were pretreated with UVA light (peak wavelength of 360 nm) or UVC light (peak wavelength of 250 nm) for up to 24 h. UVC treatment promoted the attachment, spread, proliferation and differentiation of MG-63 osteoblast-like cells on the titanium surface, as well as the capacity for apatite formation in simulated body fluid (SBF). These biological influences were not observed after UVA treatment, apart from a weaker effect on apatite formation. The enhanced bioactivity was substantially correlated with the amount of Ti-OH groups, which play an important role in improving the hydrophilicity, along with the removal of hydrocarbons on the titanium surface. Our results showed that both UVA and UVC irradiation altered the chemical properties of the titanium surface without sacrificing its excellent physical characteristics, suggesting that this technology has extensive potential applications and merits further investigation. PMID:23861853

Investigation of surface potentials in reduced graphene oxide flake by Kelvin probe force microscopy

NASA Astrophysics Data System (ADS)

Negishi, Ryota; Takashima, Kai; Kobayashi, Yoshihiro

2018-06-01

The surface potential (SP) of reduced graphene oxide (rGO) flakes prepared by thermal treatments of GO under several conditions was analyzed by Kelvin probe force microscopy. The low-crystalline rGO flakes in which a significant amount of oxygen functional groups and structural defects remain have a much lower SP than mechanically exfoliated graphene free from oxygen and defects. On the other hand, the highly crystalline rGO flake after a thermal treatment for the efficient removal of oxygen functional groups and healing of structural defects except for domain boundary shows SP equivalent to that of the mechanically exfoliated graphene. These results indicate that the work function of rGO is sensitively modulated by oxygen functional groups and structural defects remaining after the thermal reduction process, but is not affected significantly by the domain boundary remaining after the healing of structural defects through the thermal treatment at high temperature.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vega-Arroyo, M.; LeBreton, P. R.; Zapol, P.

Photoinduced charge separation in triads of DNA covalently linked to an anatase nanoparticle via a dopamine bridge was studied by ab initio calculations of the oxidation potentials of carboxyl-DNA trimers and the TiO2/dopamine complex. Conjugation of dopamine to the TiO2 surface results in a lower oxidation potential of the complex relative to the surface and in localization of photogenerated holes on dopamine, while photogenerated electrons are excited into the conduction band of TiO2. Linking dopamine to the DNA trimers at the 5? end of the oligonucleotide may lead to further hole migration to the DNA. Calculations show that for severalmore » different sequences hole migration is favorable in double stranded DNA and unfavorable in single-stranded DNA. This extended charge separation was shown to follow from the redox properties of DNA sequence rather than from the modification of DNA's electron donating properties by the dopamine linker, which explains experimental observations.« less

Colloidal aluminum nanoparticles with tunable localized surface plasmon resonances for energy applications

NASA Astrophysics Data System (ADS)

Cheng, Yan; Smith, Kenneth; Arinze, Ebuka; Nyirjesy, Gabrielle; Bragg, Arthur; Thon, Susanna

Localized surface plasmon resonances (LSPRs) of noble metal nanoparticles are of interest for energy applications due to their visible and near infrared wavelength sensitivity. However, application of these materials in optoelectronic devices is limited by their rarity and high cost. Earth-abundant, inexpensive and non-toxic aluminum is a promising alternative material with a plasmon resonance that can also be tuned via size-, shape- and surface-oxide-control. Here, we employ solution-processed methods to synthesize stable colloidal aluminum nanoparticles. We systematically investigate parameters in the synthesis that control size, shape and oxidation of the aluminum nanoparticles and tune their LSPRs over the ultraviolet and visible spectral regions. We optically characterize the nanoparticle solutions and evaluate their potential for future integration into photovoltaic, photocatalytic and photosensing systems.

Statistical analysis of the electrocatalytic activity of Pt nanoparticles supported on novel functionalized reduced graphene oxide-chitosan for methanol electrooxidation

NASA Astrophysics Data System (ADS)

Ekrami-Kakhki, Mehri-Saddat; Abbasi, Sedigheh; Farzaneh, Nahid

2018-01-01

The purpose of this study is to statistically analyze the anodic current density and peak potential of methanol oxidation at Pt nanoparticles supported on functionalized reduced graphene oxide (RGO), using design of experiments methodology. RGO is functionalized with methyl viologen (MV) and chitosan (CH). The novel Pt/MV-RGO-CH catalyst is successfully prepared and characterized with transmission electron microscopy (TEM) image. The electrocatalytic activity of Pt/MV-RGOCH catalyst is experimentally evaluated for methanol oxidation. The effects of methanol concentration and scan rate factors are also investigated experimentally and statistically. The effects of these two main factors and their interactions are investigated, using analysis of variance test, Duncan's multiple range test and response surface method. The results of the analysis of variance show that all the main factors and their interactions have a significant effect on anodic current density and peak potential of methanol oxidation at α = 0.05. The suggested models which encompass significant factors can predict the variation of the anodic current density and peak potential of methanol oxidation. The results of Duncan's multiple range test confirmed that there is a significant difference between the studied levels of the main factors. [Figure not available: see fulltext.

Distribution and speciation of trace elements in iron and manganese oxide cave deposits

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frierdich, Andrew J.; Catalano, Jeffrey G.

2012-10-24

Fe and Mn oxide minerals control the distribution and speciation of heavy metals and trace elements in soils and aquatic systems through chemical mechanisms involving adsorption, incorporation, and electron transfer. The Pautler Cave System in Southwest Illinois, an analog to other temperate carbonate-hosted karst systems, contains Fe and Mn oxide minerals that form in multiple depositional environments and have high concentrations of associated trace elements. Synchrotron-based micro-scanning X-ray fluorescence ({mu}-SXRF) shows unique spatial distributions of Fe, Mn, and trace elements in mineral samples. Profile maps of Mn oxide cave stream pebble coatings show Fe- and As-rich laminations, indicating dynamic redoxmore » conditions in the cave stream. {mu}-SXRF maps demonstrate that Ni, Cu, and Zn correlate primarily with Mn whereas As correlates with both Mn and Fe; As is more enriched in the Fe phase. Zn is concentrated in the periphery of Mn oxide stream pebble coatings, and may be an indication of recent anthropogenic surface activity. X-ray absorption fine structure spectroscopy measurements reveal that As(V) occurs as surface complexes on Mn and Fe oxides whereas Zn(II) associated with Mn oxides is adsorbed to the basal planes of phyllomanganates in a tetrahedral coordination. Co(III) and Se(IV) are also observed to be associated with Mn oxides. The observation of Fe, Mn, and trace element banding in Mn oxide cave stream pebble coatings suggests that these materials are sensitive to and document aqueous redox conditions, similar to ferromanganese nodules in soils and in marine and freshwater sediments. Furthermore, speciation and distribution measurements indicate that these minerals scavenge trace elements and limit the transport of micronutrients and contaminants in karst aquifer systems while also potentially recording changes in anthropogenic surface activity and land-use.« less

Hybrid Nanomaterials with Single-Site Catalysts by Spatially Controllable Immobilization of Nickel Complexes via Photoclick Chemistry for Alkene Epoxidation.

PubMed

Ghosh, Dwaipayan; Febriansyah, Benny; Gupta, Disha; Ng, Leonard Kia-Sheun; Xi, Shibo; Du, Yonghua; Baikie, Tom; Dong, ZhiLi; Soo, Han Sen

2018-05-22

Catalyst deactivation is a persistent problem not only for the scientific community but also in industry. Isolated single-site heterogeneous catalysts have shown great promise to overcome these problems. Here, a versatile anchoring strategy for molecular complex immobilization on a broad range of semiconducting or insulating metal oxide ( e. g., titanium dioxide, mesoporous silica, cerium oxide, and tungsten oxide) nanoparticles to synthesize isolated single-site catalysts has been studied systematically. An oxidatively stable anchoring group, maleimide, is shown to form covalent linkages with surface hydroxyl functionalities of metal oxide nanoparticles by photoclick chemistry. The nanocomposites have been thoroughly characterized by techniques including UV-visible diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and X-ray absorption spectroscopy (XAS). The IR spectroscopic studies confirm the covalent linkages between the maleimide group and surface hydroxyl functionalities of the oxide nanoparticles. The hybrid nanomaterials function as highly efficient catalysts for essentially quantitative oxidations of terminal and internal alkenes and show molecular catalyst product selectivities even in more eco-friendly solvents. XAS studies verify the robustness of the catalysts after several catalytic cycles. We have applied the photoclick anchoring methodology to precisely control the deposition of a luminescent variant of our catalyst on the metal oxide nanoparticles. Overall, we demonstrate a general approach to use irradiation to anchor molecular complexes on oxide nanoparticles to create recyclable, hybrid, single-site catalysts that function with high selectivity in a broad range of solvents. We have achieved a facile, spatially and temporally controllable photoclick method that can potentially be extended to other ligands, catalysts, functional molecules, and surfaces.

Band positions of Rutile surfaces and the possibility of water splitting

NASA Astrophysics Data System (ADS)

Esch, Tobit R.; Bredow, Thomas

2017-11-01

It is well known that both the band gap and the band edge positions of oxide semiconductors are important for the photocatalytic water splitting. In this study, we show that different surface terminations of the same crystalline solid lead to considerable variations of the band gaps and band edges. As an example, we investigate the low-index surfaces of rutile TiO2. A series of hybrid methods based on the PBE exchange-correlation functional, PBE0, HSE06 and HISS, are employed to study the effect of long-range exchange on the electronic properties. In aqueous solution, the oxide particles employed in photocatalysis are fully covered with water molecules. We therefore study the influence of molecularly and dissociatively adsorbed water on the band positions. It is found that water adsorption leads to significant shifts of the band edge positions due to changes of the electrostatic potential at the surface atom positions.

Atomic layer deposition of ruthenium on plasma-treated vertically aligned carbon nanotubes for high-performance ultracapacitors.

PubMed

Kim, Jun Woo; Kim, Byungwoo; Park, Suk Won; Kim, Woong; Shim, Joon Hyung

2014-10-31

It is challenging to realize a conformal metal coating by atomic layer deposition (ALD) because of the high surface energy of metals. In this study, ALD of ruthenium (Ru) on vertically aligned carbon nanotubes (CNTs) was carried out. To activate the surface of CNTs that lack surface functional groups essential for ALD, oxygen plasma was applied ex situ before ALD. X-ray photoelectron spectroscopy and Raman spectroscopy confirmed surface activation of CNTs by the plasma pretreatment. Transmission electron microscopy analysis with energy-dispersive x-ray spectroscopy composition mapping showed that ALD Ru grew conformally along CNTs walls. ALD Ru/CNTs were electrochemically oxidized to ruthenium oxide (RuOx) that can be a potentially useful candidate for use in the electrodes of ultracapacitors. Electrode performance of RuOx/CNTs was evaluated using cyclic voltammetry and galvanostatic charge-discharge measurements.

Patterning of a-C DLC films: exploration of an aqueous electro-oxidative mechanism

NASA Astrophysics Data System (ADS)

Mühl, Thomas; Myhra, Sverre

2007-06-01

Conducting ion-beam assisted CVD deposited a-C type DLC films can be patterned electro-oxidatively by masked and maskless probe-induced STM-based lithography. The former constitutes a parallel rapid processing technology, with the tip acting as a distant stationary electrode. The latter is a higher spatial resolution serial technology, with the tip defining a travelling local electro-chemical cell. The mechanism is based on electro-oxidative conversion of solid carbon to gaseous CO or CO2 in the presence of an aqueous phase, either as a bulk fluid or as a thin adsorbed film. The process is constrained kinetically in the early stages by limitations on charge transport through the surface barrier at the fluid-to-solid interface and subsequently by the availability of oxidants and by their transport to reactive sites. The as-received surface is terminated by chemisorbed oxygen, leading to the formation of an insulating surface barrier. The threshold potential for initiation of conversion depends on the width of the barrier. The results may have implications for new technologies exploiting the properties of carbon-based materials, but may also add to the present understanding of the electrochemistry of carbon solids.

Evaluation of fatty acid oxidation by reactive oxygen species induced in liquids using atmospheric-pressure nonthermal plasma jets

NASA Astrophysics Data System (ADS)

Tani, Atsushi; Fukui, Satoshi; Ikawa, Satoshi; Kitano, Katsuhisa

2015-10-01

We investigated fatty acid oxidation by atmospheric-pressure nonthermal helium plasma using linoleic acid, an unsaturated fatty acid, together with evaluating active species induced in liquids. If the ambient gas contains oxygen, direct plasma such as plasma jets coming into contact with the liquid surface supplies various active species, such as singlet oxygen, ozone, and superoxide anion radicals, to the liquid. The direct plasma easily oxidizes linoleic acid, indicating that fatty acid oxidation will occur in the direct plasma. In contrast, afterglow flow, where the plasma is terminated in a glass tube and does not touch the surface of the liquid sample, supplies mainly superoxide anion radicals. The fact that there was no clear observation of linoleic acid oxidation using the afterglow reveals that it may not affect lipids, even in an atmosphere containing oxygen. The afterglow flow can potentially be used for the sterilization of aqueous solutions using the reduced pH method, in medical and dental applications, because it provides bactericidal activity in the aqueous solution despite containing a smaller amount of active species.

Surface modification of poly(dimethylsiloxane) for microfluidic assay applications

NASA Astrophysics Data System (ADS)

Séguin, Christine; McLachlan, Jessica M.; Norton, Peter R.; Lagugné-Labarthet, François

2010-02-01

The surface of a poly(dimethylsiloxane) (PDMS) film was imparted with patterned functionalities at the micron-scale level. Arrays of circles with diameters of 180 and 230 μm were functionalized using plasma oxidation coupled with aluminum deposition, followed by silanization with solutions of 3-aminopropyltrimethoxy silane (3-APTMS) and 3-mercaptopropyltrimethoxy silane (3-MPTMS), to obtain patterned amine and thiol functionalities, respectively. The modification of the samples was confirmed using X-ray photoelectron spectroscopy (XPS), gold nanoparticle adhesion coupled with optical microscopy, as well as by derivatization with fluorescent dyes. To further exploit the novel surface chemistry of the modified PDMS, samples with surface amine functionalities were used to develop a protein assay as well as an array capable of cellular capture and patterning. The modified substrate was shown to successfully selectively immobilize fluorescently labeled immunoglobulin G (IgG) by tethering Protein A to the surface, and, for the cellular arrays, C2C12 rat endothelial cells were captured. Finally, this novel method of patterning chemical functionalities onto PDMS has been incorporated into microfluidic channels. Finally, we demonstrate the in situ chemical modification of the protected PDMS oxidized surface within a microfluidic device. This emphasizes the potential of our method for applications involving micron-scale assays since the aluminum protective layer permits to functionalize the oxidized PDMS surface several weeks after plasma treatment simply after etching away the metallic thin film.

Oxidation-driven surface dynamics on NiAl(100)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qin, Hailang; Chen, Xidong; Li, Liang

Atomic steps, a defect common to all crystal surfaces, can play an important role in many physical and chemical processes. However, attempts to predict surface dynamics under nonequilibrium conditions are usually frustrated by poor knowledge of the atomic processes of surface motion arising from mass transport from/to surface steps. Using low-energy electron microscopy that spatially and temporally resolves oxide film growth during the oxidation of NiAl(100) we demonstrate that surface steps are impermeable to oxide film growth. The advancement of the oxide occurs exclusively on the same terrace and requires the coordinated migration of surface steps. The resulting piling upmore » of surface steps ahead of the oxide growth front progressively impedes the oxide growth. This process is reversed during oxide decomposition. The migration of the substrate steps is found to be a surface-step version of the well-known Hele-Shaw problem, governed by detachment (attachment) of Al atoms at step edges induced by the oxide growth (decomposition). As a result, by comparing with the oxidation of NiAl(110) that exhibits unimpeded oxide film growth over substrate steps, we suggest that whenever steps are the source of atoms used for oxide growth they limit the oxidation process; when atoms are supplied from the bulk, the oxidation rate is not limited by the motion of surface steps.« less

Oxidation-driven surface dynamics on NiAl(100)

DOE PAGES

Qin, Hailang; Chen, Xidong; Li, Liang; ...

2014-12-29

Atomic steps, a defect common to all crystal surfaces, can play an important role in many physical and chemical processes. However, attempts to predict surface dynamics under nonequilibrium conditions are usually frustrated by poor knowledge of the atomic processes of surface motion arising from mass transport from/to surface steps. Using low-energy electron microscopy that spatially and temporally resolves oxide film growth during the oxidation of NiAl(100) we demonstrate that surface steps are impermeable to oxide film growth. The advancement of the oxide occurs exclusively on the same terrace and requires the coordinated migration of surface steps. The resulting piling upmore » of surface steps ahead of the oxide growth front progressively impedes the oxide growth. This process is reversed during oxide decomposition. The migration of the substrate steps is found to be a surface-step version of the well-known Hele-Shaw problem, governed by detachment (attachment) of Al atoms at step edges induced by the oxide growth (decomposition). As a result, by comparing with the oxidation of NiAl(110) that exhibits unimpeded oxide film growth over substrate steps, we suggest that whenever steps are the source of atoms used for oxide growth they limit the oxidation process; when atoms are supplied from the bulk, the oxidation rate is not limited by the motion of surface steps.« less

Analysis of polymer/oxide interfaces under ambient conditions - An experimental perspective

NASA Astrophysics Data System (ADS)

González-Orive, A.; Giner, I.; de los Arcos, T.; Keller, A.; Grundmeier, G.

2018-06-01

In many different hybrid materials and materials composites polymers adhere to bulk oxides or oxide covered metal. The formed polymer/oxide interfaces are of crucial importance for the functionality and durability of such complex materials. Especially, under humid and corrosive conditions such interfaces tend to degrade due to permeability of polymers for water, the high adsorption energy of water on oxide surfaces and even corrosion processes of the metal. Different experimental studies considered such interfaces ranging from spectroscopy to electrochemical analysis. However, it is still a challenge to understand the complex interaction especially under non-ideal ambient conditions. The perspective article presents an overview on the existing experimental approaches and considers most recent experimental developments with regard to their potential applications in the area of polymer/oxide interfaces in the future.

Methylmercury oxidative degradation potentials in contaminated and pristine sediments of the Carson River, Nevada

USGS Publications Warehouse

Oremland, R.S.; Miller, L.G.; Dowdle, P.; Connell, T.; Barkay, T.

1995-01-01

Sediments from mercury-contaminated and uncontaminated reaches of the Carson River, Nevada, were assayed for sulfate reduction, methanogenesis, denitrification, and monomethylmercury (MeHg) degradation. Demethylation of [14C]MeHg was detected at all sites as indicated by the formation of 14CO2 and 14CH4. Oxidative demethylation was indicated by the formation of 14CO2 and was present at significant levels in all samples. Oxidized/reduced demethylation product ratios (i.e., 14CO2/14CH4 ratios) generally ranged from 4.0 in surface layers to as low as 0.5 at depth. Production of 14CO2 was most pronounced at sediment surfaces which were zones of active denitrification and sulfate reduction but was also significant within zones of methanogenesis. In a core taken from an uncontaminated site having a high proportion of oxidized, coarse-grain sediments, sulfate reduction and methanogenic activity levels were very low and 14CO2 accounted for 98% of the product formed from [14C]MeHg. There was no apparent relationship between the degree of mercury contamination of the sediments and the occurrence of oxidative demethylation. However, sediments from Fort Churchill, the most contaminated site, were most active in terms of demethylation potentials. Inhibition of sulfate reduction with molybdate resulted in significantly depressed oxidized/reduced demethylation product ratios, but overall demethylation rates of inhibited and uninhibited samples were comparable. Addition of sulfate to sediment slurries stimulated production of 14CO2 from [14C]MeHg, while 2-bromoethanesulfonic acid blocked production of 14CH4. These results reveal the importance of sulfate-reducing and methanogenic bacteria in oxidative demethylation of MeHg in anoxic environments.

Nanopatterning of Crystalline Silicon Using Anodized Aluminum Oxide Templates for Photovoltaics

NASA Astrophysics Data System (ADS)

Chao, Tsu-An

A novel thin film anodized aluminum oxide templating process was developed and applied to make nanopatterns on crystalline silicon to enhance the optical properties of silicon. The thin film anodized aluminum oxide was created to improve the conventional thick aluminum templating method with the aim for potential large scale fabrication. A unique two-step anodizing method was introduced to create high quality nanopatterns and it was demonstrated that this process is superior over the original one-step approach. Optical characterization of the nanopatterned silicon showed up to 10% reduction in reflection in the short wavelength range. Scanning electron microscopy was also used to analyze the nanopatterned surface structure and it was found that interpore spacing and pore density can be tuned by changing the anodizing potential.

Probing electronic and vibrational properties at the electrochemical interface using SFG spectroscopy: Methanol electro-oxidation on Pt(1 1 0)

NASA Astrophysics Data System (ADS)

Vidal, F.; Busson, B.; Tadjeddine, A.

2005-02-01

We report the study of methanol electro-oxidation on Pt(1 1 0) using infrared-visible sum-frequency generation (SFG) vibrational spectroscopy. The use of this technique enables to probe the vibrational and electronic properties of the interface simultaneously in situ. We have investigated the vibrational properties of the interface in the CO ads internal stretch spectral region (1700-2150 cm -1) over a wide range of potentials. The analysis of the evolution of the C-O stretch line shape, which is related to the interference between the vibrational and electronic parts of the non-linear response, with the potential allows us to show that the onset of bulk methanol oxidation corresponds to the transition from a negatively to a positively charged surface.

Tuning oxidation level, electrical conductance and band gap structure on graphene sheets by cyclic atomic layer reduction technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gu, Si-Yong; Hsieh, Chien-Te; Lin, Tzu-Wei

The present work develops an atomic layer reduction (ALR) method to accurately tune oxidation level, electrical conductance, band-gap structure, and photoluminescence (PL) response of graphene oxide (GO) sheets. The ALR route is carried out at 200 °C within ALR cycle number of 10–100. The ALR treatment is capable of striping surface functionalities (e.g., hydroxyl, carbonyl, and carboxylic groups), producing thermally-reduced GO sheets. The ALR cycle number serves as a controlling factor in adjusting the crystalline, surface chemistry, electrical, optical properties of GO sheets. With increasing the ALR cycle number, ALR-GO sheets display a high crystallinity, a low oxidation level, anmore » improved electrical conductivity, a narrow band gap, and a tunable PL response. Finally, on the basis of the results, the ALR technique offers a great potential for accurately tune electrical and optical properties of carbon materials through the cyclic removal of oxygen functionalities, without any complicated thermal and chemical desorption processes.« less

Surface interactions affect the toxicity of engineered metal oxide nanoparticles toward Paramecium.

PubMed

Li, Kungang; Chen, Ying; Zhang, Wen; Pu, Zhichao; Jiang, Lin; Chen, Yongsheng

2012-08-20

To better understand the potential impacts of engineered metal oxide nanoparticles (NPs) in the ecosystem, we investigated the acute toxicity of seven different types of engineered metal oxide NPs against Paramecium multimicronucleatum, a ciliated protozoan, using the 48 h LC(50) (lethal concentration, 50%) test. Our results showed that the 48 h LC(50) values of these NPs to Paramecium ranged from 0.81 (Fe(2)O(3) NPs) to 9269 mg/L (Al(2)O(3) NPs); their toxicity to Paramecium increased as follows: Al(2)O(3) < TiO(2) < CeO(2) < ZnO < SiO(2) < CuO < Fe(2)O(3) NPs. On the basis of the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, interfacial interactions between NPs and cell membrane were evaluated, and the magnitude of interaction energy barrier correlated well with the 48 h LC(50) data of NPs to Paramecium; this implies that metal oxide NPs with strong association with the cell surface might induce more severe cytotoxicity in unicellular organisms.

Mobility and Oxidation of Adsorbed CO on Shape-Controlled Pt Nanoparticles in Acidic Medium.

PubMed

Farias, Manuel J S; Busó-Rogero, Carlos; Vidal-Iglesias, Francisco J; Solla-Gullón, José; Camara, Giuseppe A; Feliu, Juan M

2017-01-31

The knowledge about how CO occupies and detaches from specific surface sites on well-structured Pt surfaces provides outstanding information on both dynamics/mobility of CO ads and oxidation of this molecule under electrochemical conditions. This work reports how the potentiostatic growth of different coverage CO adlayers evolves with time on both cubic and octahedral Pt nanoparticles in acidic medium. Data suggest that during the growth of the CO adlayer, CO ads molecules slightly shift toward low coordination sites only on octahedral Pt nanoparticles, so that these undercoordinated sites are the first filled on octahedral Pt nanoparticles. Conversely, on cubic Pt nanoparticles, adsorbed CO behaves as an immobile species, and low coordinated sites as well as (100) terraces are apparently filled uniformly and simultaneously. However, once the adlayer is complete, irrespectively of whether the CO is oxidized in a single step or in a sequence of different potential steps, results suggest that CO ads behaves as an immobile species during its oxidation on both octahedral and cubic Pt nanoparticles.

Synthesis of porous graphene powder through improved Hummers' method

NASA Astrophysics Data System (ADS)

Gupta, Siddhant; Bonageri, Shrilakshmi; Achar, Siddarth Krishnaraja; Menon, Atul; Basavaraja R., J.

2018-05-01

Graphene due to its high specific surface area is considered to be a potential adsorbent for air and water purification systems. In this study, graphene was synthesized using the recently developed Improved Hummers' method to achieve a high oxidation rate and thermal treatment of the synthesized graphene was done to increase its pore size and make it more capable for applications in purification systems. Graphite flakes were oxidized to obtain graphene oxide which was then reduced to obtain graphene. The synthesized graphene was then thermally treated at 200 °C for two hours in a muffle furnace to improve its surface properties. The characterization results of graphene oxide and graphene show the presence of many impurities which is inferred to be the result of contaminated water used in the experimentation. The analysis of the characterization results also shows that the thermally treated graphene has more spacing and voids when compared to graphene which makes it a better suit for adsorption of gases such as carbon dioxide.

An oral absorbent, surface-deacetylated chitin nano-fiber ameliorates renal injury and oxidative stress in 5/6 nephrectomized rats.

PubMed

Anraku, Makoto; Tabuchi, Ryo; Ifuku, Shinsuke; Nagae, Tomone; Iohara, Daisuke; Tomida, Hisao; Uekama, Kaneto; Maruyama, Toru; Miyamura, Shigeyuki; Hirayama, Fumitoshi; Otagiri, Masaki

2017-04-01

In this study, we report that surface-deacetylated chitin nano-fibers (SDACNFs) are more effective in decreasing renal injury and oxidative stress than deacetylated chitin powder (DAC) in 5/6 nephrectomized rats. An oral administration of low doses of SDACNFs (40mg/kg/day) over a 4 week period resulted in a significant decrease in serum indoxyl sulfate, creatinine and urea nitrogen levels, compared with a similar treatment with DAC or AST-120. The SDACNFs treatment also resulted in an increase in antioxidant potential, compared with that for DAC or AST-120. Immunohistochemical analyses also demonstrated that SDACNFs treated CRF rats showed a decrease in the amount of accumulated 8-OHdG compared with the CRF group. These results suggest that the ingestion of SDCH-NF results in a significant reduction in the levels of pro-oxidants, such as uremic toxins, in the gastrointestinal tract, thereby inhibiting the subsequent development of oxidative stress in the systemic circulation. Copyright © 2016. Published by Elsevier Ltd.

Tuning oxidation level, electrical conductance and band gap structure on graphene sheets by cyclic atomic layer reduction technique

DOE PAGES

Gu, Si-Yong; Hsieh, Chien-Te; Lin, Tzu-Wei; ...

2018-05-12

The present work develops an atomic layer reduction (ALR) method to accurately tune oxidation level, electrical conductance, band-gap structure, and photoluminescence (PL) response of graphene oxide (GO) sheets. The ALR route is carried out at 200 °C within ALR cycle number of 10–100. The ALR treatment is capable of striping surface functionalities (e.g., hydroxyl, carbonyl, and carboxylic groups), producing thermally-reduced GO sheets. The ALR cycle number serves as a controlling factor in adjusting the crystalline, surface chemistry, electrical, optical properties of GO sheets. With increasing the ALR cycle number, ALR-GO sheets display a high crystallinity, a low oxidation level, anmore » improved electrical conductivity, a narrow band gap, and a tunable PL response. Finally, on the basis of the results, the ALR technique offers a great potential for accurately tune electrical and optical properties of carbon materials through the cyclic removal of oxygen functionalities, without any complicated thermal and chemical desorption processes.« less

Topological Dirac semimetal phase in Pd and Pt oxides

NASA Astrophysics Data System (ADS)

Li, Gang; Yan, Binghai; Wang, Zhijun; Held, Karsten

2017-01-01

Topological Dirac semimetals (DSMs) exhibit nodal points through which energy bands disperse linearly in three-dimensional (3D) momentum space, a 3D analog of graphene. The first experimentally confirmed DSMs with a pair of Dirac points (DPs), Na3Bi and Cd3As2 , show topological surface Fermi arc states and exotic magnetotransport properties, boosting the interest in the search for stable and nontoxic DSM materials. Based on density-functional theory and dynamical mean-field theory calculations, we predict a family of palladium and platinum oxides to be robust 3D DSMs with three pairs of Dirac points that are well separated from bulk bands. The Fermi arcs at the surface display a Lifshitz transition upon a continuous change of the chemical potential. Corresponding oxides are already available as high-quality single crystals, an excellent precondition for the verification of our predictions by photoemission and magnetotransport experiments, extending DSMs to the versatile family of transition-metal oxides.

An electrochemical approach to monitor pH change in agar media during plant tissue culture.

PubMed

Wang, Min; Ha, Yang

2007-05-15

In this work, metal oxide microelectrodes were developed to monitor pH change in agar media during plant tissue culture. An antimony wire was produced by a new approach "capillary melt method". The surface of the obtained antimony wire was oxidized in a potassium nitrate melt to fabricate an antimony oxide film for pH sensing. Characterization results show that the oxide layer grown on the wire surface consists of Sb(2)O(3) crystal phase. The sensing response, open-circuit potential, of the electrode has a good linear relationship (R(2)=1.00) with pH value of the test solution. Adding organic compounds into the test media would not affect the linear relationship, although the slope of the lines varied with different ingredients added. The antimony oxide electrodes were employed to continuously monitor pH change of agar culture media during a 2-week plant tissue culture of Dendrobium candidum. The antimony oxide electrode fabricated this way has the advantages of low cost, easy fabrication, fast response, and almost no contamination introduced into the system. It would be suitable for in situ and continuous pH measurement in many bio applications.

Silicide Schottky Barrier For Back-Surface-Illuminated CCD

NASA Technical Reports Server (NTRS)

Hecht, Michael H.

1990-01-01

Quantum efficiency of back-surface-illuminated charge-coupled device (CCD) increased by coating back surface with thin layer of PtSi or IrSi on thin layer of SiO2. In its interaction with positively-doped bulk Si of CCD, silicide/oxide layer forms Schottky barrier that repels electrons, promoting accumulation of photogenerated charge carriers in front-side CCD potential wells. Physical principle responsible for improvement explained in "Metal Film Increases CCD Output" (NPO-16815).

Orientation dependent ionization potential of In2O3: a natural source for inhomogeneous barrier formation at electrode interfaces in organic electronics.

PubMed

Hohmann, Mareike V; Ágoston, Péter; Wachau, André; Bayer, Thorsten J M; Brötz, Joachim; Albe, Karsten; Klein, Andreas

2011-08-24

The ionization potentials of In(2)O(3) films grown epitaxially by magnetron sputtering on Y-stabilized ZrO(2) substrates with (100) and (111) surface orientation are determined using photoelectron spectroscopy. Epitaxial growth is verified using x-ray diffraction. The observed ionization potentials, which directly affect the work functions, are in good agreement with ab initio calculations using density functional theory. While the (111) surface exhibits a stable surface termination with an ionization potential of ∼ 7.0 eV, the surface termination and the ionization potential of the (100) surface depend strongly on the oxygen chemical potential. With the given deposition conditions an ionization potential of ∼ 7.7 eV is obtained, which is attributed to a surface termination stabilized by oxygen dimers. This orientation dependence also explains the lower ionization potentials observed for In(2)O(3) compared to Sn-doped In(2)O(3) (ITO) (Klein et al 2009 Thin Solid Films 518 1197-203). Due to the orientation dependent ionization potential, a polycrystalline ITO film will exhibit a laterally varying work function, which results in an inhomogeneous charge injection into organic semiconductors when used as electrode material. The variation of work function will become even more pronounced when oxygen plasma or UV-ozone treatments are performed, as an oxidation of the surface is only possible for the (100) surface. The influence of the deposition technique on the formation of stable surface terminations is also discussed. © 2011 IOP Publishing Ltd

Thermal effect of Zn quantum dots grown on Si(111): competition between relaxation and reconstraint

NASA Astrophysics Data System (ADS)

Kao, Li-Chi; Huang, Bo-Jia; Zheng, Yu-En; Tu, Kai-Teng; Chiu, Shang-Jui; Ku, Ching-Shun; Lo, Kuang Yao

2018-01-01

Zn dots are potential solutions for metal contacts in future nanodevices. The metastable states that exist at the interface between Zn quantum dots and oxide-free Si(111) surfaces can suppress the development of the complete relaxation and increase the size of Zn dots. In this work, the actual heat consumption of the structural evolution of Zn dots resulting from extrinsic thermal effect was analyzed. Zn dots were coherently grown on oxide-free Si(111) through magnetron RF sputtering. A compensative optical method combined with reflective second harmonic generation and synchrotron x-ray diffraction (XRD) was developed to statistically analyze the thermal effect on the Zn dot system. Pattern matching (3 m) between the Zn and oxide-free Si(111) surface enabled Si(111) to constrain Zn dots from a liquid to solid phase. Annealing under vacuum induced smaller, loose Zn dots to be reconstrained by Si(111). When the size of the Zn dots was in the margin of complete relaxation, the Zn dot was partially constrained by potential barriers (metastable states) between Zn(111) and one of the six in-planes of Si〈110〉. The thermal disturbance exerted by annealing would enable partially constrained ZnO/Zn dots to overcome the potential barrier and be completely relaxed, which is obvious on the transition between Zn(111) and Zn(002) peak in synchrotron XRD. Considering the actual irradiated surface area of dots array in a wide-size distribution, the competition between reconstrained and relaxed Zn dots on Si(111) during annealing was statistically analyzed.

The role of mineral surface chemistry in modified dextrin adsorption.

PubMed

Beaussart, Audrey; Mierczynska-Vasilev, Agnieszka M; Harmer, Sarah L; Beattie, David A

2011-05-15

The adsorption of two modified dextrins (phenyl succinate dextrin--PS Dextrin; styrene oxide dextrin--SO Dextrin) on four different mineral surfaces has been studied using X-ray photoelectron spectroscopy (XPS), in situ atomic force microscopy (AFM) imaging, and captive bubble contact angle measurements. The four surfaces include highly orientated pyrolytic graphite (HOPG), freshly cleaved synthetic sphalerite (ZnS), and two surfaces produced through surface reactions of sphalerite: one oxidized in alkaline solution (pH 9, 1 h immersion); and one subjected to metal ion exchange between copper and zinc (i.e. copper activation: exposed to 1×10(-3) M CuSO(4) solution for 1 h). XPS measurements indicate that the different sphalerite surfaces contain varying amounts of sulfur, zinc, oxygen, and copper, producing substrates for polymer adsorption with a range of possible binding sites. AFM imaging has shown that the two polymers adsorb to a similar extent on HOPG, and that the two polymers display very different propensities for adsorption on the three sphalerite surface types, with freshly cleaved sphalerite encouraging the least adsorption, and copper activated and oxidized sphalerite encouraging significantly more adsorption. Contact angle measurements of the four surfaces indicate that synthetic sphalerite has a low contact angle upon fracture, and that oxidation on the timescale of one hour substantially alters the hydrophobicity. HOPG and copper-activated sphalerite were the most hydrophobic, as expected due to the carbon and di/poly-sulfide rich surfaces of the two samples, respectively. SO Dextrin is seen to have a significant impact on the wettability of HOPG and the surface reacted sphalerite samples, highlighting the difficulty in selectively separating sphalerite from carbonaceous unwanted minerals in flotation. PS Dextrin has the least effect on the hydrophobicity of the reacted sphalerite surfaces, whilst still significantly increasing the wettability of graphite, and thus has more potential for use as a polymer depressant in this separation. Copyright © 2011 Elsevier Inc. All rights reserved.

Pure and Oxidized Copper Materials as Potential Antimicrobial Surfaces for Spaceflight Activities.

PubMed

Hahn, C; Hans, M; Hein, C; Mancinelli, R L; Mücklich, F; Wirth, R; Rettberg, P; Hellweg, C E; Moeller, R

2017-12-01

Microbial biofilms can lead to persistent infections and degrade a variety of materials, and they are notorious for their persistence and resistance to eradication. During long-duration space missions, microbial biofilms present a danger to crew health and spacecraft integrity. The use of antimicrobial surfaces provides an alternative strategy for inhibiting microbial growth and biofilm formation to conventional cleaning procedures and the use of disinfectants. Antimicrobial surfaces contain organic or inorganic compounds, such as antimicrobial peptides or copper and silver, that inhibit microbial growth. The efficacy of wetted oxidized copper layers and pure copper surfaces as antimicrobial agents was tested by applying cultures of Escherichia coli and Staphylococcus cohnii to these metallic surfaces. Stainless steel surfaces were used as non-inhibitory control surfaces. The production of reactive oxygen species and membrane damage increased rapidly within 1 h of exposure on pure copper surfaces, but the effect on cell survival was negligible even after 2 h of exposure. However, longer exposure times of up to 4 h led to a rapid decrease in cell survival, whereby the survival of cells was additionally dependent on the exposed cell density. Finally, the release of metal ions was determined to identify a possible correlation between copper ions in suspension and cell survival. These measurements indicated a steady increase of free copper ions, which were released indirectly by cells presumably through excreted complexing agents. These data indicate that the application of antimicrobial surfaces in spaceflight facilities could improve crew health and mitigate material damage caused by microbial contamination and biofilm formation. Furthermore, the results of this study indicate that cuprous oxide layers were superior to pure copper surfaces related to the antimicrobial effect and that cell density is a significant factor that influences the time dependence of antimicrobial activity. Key Words: Contact killing-E. coli-S. cohnii-Antimicrobial copper surfaces-Copper oxide layers-Human health-Planetary protection. Astrobiology 17, 1183-1191.

RGO modified Ni doped FeOOH for enhanced electrochemical and photoelectrochemical water oxidation

NASA Astrophysics Data System (ADS)

Zhang, Xiaofan; Zhang, Bingyan; Liu, Shuangshuang; Kang, Hongwei; Kong, Weiqian; Zhang, Shouren; Shen, Yan; Yang, Baocheng

2018-04-01

Ni,Fe-based (oxy)hydroxides have been one of the most active catalysts for the oxygen evolution reaction. In this article, reduced graphene oxide supported Ni doped FeOOH (RGO/Ni:FeOOH) was prepared for electrochemical and photoelectrochemical (PEC) water oxidation. The RGO/Ni:FeOOH exhibited a lower over-potential (260 mV at 10 mA cm-2) and smaller Tafel slope (32.3 mV dec-1) than that of the FeOOH and Ni:FeOOH. Such significant enhancement is attributed to Ni doping and RGO, which reduce the over-potential, improve the conductivity and enlarge surface areas. Besides, RGO/Ni:FeOOH decorated the TiO2 nanorods (NRs) was also fabricated for photoelectrochemical (PEC) water oxidation, which exhibited a higher photocurrent density and lower onset potential than that of TiO2 NRs the bare under illumination due to the synergistic effect of RGO and Ni:FeOOH. These results demonstrate the RGO/Ni:FeOOH has great promising as a co-catalyst to improve the PEC performance.

Using Indium Tin Oxide To Mitigate Dust on Viewing Ports

NASA Technical Reports Server (NTRS)

2008-01-01

NASA plans to use a number of onboard viewing ports to measure lunar regolith in situ and to monitor robotic and human activities on the lunar or Martian surface. Because of the size and abundance of dust particles on these bodies, the potential for dust to occlude viewing ports and windows is high enough to threaten system lifetime and reliability, especially when activities rely on relaying video to either a habitat module or controllers on Earth. This project uses a technology being developed by KSC's Electrostatics and Surface Physics Laboratory to remove dust from windowlike surfaces. The technology applies an alternating electric potential to interlaced electrodes. In this application, we use indium tin oxide (ITO) to create various electrode patterns in order to determine the most reliable pattern for dust removal. This technology has application to systems where optical clarity is important. Specifically, this project considers the in situ resource utilization (ISRU) application of a viewing port for Raman spectroscopy, where the electrode pattern on glass would be coated with a scratch-resistant sapphire film (Al2O3).

Restructuring of an Ir(210) electrode surface by potential cycling

PubMed Central

Soliman, Khaled A; Kolb, Dieter M; Jacob, Timo

2014-01-01

Summary This study addresses the electrochemical surface faceting and restructuring of Ir(210) single crystal electrodes. Cyclic voltammetry measurements and in situ scanning tunnelling microscopy are used to probe structural changes and variations in the electrochemical behaviour after potential cycling of Ir(210) in 0.1 M H2SO4. Faceted structures are obtained electrochemically as a function of time by cycling at a scanrate of 1 V·s−1 between −0.28 and 0.70 V vs SCE, i.e., between the onset of hydrogen evolution and the surface oxidation regime. The electrochemical behaviour in sulfuric acid solution is compared with that of thermally faceted Ir(210), which shows a sharp characteristic voltammetric peak for (311) facets. Structures similar to thermally-induced faceted Ir(210) are obtained electrochemically, which typically correspond to polyoriented facets at nano-pyramids. These structures grow anisotropically in a preferred direction and reach a height of about 5 nm after 4 h of cycling. The structural changes are reflected in variations of the electrocatalytic activity towards carbon monoxide adlayer oxidation. PMID:25247118

Restructuring of an Ir(210) electrode surface by potential cycling.

PubMed

Soliman, Khaled A; Kolb, Dieter M; Kibler, Ludwig A; Jacob, Timo

2014-01-01

This study addresses the electrochemical surface faceting and restructuring of Ir(210) single crystal electrodes. Cyclic voltammetry measurements and in situ scanning tunnelling microscopy are used to probe structural changes and variations in the electrochemical behaviour after potential cycling of Ir(210) in 0.1 M H2SO4. Faceted structures are obtained electrochemically as a function of time by cycling at a scanrate of 1 V·s(-1) between -0.28 and 0.70 V vs SCE, i.e., between the onset of hydrogen evolution and the surface oxidation regime. The electrochemical behaviour in sulfuric acid solution is compared with that of thermally faceted Ir(210), which shows a sharp characteristic voltammetric peak for (311) facets. Structures similar to thermally-induced faceted Ir(210) are obtained electrochemically, which typically correspond to polyoriented facets at nano-pyramids. These structures grow anisotropically in a preferred direction and reach a height of about 5 nm after 4 h of cycling. The structural changes are reflected in variations of the electrocatalytic activity towards carbon monoxide adlayer oxidation.

Synthesizing new types of ultrathin 2D metal oxide nanosheets via half-successive ion layer adsorption and reaction

NASA Astrophysics Data System (ADS)

Gao, Linjie; Li, Yaguang; Xiao, Mu; Wang, Shufang; Fu, Guangsheng; Wang, Lianzhou

2017-06-01

Two-dimensional (2D) metal oxide nanosheets have demonstrated their great potential in a broad range of applications. The existing synthesis strategies are mainly preparing 2D nanosheets from layered and specific transition metal oxides. How to prepare the other types of metal oxides as ultrathin 2D nanosheets remains unsolved, especially for metal oxides containing alkali, alkaline earth metal, and multiple metal elements. Herein, we developed a half-successive ion layer adsorption and reaction (SILAR) method, which could synthesize those types of metal oxides as ultrathin 2D nanosheets. The synthesized 2D metal oxides nanosheets are within 1 nm level thickness and 500 m2 · g-1 level surface area. This method allows us to develop many new types of ultrathin 2D metal oxides nanosheets that have never been prepared before.

Oxygen Activation and Photoelectrochemical Oxidation on Oxide Surfaces

DTIC Science & Technology

2013-12-04

electrolysis followed by product determination from mass spectroscopy showed that acetophenone was produced with a 95% Faradaic efficiency. The H/D kinetic...vs. NHE) 10 electrode: scan rate, 100mV/s. (b) Plot of catalytic currents during electrolysis at −1.38 V, icat (background subtracted), vs...controlled potential electrolysis at 3.0 V at two boron doped diamond electrodes (~0.85 cm2). Red line: background current without added catalyst

Iron oxide nanoparticles in geomicrobiology: from biogeochemistry to bioremediation.

PubMed

Braunschweig, Juliane; Bosch, Julian; Meckenstock, Rainer U

2013-09-25

Iron oxides are important constituents of soils and sediments and microbial iron reduction is considered to be a significant anaerobic respiration process in the subsurface, however low microbial reduction rates of macroparticulate Fe oxides in laboratory studies led to an underestimation of the role of Fe oxides in the global Fe redox cycle. Recent studies show the high potential of nano-sized Fe oxides in the environment as, for example, electron acceptor for microbial respiration, electron shuttle between different microorganisms, and scavenger for heavy metals. Biotic and abiotic reactivity of iron macroparticles differ significantly from nano-sized Fe oxides, which are usually much more reactive. Factors such as particle size, solubility, ferrous iron, crystal structure, and organic molecules were identified to influence the reactivity. This review discusses factors influencing the microbial reactivity of Fe oxides. It highlights the differences between natural and synthetic Fe oxides especially regarding the presence of organic molecules such as humic acids and natural organic matter. Attention is given to the transport behavior of Fe oxides in laboratory systems and in the environment, because of the high affinity of different contaminants to Fe oxide surfaces and associated co-transport of pollutants. The high reactivity of Fe oxides and their potential as adsorbents for different pollutants are discussed with respect to application and development of remediation technologies. Copyright © 2013. Published by Elsevier B.V.

Illuminating Geochemical Controls of Methane Oxidation Along a Gradient of Permafrost Thaw

NASA Astrophysics Data System (ADS)

Perryman, C. R.; Kashi, N.; McCalley, C. K.; Malhotra, A.; Giesler, R.; Varner, R.

2017-12-01

Increases in annual mean temperature in the subarctic have accelerated the thaw of organic-rich permafrost peatlands, exacerbating methane (CH4) production from microbial decomposition of peat deposits and subsequent CH4 emissions. Methanotrophic bacteria may oxidize/consume upwards of 90% of produced CH4 in some settings, pending substrate availability and environmental conditions. Redox chemistry may also control the rate of CH4 oxidation in thawing permafrost areas, particularly redox potential (Eh) and the availability of oxygen (O2) and other terminal electron receptors. We investigated potential CH4 oxidation rates across a permafrost thaw gradient in Stordalen Mire (68°21'N,18°49'E) near Abisko, Sweden. Methane oxidation rates for sites from thawing and collapsed palsa, semi-wet Sphagnum, and open-water sedge sites were determined through laboratory incubations. Peat cores were extracted from two depths at each site and incubated at in situ temperatures and CH4 concentrations. Headspace samples were collected over a 48-hour period and analyzed for CH4 concentration using flame ionization detection gas chromatography (GC-FID). Dissolved O2, Eh, and dissolved CH4 were measured in sites with porewater. Oxidation rates ranged from <0.1 to 19 μg of CH4 per gram of dry biomass per day. Eh remained positive (41.6 to 316.8 mV) with available dissolved O2 (0.3 - 5.2 mg/L) in all measurement locations down to 20cm, indicating in situ aerobic CH4 oxidation is viable across these environments. Potential CH4 oxidation rates increased with increasing dissolved CH4 concentration. Highest potential CH4 oxidation rates were found in open-water sedge sites. Eh and dissolved O2 were lowest at these sites, suggesting that methanotrophs with low-O2 demand may populate sedge areas. Furthermore, potential CH4 oxidation rates were higher at depth than at the surface in thawing palsa, suggesting CH4 oxidation may mitigate CH4 production triggered by warming in these actively thawing environments. Forthcoming elemental analyses of peat and pore water will further elucidate trends and geochemical controls of CH4 oxidation rates in thawing permafrost areas.

AN ASSESSMENT OF THE FATE OF METAL OXIDE NANOMATERIALS IN POROUS MEDIA

EPA Science Inventory

Developing procedures for assessing the potential environmental fate and transport of nanomaterials is an active endeavor of the environmental technical research community. Insufficient information exists for estimating the likelihood of nanomaterial deposition on natural surface...

Influence of corrosive solutions on microhardness and chemistry of magnesium oxide /001/ surfaces

NASA Technical Reports Server (NTRS)

Ishigaki, H.; Miyoshi, K.; Buckley, D. H.

1982-01-01

X-ray photoelectron spectroscopy analyses and hardness experiments were conducted on cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved to specimen size along the /001/ surface, and indentations were made on the cleaved surface in corrosive solutions containing HCl, NaOH, or HNO3 and in water without exposing the specimen to any other environment. The results indicated that chloride (such as MgCl2) and sodium films are formed on the magnesium oxide surface as a result of interactions between an HCl-containing solution and a cleaved magnesium oxide surface. The chloride films soften the magnesium oxide surface. In this case microhardness is strongly influenced by the pH value of the solution. The lower the pH, the lower the microhardness. Sodium films, which are formed on the magnesium oxide surface exposed to an NaOH containing solution, do not soften the magnesium oxide surface.

1,3,5-trinitro-1,3,5-triazine decomposition and chemisorption on Al(111) surface: first-principles molecular dynamics study.

PubMed

Umezawa, Naoto; Kalia, Rajiv K; Nakano, Aiichiro; Vashista, Priya; Shimojo, Fuyuki

2007-06-21

We have investigated the decomposition and chemisorption of a 1,3,5-trinitro-1,3,5-triazine (RDX) molecule on Al(111) surface using molecular dynamics simulations, in which interatomic forces are computed quantum mechanically in the framework of the density functional theory (DFT). The real-space DFT calculations are based on higher-order finite difference and norm-conserving pseudopotential methods. Strong attractive forces between oxygen and aluminum atoms break N-O and N-N bonds in the RDX and, subsequently, the dissociated oxygen atoms and NO molecules oxidize the Al surface. In addition to these Al surface-assisted decompositions, ring cleavage of the RDX molecule is also observed. These reactions occur spontaneously without potential barriers and result in the attachment of the rest of the RDX molecule to the surface. This opens up the possibility of coating Al nanoparticles with RDX molecules to avoid the detrimental effect of oxidation in high energy density material applications.

Chemical states of surface oxygen during CO oxidation on Pt(1 1 0) surface revealed by ambient pressure XPS

DOE PAGES

Yu, Youngseok; Koh, Yoobin Esther; Lim, Hojoon; ...

2017-10-20

Here, the study of CO oxidation on Pt(110) surface is revisited using ambient pressure x-ray photoemission spectroscopy. When the surface temperature reaches the activation temperature for CO oxidation under elevated pressure conditions, both the α-phase of PtO 2 oxide and chemisorbed oxygen are formed simultaneously on the surface. Due to the exothermic nature of CO oxidation, the temperature of the Pt surface increases as CO oxidation takes place. As the CO/O 2 ratio increases, the production of CO 2 increases continuously and the surface temperature also increases. Interestingly, within the diffusion limited regions, the amount of surface oxide changes littlemore » while the chemisorbed oxygen is reduced.« less

Chemical states of surface oxygen during CO oxidation on Pt(1 1 0) surface revealed by ambient pressure XPS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Youngseok; Koh, Yoobin Esther; Lim, Hojoon

Here, the study of CO oxidation on Pt(110) surface is revisited using ambient pressure x-ray photoemission spectroscopy. When the surface temperature reaches the activation temperature for CO oxidation under elevated pressure conditions, both the α-phase of PtO 2 oxide and chemisorbed oxygen are formed simultaneously on the surface. Due to the exothermic nature of CO oxidation, the temperature of the Pt surface increases as CO oxidation takes place. As the CO/O 2 ratio increases, the production of CO 2 increases continuously and the surface temperature also increases. Interestingly, within the diffusion limited regions, the amount of surface oxide changes littlemore » while the chemisorbed oxygen is reduced.« less

Activation of Magnesium Lignosulfonate and Kraft Lignin: Influence on the Properties of Phenolic Resin-Based Composites for Potential Applications in Abrasive Materials

PubMed Central

Klapiszewski, Lukasz; Jamrozik, Artur; Strzemiecka, Beata; Matykiewicz, Danuta; Voelkel, Adam; Jesionowski, Teofil

2017-01-01

Magnesium lignosulfonate and kraft lignin were activated by different oxidizing agents for use in phenolic resin composites used for the production of abrasive components. The physicochemical properties of the oxidized materials were analyzed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), dynamic mechanical-thermal analysis (DMTA) and inverse gas chromatography (IGC). The homogeneity of the model abrasive composites containing the studied products was assessed based on observations obtained using a scanning electron microscope (SEM). FTIR and XPS analysis of the oxidized products indicated that the activation process leads mainly to the formation of carbonyl groups. The IGC technique was used to assess changes in the surface energy and the acid–base properties of the studied biopolymers. The changes in the acid–base properties suggest that more groups acting as electron donors appear on the oxidized surface of the materials. DMTA studies showed that the model composites with 5% magnesium lignosulfonate oxidized by H2O2 had the best thermomechanical properties. Based on the results it was possible to propose a hypothetical mechanism of the oxidation of the natural polymers. The use of such oxidized products may improve the thermomechanical properties of abrasive articles. PMID:28594358

Design Principles for Metal Oxide Redox Materials for Solar-Driven Isothermal Fuel Production.

PubMed

Michalsky, Ronald; Botu, Venkatesh; Hargus, Cory M; Peterson, Andrew A; Steinfeld, Aldo

2015-04-01

The performance of metal oxides as redox materials is limited by their oxygen conductivity and thermochemical stability. Predicting these properties from the electronic structure can support the screening of advanced metal oxides and accelerate their development for clean energy applications. Specifically, reducible metal oxide catalysts and potential redox materials for the solar-thermochemical splitting of CO 2 and H 2 O via an isothermal redox cycle are examined. A volcano-type correlation is developed from available experimental data and density functional theory. It is found that the energy of the oxygen-vacancy formation at the most stable surfaces of TiO 2 , Ti 2 O 3 , Cu 2 O, ZnO, ZrO 2 , MoO 3 , Ag 2 O, CeO 2 , yttria-stabilized zirconia, and three perovskites scales with the Gibbs free energy of formation of the bulk oxides. Analogously, the experimental oxygen self-diffusion constants correlate with the transition-state energy of oxygen conduction. A simple descriptor is derived for rapid screening of oxygen-diffusion trends across a large set of metal oxide compositions. These general trends are rationalized with the electronic charge localized at the lattice oxygen and can be utilized to predict the surface activity, the free energy of complex bulk metal oxides, and their oxygen conductivity.

Laser induced single spot oxidation of titanium

NASA Astrophysics Data System (ADS)

Jwad, Tahseen; Deng, Sunan; Butt, Haider; Dimov, S.

2016-11-01

Titanium oxides have a wide range of applications in industry, and they can be formed on pure titanium using different methods. Laser-induced oxidation is one of the most reliable methods due to its controllability and selectivity. Colour marking is one of the main applications of the oxidation process. However, the colourizing process based on laser scanning strategies is limited by the relative large processing area in comparison to the beam size. Single spot oxidation of titanium substrates is proposed in this research in order to increase the resolution of the processed area and also to address the requirements of potential new applications. The method is applied to produce oxide films with different thicknesses and hence colours on titanium substrates. High resolution colour image is imprinted on a sheet of pure titanium by converting its pixels' colours into laser parameter settings. Optical and morphological periodic surface structures are also produced by an array of oxide spots and then analysed. Two colours have been coded into one field and the dependencies of the reflected colours on incident and azimuthal angles of the light are discussed. The findings are of interest to a range of application areas, as they can be used to imprint optical devices such as diffusers and Fresnel lenses on metallic surfaces as well as for colour marking.

Atomic-scale visualization of oxide thin-film surfaces.

PubMed

Iwaya, Katsuya; Ohsawa, Takeo; Shimizu, Ryota; Okada, Yoshinori; Hitosugi, Taro

2018-01-01

The interfaces of complex oxide heterostructures exhibit intriguing phenomena not observed in their constituent materials. The oxide thin-film growth of such heterostructures has been successfully controlled with unit-cell precision; however, atomic-scale understandings of oxide thin-film surfaces and interfaces have remained insufficient. We examined, with atomic precision, the surface and electronic structures of oxide thin films and their growth processes using low-temperature scanning tunneling microscopy. Our results reveal that oxide thin-film surface structures are complicated in contrast to the general perception and that atomically ordered surfaces can be achieved with careful attention to the surface preparation. Such atomically ordered oxide thin-film surfaces offer great opportunities not only for investigating the microscopic origins of interfacial phenomena but also for exploring new surface phenomena and for studying the electronic states of complex oxides that are inaccessible using bulk samples.

Microstructures and Properties of Plasma Electrolytic Oxidized Ti Alloy (Ti-6Al-4V) for Bio-implant Application

NASA Astrophysics Data System (ADS)

Kumari, Renu; Blawert, Carsten; Majumdar, J. Dutta

2016-02-01

In the present study, plasma electrolytic oxidation (PEO) of Ti6Al4V has been performed in an electrolyte containing 20 g/L of Na2SiO3, 10 g/L of Na3PO4, 2 g/L of KOH, and 5 g/L of hydroxyapatite at an optimum constant potential of 430 V for 10 minutes. Followed by PEO treatment, surface roughness was measured using non-contact optical profilometer. A detailed characterization of microstructure, composition and phase analysis was carried out using scanning electron microscopy, energy-dispersive X-ray spectroscopic analysis, Fourier-transform infrared, and X-ray diffraction study. The mechanical properties of the surface have been evaluated by measuring nano-hardness and wear resistance. The effect of surface modification on corrosion resistance property has also been evaluated in Hank's solution. Finally, wettability and bioactivity test have been also performed. PEO developed a thick (150 μm) porous (35 pct) oxide film on the surface of Ti-6Al-4V consisting of anatase, rutile, and SiO2. The nano-hardness of the PEO-treated surface is increased to 8 ± 0.5 GPa as compared to 2 ± 0.4 GPa of the as-received Ti-6Al-4V. Wear and corrosion resistance were improved following oxidation. There is an improvement in wettability in terms of decrease in contact angle from 60 ± 1.5 to 45 ± 1 deg. Total surface energy and its polar component were also increased significantly on PEO-treated surface as compared to the as-received Ti6Al4V.

Ambient Pressure XPS Study of Mixed Conducting Perovskite-Type SOFC Cathode and Anode Materials under Well-Defined Electrochemical Polarization

PubMed Central

2015-01-01

The oxygen exchange activity of mixed conducting oxide surfaces has been widely investigated, but a detailed understanding of the corresponding reaction mechanisms and the rate-limiting steps is largely still missing. Combined in situ investigation of electrochemically polarized model electrode surfaces under realistic temperature and pressure conditions by near-ambient pressure (NAP) XPS and impedance spectroscopy enables very surface-sensitive chemical analysis and may detect species that are involved in the rate-limiting step. In the present study, acceptor-doped perovskite-type La0.6Sr0.4CoO3-δ (LSC), La0.6Sr0.4FeO3-δ (LSF), and SrTi0.7Fe0.3O3-δ (STF) thin film model electrodes were investigated under well-defined electrochemical polarization as cathodes in oxidizing (O2) and as anodes in reducing (H2/H2O) atmospheres. In oxidizing atmosphere all materials exhibit additional surface species of strontium and oxygen. The polaron-type electronic conduction mechanism of LSF and STF and the metal-like mechanism of LSC are reflected by distinct differences in the valence band spectra. Switching between oxidizing and reducing atmosphere as well as electrochemical polarization cause reversible shifts in the measured binding energy. This can be correlated to a Fermi level shift due to variations in the chemical potential of oxygen. Changes of oxidation states were detected on Fe, which appears as FeIII in oxidizing atmosphere and as mixed FeII/III in H2/H2O. Cathodic polarization in reducing atmosphere leads to the reversible formation of a catalytically active Fe0 phase. PMID:26877827

Monitoring bisphosphonate surface functionalization and acid stability of hierarchically porous titanium zirconium oxides.

PubMed

Ide, Andreas; Drisko, Glenna L; Scales, Nicholas; Luca, Vittorio; Schiesser, Carl H; Caruso, Rachel A

2011-11-01

To take advantage of the full potential of functionalized transition metal oxides, a well-understood nonsilane based grafting technique is required. The functionalization of mixed titanium zirconium oxides was studied in detail using a bisphosphonic acid, featuring two phosphonic acid groups with high surface affinity. The bisphosphonic acid employed was coupled to a UV active benzamide moiety in order to track the progress of the surface functionalization in situ. Using different material compositions, altering the pH environment, and looking at various annealing conditions, key features of the functionalization process were identified that consequently will allow for intelligent material design. Loading with bisphosphonic acid was highest on supports calcined at 650 °C compared to lower calcination temperatures: A maximum capacity of 0.13 mmol g(-1) was obtained and the adsorption process could be modeled with a pseudo-second-order rate relationship. Heating at 650 °C resulted in a phase transition of the mixed binary oxide to a ternary oxide, titanium zirconium oxide in the srilankite phase. This phase transition was crucial in order to achieve high loading of the bisphosphonic acid and enhanced chemical stability in highly acidic solutions. Due to the inert nature of phosphorus-oxygen-metal bonds, materials functionalized by bisphosphonic acids showed increased chemical stability compared to their nonfunctionalized counterparts in harshly acidic solutions. Leaching studies showed that the acid stability of the functionalized material was improved with a partially crystalline srilankite phase. The materials were characterized using nitrogen sorption, X-ray powder diffraction, and UV-vis spectroscopy; X-ray photoelectron spectroscopy was used to study surface coverage with the bisphosphonic acid molecules.

Zwitterion-Coated Iron Oxide Nanoparticles: Surface Chemistry and Intracellular Uptake by Hepatocarcinoma (HepG2) Cells.

PubMed

Mondini, Sara; Leonzino, Marianna; Drago, Carmelo; Ferretti, Anna M; Usseglio, Sandro; Maggioni, Daniela; Tornese, Paolo; Chini, Bice; Ponti, Alessandro

2015-07-07

Nanoparticles (NPs) have received much attention in recent years for their diverse potential biomedical applications. However, the synthesis of NPs with desired biodistribution and pharmacokinetics is still a major challenge, with NP size and surface chemistry being the main factors determining the behavior of NPs in vivo. Here we report on the surface chemistry and in vitro cellular uptake of magnetic iron oxide NPs coated with zwitterionic dopamine sulfonate (ZDS). ZDS-coated NPs were compared to similar iron oxide NPs coated with PEG-like 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (MEEA) to investigate how surface chemistry affects their in vitro behavior. ZDS-coated NPs had a very dense coating, guaranteeing high colloidal stability in several aqueous media and negligible interaction with proteins. Treatment of HepG2 cells with increasing doses (2.5-100 μg Fe/mL) of ZDS-coated iron oxide NPs had no effect on cell viability and resulted in a low, dose-dependent NP uptake, inferior than most reported data for the internalization of iron oxide NPs by HepG2 cells. MEEA-coated NPs were scarcely stable and formed micrometer-sized aggregates in aqueous media. They decreased cell viability for dose ≥50 μg Fe/mL, and were more efficiently internalized than ZDS-coated NPs. In conclusion, our data indicate that the ZDS layer prevented both aggregation and sedimentation of iron oxide NPs and formed a biocompatible coating that did not display any biocorona effect. The very low cellular uptake of ZDS-coated iron NPs can be useful to achieve highly selective targeting upon specific functionalization.

Wood surface modification by in-situ sol-gel deposition of hybrid inorganic-organic thin films

Treesearch

Mandla A. Tshabalala; Li-Piin Sung

2007-01-01

Interest in the use of nanoparticles of iron, titanium, aluminum, and zinc oxides in transparent coatings for wood is increasing. Such nano-composite coatings have the potential of not only preserving the natural color of the wood, but also stabilizing the wood surface against the combined degradative effects of sunlight and moisture. The nanoparticles can be used as...

Untangling the biological effects of cerium oxide nanoparticles: the role of surface valence states

PubMed Central

Pulido-Reyes, Gerardo; Rodea-Palomares, Ismael; Das, Soumen; Sakthivel, Tamil Selvan; Leganes, Francisco; Rosal, Roberto; Seal, Sudipta; Fernández-Piñas, Francisca

2015-01-01

Cerium oxide nanoparticles (nanoceria; CNPs) have been found to have both pro-oxidant and anti-oxidant effects on different cell systems or organisms. In order to untangle the mechanisms which underlie the biological activity of nanoceria, we have studied the effect of five different CNPs on a model relevant aquatic microorganism. Neither shape, concentration, synthesis method, surface charge (ζ-potential), nor nominal size had any influence in the observed biological activity. The main driver of toxicity was found to be the percentage of surface content of Ce3+ sites: CNP1 (58%) and CNP5 (40%) were found to be toxic whereas CNP2 (28%), CNP3 (36%) and CNP4 (26%) were found to be non-toxic. The colloidal stability and redox chemistry of the most and least toxic CNPs, CNP1 and CNP2, respectively, were modified by incubation with iron and phosphate buffers. Blocking surface Ce3+ sites of the most toxic CNP, CNP1, with phosphate treatment reverted toxicity and stimulated growth. Colloidal destabilization with Fe treatment only increased toxicity of CNP1. The results of this study are relevant in the understanding of the main drivers of biological activity of nanoceria and to define global descriptors of engineered nanoparticles (ENPs) bioactivity which may be useful in safer-by-design strategies of nanomaterials. PMID:26489858

Graphene nanosheets and graphite oxide as promising adsorbents for removal of organic contaminants from aqueous solution.

PubMed

Ji, Liangliang; Chen, Wei; Xu, Zhaoyi; Zheng, Shourong; Zhu, Dongqiang

2013-01-01

Graphenes are an emerging class of carbon nanomaterials whose adsorption properties toward organic compounds have not been well understood. In the present study, graphene nanosheets were prepared by reoxidation and abrupt heating of graphite oxide, which was prepared by sequential chemical oxidation of commercial nonporous graphite powder. Adsorption properties of three aromatic compounds (naphthalene, 2-naphthol, and 1-naphthylamine) and one pharmaceutical compound (tylosin) on graphene nanosheets and graphite oxide were examined to explore the potential of these two adsorbents for the removal of organic contaminants from aqueous solutions. Compared with the literature data of adsorption on carbon nanotubes, adsorption of bulky, flexible tylosin on graphene nanosheets exhibited markedly faster adsorption kinetics, which can be attributed to their opened-up layer structure. Graphene nanosheets and graphite oxide showed similar sequences of adsorption affinity: 1-naphthylamine > 2-naphthol > tylosin > naphthalene (with much larger differences observed on graphite oxide). It was proposed that the strong adsorption of the three aromatic compounds was mainly due to π-π electron donor-acceptor interactions with the graphitic surfaces of adsorbents. Additionally, Lewis acid-base interaction was likely an important factor contributing to the strong adsorption of 1-naphthylamine and tylosin, especially for the O-functionality-abundant graphite oxide. After being normalized on the basis of adsorbent surface area, adsorption affinities of all four tested adsorbates on graphene nanosheets were very close to those on nonporous graphite powder, reflecting complete accessibility of the adsorbent surface area in adsorption. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Multi-Scale Investigation of the Formation and Breakdown of Passive Films on Carbon Steel Rebar in Concrete

NASA Astrophysics Data System (ADS)

Ghods, Pouria

The multi-scale investigation presented in this thesis was carried out to understand better the mechanisms of passivation and chloride-induced depassivation of carbon steel reinforcement in concrete. The study consisted of electrochemical experiments (electrochemical impedance spectroscopy, linear polarization resistance, free corrosion potential, anodic polarization), microscopic examinations (scanning electron microscopy, transmission electron microscopy, selected area diffraction, convergent beam electron diffraction), numerical modeling (finite element method), and spectroscopic studies (x-ray photoelectron, energy dispersed x-ray, electron energy loss). Electrochemical and microscopic studies showed that the composition of the pore solution and the surface conditions of the rebar affect the passivity and depassivation of carbon steel in concrete. It was demonstrated that crevices between mill scale and steel may become potential sites for depassivation and pit nucleation. The numerical investigation that was carried out to test this hypothesis confirmed that the ratio of chloride to hydroxide concentrations, Cl-/OH-, in crevices increased to levels higher than that of the bulk pore solution, making crevices more vulnerable to depassivation. Therefore, it was concluded that the variability associated with reported chloride thresholds might be attributed, at least in part, to the variability in mill scale properties resulting from the variability in manufacturing. The nano-scale microscopic and spectroscopic studies indicated the formation of 4-10 nm-thick passive oxide films on carbon steel in simulated concrete pore solutions, and these films consisted of two layers separated with an indistinct border. The inner layer was mainly composed of protective Fe2+-rich oxides that are in epitaxial relationship with the underlying steel surface; while the outer layer mostly consisted of (possibly porous) Fe3+-rich oxides, through which chlorides can penetrate. It was proposed that, in the presence of chlorides, Fe+2-rich oxides in the inner layer transform into Fe+3-rich oxides and potentially become un-protective. Although how this transformation occurs is still subject of future research, there are evidences showing that the process most likely leads to the formation of local anodic and cathodic sites on the steel surface.

Surface-charge-dependent cell localization and cytotoxicity of cerium oxide nanoparticles.

PubMed

Asati, Atul; Santra, Santimukul; Kaittanis, Charalambos; Perez, J Manuel

2010-09-28

Cerium oxide nanoparticles (nanoceria) have shown great potential as antioxidant and radioprotective agents for applications in cancer therapy. Recently, various polymer-coated nanoceria preparations have been developed to improve their aqueous solubility and allow for surface functionalization of these nanoparticles. However, the interaction of polymer-coated nanoceria with cells, their uptake mechanism, and subcellular localization are poorly understood. Herein, we engineered polymer-coated cerium oxide nanoparticles with different surface charges (positive, negative, and neutral) and studied their internalization and toxicity in normal and cancer cell lines. The results showed that nanoceria with a positive or neutral charge enters most of the cell lines studied, while nanoceria with a negative charge internalizes mostly in the cancer cell lines. Moreover, upon entry into the cells, nanoceria is localized to different cell compartments (e.g., cytoplasm and lysosomes) depending on the nanoparticle's surface charge. The internalization and subcellular localization of nanoceria plays a key role in the nanoparticles' cytotoxicity profile, exhibiting significant toxicity when they localize in the lysosomes of the cancer cells. In contrast, minimal toxicity is observed when they localize into the cytoplasm or do not enter the cells. Taken together, these results indicate that the differential surface-charge-dependent localization of nanoceria in normal and cancer cells plays a critical role in the nanoparticles' toxicity profile.

The preparation of polytrifluorochloroethylene (PCTFE) micro-particles and application on treating bearing steel surfaces to improve the lubrication effect for copper-graphite (Cu/C)

NASA Astrophysics Data System (ADS)

Lu, Hailin; Zhang, Pengpeng; Ren, Shanshan; Guo, Junde; Li, Xing; Dong, Guangneng

2018-01-01

Contact mechanical seal is a normal technology applied on middle axis of liquid rocket turbo pump, and the kinetic and static seal rings contact low temperature rocket propellant. Copper-graphite (Cu/C) composite as an excellent self-lubrication material was widely used in aerospace industry, this study took Cu/C as ball and bearing steel as disk to investigate the tribology properties, and distilled water were used to simulate the lox tribology performances. This study prepared polytrifluorochloroethylene (PCTFE) micro-particles which were coated on the oxide surfaces of bearing steel disk at temperature of 150 °C. The tribology results showed that the oxide surfaces treated with micro PCTFE particles have lower fiction coefficient and lower wear rate than original disk in water, and the wear morphology revealed that the treated surfaces obviously had less Cu/C composite transfer film than original disk. Meanwhile SEM, EDS, XRD, XPS and light microscope etc revealed that PCTFE micro-particles could associate with the oxide surfaces and caused higher water contact angle, due to the properties of the fluorine-containing composite may cause the good lubrication effect in water. Thus this technology shows great potential to enhance tribological performances for aerospace industry on a large scale.

Multifunctional Polyphenols- and Catecholamines-Based Self-Defensive Films for Health Care Applications.

PubMed

Dhand, Chetna; Harini, Sriram; Venkatesh, Mayandi; Dwivedi, Neeraj; Ng, Alice; Liu, Shouping; Verma, Navin Kumar; Ramakrishna, Seeram; Beuerman, Roger W; Loh, Xian Jun; Lakshminarayanan, Rajamani

2016-01-20

In an era of relentless evolution of antimicrobial resistance, there is an increasing demand for the development of efficient antimicrobial coatings or surfaces for food, biomedical, and industrial applications. This study reports the laccase-catalyzed room-temperature synthesis of mechanically robust, thermally stable, broad spectrum antimicrobial films employing interfacial interactions between poly(vinyl alcohol), PVA, and 14 naturally occurring catecholamines and polyphenols. The oxidative products of catecholamines and polyphenols reinforce the PVA films and also alter their surface and bulk properties. Among the catecholamines-reinforced films, optimum surface and bulk properties can be achieved by the oxidative products of epinephrine. For polyphenols, structure-property correlation reveals an increase in surface roughness and elasticity of PVA films with increasing number of phenolic groups in the precursors. Interestingly, PVA films reinforced with oxidized/polymerized products of pyrogallol (PG) and epinephrine (EP) display potent antimicrobial activity against pathogenic Gram-positive and Gram-negative strains, whereas hydroquinone (HQ)-reinforced PVA films display excellent antimicrobial properties against Gram-positive bacteria only. We further demonstrate that HQ and PG films retain their antimicrobial efficacy after steam sterilization. With an increasing trend of giving value to natural and renewable resources, our results have the potential as durable self-defensive antimicrobial surfaces/films for advanced healthcare and industrial applications.

Competitive and Cooperative Effects during Nickel Adsorption to Iron Oxides in the Presence of Oxalate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Flynn, Elaine D.; Catalano, Jeffrey G.

Iron oxides are ubiquitous in soils and sediments and play a critical role in the geochemical distribution of trace elements and heavy metals via adsorption and coprecipitation. The presence of organic acids may potentially alter how metals associate with iron oxide minerals through a series of cooperative or competitive processes: solution complexation, ternary surface complexation, and surface site competition. The macroscopic and molecular-scale effects of these processes were investigated for Ni adsorption to hematite and goethite at pH 7 in the presence of oxalate. The addition of this organic acid suppresses Ni uptake on both minerals. Aqueous speciation suggests thatmore » this is dominantly the result of oxalate complexing and solubilizing Ni. Comparison of the Ni surface coverage to the concentration of free (uncomplexed) Ni 2+ in solution suggests that the oxalate also alters Ni adsorption affinity. EXAFS and ATR-FTIR spectroscopies indicate that these changes in binding affinity are due to the formation of Ni–oxalate ternary surface complexes. These observations demonstrate that competition between dissolved oxalate and the mineral surface for Ni overwhelms the enhancement in adsorption associated with ternary complexation. Oxalate thus largely enhances Ni mobility, thereby increasing micronutrient bioavailability and inhibiting contaminant sequestration.« less

Facilitation of NADH Electrooxidation at Treated Carbon Nanotubes

PubMed Central

Wooten, Marilyn; Gorski, Waldemar

2010-01-01

The relationship between the state of the surface of carbon nanotubes (CNT) and their electrochemical activity was investigated using the enzyme cofactor dihydronicotinamide adenine dinucleotide (NADH) as a redox probe. The boiling of CNT in water, while nondestructive, activated them toward the oxidation of NADH as indicated by a shift in the anodic peak potential of NADH (ENADH) from 0.4 to 0.0 V. The shift in ENADH was due to the redox mediation of NADH oxidation by traces of quinone species that were formed on the surface of treated CNT. The harsher treatment that comprised of microwaving of CNT in concentrated nitric acid had a similar effect on the ENADH and, additionally, it increased the anodic peak current of NADH. The latter correlated with the formation of defects on the surface of acid-microwaved CNT as indicated by their Raman spectra. The increase in current was discussed considering a role of surface mediators on the buckled graphene sheets of acid-microwaved CNT. The other carbon allotropes including the edge plane pyrolytic graphite, graphite powder, and glassy carbon did not display a comparable activation toward the oxidation of NADH. PMID:20088562

Liquid gallium and the eutectic gallium indium (EGaIn) alloy: Dielectric functions from 1.24 to 3.1 eV by electrochemical reduction of surface oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morales, Daniel; Yu, Zhiyuan; Dickey, Michael D., E-mail: mddickey@ncsu.edu, E-mail: aspnes@ncsu.edu

Liquid metals based on gallium are promising materials for soft, stretchable, and shape reconfigurable electromagnetic devices. The behavior of these metals relates directly to the thicknesses of their surface oxide layers, which can be determined nondestructively by ellipsometry if their dielectric functions ε are known. This paper reports on the dielectric functions of liquid gallium and the eutectic gallium indium (EGaIn) alloy from 1.24 to 3.1 eV at room temperature, measured by spectroscopic ellipsometry. Overlayer-induced artifacts, a continuing problem in optical measurements of these highly reactive metals, are eliminated by applying an electrochemically reductive potential to the surface of the metalmore » immersed in an electrolyte. This technique enables measurements at ambient conditions while avoiding the complications associated with removing overlayers in a vacuum environment. The dielectric responses of both metals are closely represented by the Drude model. The EGaIn data suggest that in the absence of an oxide the surface is In-enriched, consistent with the previous vacuum-based studies. Possible reasons for discrepancies with previous measurements are discussed.« less

A surface-enhanced infrared absorption spectroscopic study of pH dependent water adsorption on Au

NASA Astrophysics Data System (ADS)

Dunwell, Marco; Yan, Yushan; Xu, Bingjun

2016-08-01

The potential dependent behavior of near-surface water on Au film electrodes in acidic and alkaline solutions is studied using a combination of attenuated total reflectance surface enhanced infrared spectroscopy and chronoamperometry. In acid, sharp νOH peaks appear at 3583 cm- 1 at high potentials attributed to non-H-bonded water coadsorbed in the hydration sphere of perchlorate near the electrode surface. Adsorbed hydronium bending mode at near 1680 cm- 1 is observed at low potentials in low pH solutions (1.4, 4.0, 6.8). At high pH (10.0, 12.3), a potential-dependent OH stretching band assigned to adsorbed hydroxide emerges from 3400-3506 cm- 1. The observation of adsorbed hydroxide, even on a weakly oxophilic metal such as Au, provides the framework for further studies of hydroxide adsorption on other electrodes to determine the role of adsorbed hydroxide on important reactions such as the hydrogen oxidation reaction.

Semiquantitative Performance and Mechanism Evaluation of Carbon Nanomaterials as Cathode Coatings for Microbial Fouling Reduction.

PubMed

Zhang, Qiaoying; Nghiem, Joanne; Silverberg, Gregory J; Vecitis, Chad D

2015-07-01

In this study, we examine bacterial attachment and survival on a titanium (Ti) cathode coated with various carbon nanomaterials (CNM): pristine carbon nanotubes (CNT), oxidized carbon nanotubes (O-CNT), oxidized-annealed carbon nanotubes (OA-CNT), carbon black (CB), and reduced graphene oxide (rGO). The carbon nanomaterials were dispersed in an isopropyl alcohol-Nafion solution and were then used to dip-coat a Ti substrate. Pseudomonas fluorescens was selected as the representative bacterium for environmental biofouling. Experiments in the absence of an electric potential indicate that increased nanoscale surface roughness and decreased hydrophobicity of the CNM coating decreased bacterial adhesion. The loss of bacterial viability on the noncharged CNM coatings ranged from 22% for CB to 67% for OA-CNT and was dependent on the CNM dimensions and surface chemistry. For electrochemical experiments, the total density and percentage of inactivation of the adherent bacteria were analyzed semiquantitatively as functions of electrode potential, current density, and hydrogen peroxide generation. Electrode potential and hydrogen peroxide generation were the dominant factors with regard to short-term (3-h) bacterial attachment and inactivation, respectively. Extended-time electrochemical experiments (12 h) indicated that in all cases, the density of total deposited bacteria increased almost linearly with time and that the rate of bacterial adhesion was decreased 8- to 10-fold when an electric potential was applied. In summary, this study provides a fundamental rationale for the selection of CNM as cathode coatings and electric potential to reduce microbial fouling. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Oxidation of platinum nickel nanowires to improve durability of oxygen-reducing electrocatalysts

DOE PAGES

Alia, Shaun M.; Pylypenko, Svitlana; Dameron, Arrelaine; ...

2016-01-12

In this study, the impact of heat treating platinum-coated nickel (Pt-Ni) nanowires in oxygen is examined to determine the effect on oxygen reduction (ORR) activity and durability. Pt-Ni nanowires exhibit promising ORR mass activities (3 times greater than Pt nanoparticles, 1.5 times greater than U.S. Department of Energy target) both before and after potential cycling for all but the highest annealing temperatures explored. The annealing of Pt-Ni nanowires in oxygen with increasing temperature is found to reduce surface area and ORR activity in comparison to the untreated material, but also reduces activity losses following durability testing. Following potential cycling, unannealedmore » Pt-Ni nanowires show significant losses in surface area (23%) and specific activity (18%) while Pt-Ni nanowires annealed at 200°C show modest increases in surface area (2%) and specific activity (6%) after potential cycling. Increasing annealing temperatures also show a clear trend of decreasing Ni dissolution rates. While oxygen annealing has shown the ability to improve durability of Pt-Ni nanowires, significant Ni dissolution was observed in all samples and suggests oxide passivation while showing promise for improved durability, when employed by itself is insufficient to prevent all contamination concerns involving Ni dissolution.« less

Surface coverage and corrosion inhibition effect of Rosmarinus officinalis and zinc oxide on the electrochemical performance of low carbon steel in dilute acid solutions

NASA Astrophysics Data System (ADS)

Loto, Roland Tolulope

2018-03-01

Electrochemical analysis of the corrosion inhibition and surface protection properties of the combined admixture of Rosmarinus officinalis and zinc oxide on low carbon steel in 1 M HCl and H2SO4 solution was studied by potentiodynamic polarization, open circuit potential measurement, optical microscopy and ATR-FTIR spectroscopy. Results obtained confirmed the compound to be more effective in HCl solution, with optimal inhibition efficiencies of 93.26% in HCl and 87.7% in H2SO4 acid solutions with mixed type inhibition behavior in both acids. The compound shifts the corrosion potential values of the steel cathodically in HCl and anodically in H2SO4 signifying specific corrosion inhibition behavior without applied potential. Identified functional groups of alcohols, phenols, 1°, 2° amines, amides, carbonyls (general), esters, saturated aliphatic, carboxylic acids, ethers, aliphatic amines, alkenes, aromatics, alkyl halides and alkynes within the compound completely adsorbed onto the steel forming a protective covering. Thermodynamic calculations showed physisorption molecular interaction with the steel's surface according to Langmuir and Frumkin adsorption isotherms. Optical microscopy images of the inhibited and uninhibited steels contrast each other with steel specimens from HCl solution showing a better morphology.

Phyto-reduction of graphene oxide using the aqueous extract of Eichhornia crassipes (Mart.) Solms

NASA Astrophysics Data System (ADS)

Firdhouse, M. Jannathul; Lalitha, P.

2014-10-01

The aqueous extract of Eichhornia crassipes was used as reductant to produce graphene from graphene oxide by refluxing method. The complete reduction of graphene oxide was monitored using UV-Vis spectrophotometer. Characterization of graphene was made through FTIR, XRD, and Raman spectroscopy analysis. The stability of graphene was studied by thermal gravimetric analysis and zeta potential measurements. The nature and surface morphology of the synthesized graphene was analyzed by transmission electron microscopy. The production of graphene using phytoextract as reductant emphasizes on the facile method of synthesis and greener nanotechnology.

Bioturbation determines the response of benthic ammonia-oxidizing microorganisms to ocean acidification

PubMed Central

Laverock, B.; Kitidis, V.; Tait, K.; Gilbert, J. A.; Osborn, A. M.; Widdicombe, S.

2013-01-01

Ocean acidification (OA), caused by the dissolution of increasing concentrations of atmospheric carbon dioxide (CO2) in seawater, is projected to cause significant changes to marine ecology and biogeochemistry. Potential impacts on the microbially driven cycling of nitrogen are of particular concern. Specifically, under seawater pH levels approximating future OA scenarios, rates of ammonia oxidation (the rate-limiting first step of the nitrification pathway) have been shown to dramatically decrease in seawater, but not in underlying sediments. However, no prior study has considered the interactive effects of microbial ammonia oxidation and macrofaunal bioturbation activity, which can enhance nitrogen transformation rates. Using experimental mesocosms, we investigated the responses to OA of ammonia oxidizing microorganisms inhabiting surface sediments and sediments within burrow walls of the mud shrimp Upogebia deltaura. Seawater was acidified to one of four target pH values (pHT 7.90, 7.70, 7.35 and 6.80) in comparison with a control (pHT 8.10). At pHT 8.10, ammonia oxidation rates in burrow wall sediments were, on average, fivefold greater than in surface sediments. However, at all acidified pH values (pH ≤ 7.90), ammonia oxidation rates in burrow sediments were significantly inhibited (by 79–97%; p < 0.01), whereas rates in surface sediments were unaffected. Both bacterial and archaeal abundances increased significantly as pHT declined; by contrast, relative abundances of bacterial and archaeal ammonia oxidation (amoA) genes did not vary. This research suggests that OA could cause substantial reductions in total benthic ammonia oxidation rates in coastal bioturbated sediments, leading to corresponding changes in coupled nitrogen cycling between the benthic and pelagic realms. PMID:23980243

Vertical Segregation and Phylogenetic Characterization of Ammonia-Oxidizing Bacteria and Archaea in the Sediment of a Freshwater Aquaculture Pond

PubMed Central

Lu, Shimin; Liu, Xingguo; Ma, Zhuojun; Liu, Qigen; Wu, Zongfan; Zeng, Xianlei; Shi, Xu; Gu, Zhaojun

2016-01-01

Pond aquaculture is the major freshwater aquaculture method in China. Ammonia-oxidizing communities inhabiting pond sediments play an important role in controlling culture water quality. However, the distribution and activities of ammonia-oxidizing microbial communities along sediment profiles are poorly understood in this specific environment. Vertical variations in the abundance, transcription, potential ammonia oxidizing rate, and community composition of ammonia-oxidizing bacteria (AOB) and ammonia-oxidizing archaea (AOA) in sediment samples (0–50 cm depth) collected from a freshwater aquaculture pond were investigated. The concentrations of the AOA amoA gene were higher than those of the AOB by an order of magnitude, which suggested that AOA, as opposed to AOB, were the numerically predominant ammonia-oxidizing organisms in the surface sediment. This could be attributed to the fact that AOA are more resistant to low levels of dissolved oxygen. However, the concentrations of the AOB amoA mRNA were higher than those of the AOA by 2.5- to 39.9-fold in surface sediments (0–10 cm depth), which suggests that the oxidation of ammonia was mainly performed by AOB in the surface sediments, and by AOA in the deeper sediments, where only AOA could be detected. Clone libraries of AOA and AOB amoA sequences indicated that the diversity of AOA and AOB decreased with increasing depth. The AOB community consisted of two groups: the Nitrosospira and Nitrosomonas clusters, and Nitrosomonas were predominant in the freshwater pond sediment. All AOA amoA gene sequences in the 0–2 cm deep sediment were grouped into the Nitrososphaera cluster, while other AOA sequences in deeper sediments (10–15 and 20–25 cm depths) were grouped into the Nitrosopumilus cluster. PMID:26834709

UNS S31603 Stainless Steel Tungsten Inert Gas Welds Made with Microparticle and Nanoparticle Oxides

PubMed Central

Tseng, Kuang-Hung; Lin, Po-Yu

2014-01-01

The purpose of this study was to investigate the difference between tungsten inert gas (TIG) welding of austenitic stainless steel assisted by microparticle oxides and that assisted by nanoparticle oxides. SiO2 and Al2O3 were used to investigate the effects of the thermal stability and the particle size of the activated compounds on the surface appearance, geometric shape, angular distortion, delta ferrite content and Vickers hardness of the UNS S31603 stainless steel TIG weld. The results show that the use of SiO2 leads to a satisfactory surface appearance compared to that of the TIG weld made with Al2O3. The surface appearance of the TIG weld made with nanoparticle oxide has less flux slag compared with the one made with microparticle oxide of the same type. Compared with microparticle SiO2, the TIG welding with nanoparticle SiO2 has the potential benefits of high joint penetration and less angular distortion in the resulting weldment. The TIG welding with nanoparticle Al2O3 does not result in a significant increase in the penetration or reduction of distortion. The TIG welding with microparticle or nanoparticle SiO2 uses a heat source with higher power density, resulting in a higher ferrite content and hardness of the stainless steel weld metal. In contrast, microparticle or nanoparticle Al2O3 results in no significant difference in metallurgical properties compared to that of the C-TIG weld metal. Compared with oxide particle size, the thermal stability of the oxide plays a significant role in enhancing the joint penetration capability of the weld, for the UNS S31603 stainless steel TIG welds made with activated oxides. PMID:28788704

UNS S31603 Stainless Steel Tungsten Inert Gas Welds Made with Microparticle and Nanoparticle Oxides.

PubMed

Tseng, Kuang-Hung; Lin, Po-Yu

2014-06-20

The purpose of this study was to investigate the difference between tungsten inert gas (TIG) welding of austenitic stainless steel assisted by microparticle oxides and that assisted by nanoparticle oxides. SiO₂ and Al₂O₃ were used to investigate the effects of the thermal stability and the particle size of the activated compounds on the surface appearance, geometric shape, angular distortion, delta ferrite content and Vickers hardness of the UNS S31603 stainless steel TIG weld. The results show that the use of SiO₂ leads to a satisfactory surface appearance compared to that of the TIG weld made with Al₂O₃. The surface appearance of the TIG weld made with nanoparticle oxide has less flux slag compared with the one made with microparticle oxide of the same type. Compared with microparticle SiO₂, the TIG welding with nanoparticle SiO₂ has the potential benefits of high joint penetration and less angular distortion in the resulting weldment. The TIG welding with nanoparticle Al₂O₃ does not result in a significant increase in the penetration or reduction of distortion. The TIG welding with microparticle or nanoparticle SiO₂ uses a heat source with higher power density, resulting in a higher ferrite content and hardness of the stainless steel weld metal. In contrast, microparticle or nanoparticle Al₂O₃ results in no significant difference in metallurgical properties compared to that of the C-TIG weld metal. Compared with oxide particle size, the thermal stability of the oxide plays a significant role in enhancing the joint penetration capability of the weld, for the UNS S31603 stainless steel TIG welds made with activated oxides.

Oxidative Recession, Sulfur Release, and Al203 Spallation for Y-Doped Alloys

NASA Technical Reports Server (NTRS)

Smialek, James L.

2001-01-01

Second-order spallation phenomena have been noted for Y-doped Rene'N5 after long term oxidation at 1150 degrees C. The reason for this behavior has not been conclusively identified. A mass equivalence analysis has shown that the surface recession resulting from oxidation has the potential of releasing about 0.15 monolayer of sulfur for every 1 mg/sq cm of oxygen reacted for an alloy containing 5 ppmw of sulfur. This amount is significant in comparison to levels that have been shown to result in first-order spallation behavior for undoped alloys. Oxidative recession is therefore speculated to be a contributing source of sulfur and second-order spallation for Y-doped alloys.

Flexible transparent conducting hybrid film using a surface-embedded copper nanowire network: a highly oxidation-resistant copper nanowire electrode for flexible optoelectronics.

PubMed

Im, Hyeon-Gyun; Jung, Soo-Ho; Jin, Jungho; Lee, Dasom; Lee, Jaemin; Lee, Daewon; Lee, Jung-Yong; Kim, Il-Doo; Bae, Byeong-Soo

2014-10-28

We report a flexible high-performance conducting film using an embedded copper nanowire transparent conducting electrode; this material can be used as a transparent electrode platform for typical flexible optoelectronic devices. The monolithic composite structure of our transparent conducting film enables simultaneously an outstanding oxidation stability of the copper nanowire network (14 d at 80 °C), an exceptionally smooth surface topography (R(rms) < 2 nm), and an excellent opto-electrical performances (Rsh = 25 Ω sq(-1) and T = 82%). A flexible organic light emitting diode device is fabricated on the transparent conducting film to demonstrate its potential as a flexible copper nanowire electrode platform.

Humidity sensing properties of Al-doped zinc oxide coating films

NASA Astrophysics Data System (ADS)

Saidi, S. A.; Mamat, M. H.; Ismail, A. S.; Malek, M. F.; Yusoff, M. M.; Sin, N. D. Md.; Zoolfakar, A. S.; Khusaimi, Z.; Rusop, M.

2018-05-01

Humidity sensor was fabricated using Al-doped zinc oxide (ZnO) coating films through spin-coating at room temperature. The sensing mechanism was discussed based on their nanostructures, such as surface area and porous nanostructures. Surface area and water adsorption are an important component in the low humidity, while at high humidity, porous nanostructures and capillary condensation become important. The results showed that the sensitivity of the Al-doped ZnO coating improved compared to that of the Al-doped ZnO nanorod arrays, with values of 7.38 at 40% to 90%RH (Relative humidity). All these results indicated that Al-doped ZnO coating had high potential for humidity-sensor applications.

Method of adhesion between an oxide layer and a metal layer

DOEpatents

Jennison, Dwight R.; Bogicevic, Alexander; Kelber, Jeffry A.; Chambers, Scott A.

2004-09-14

A method of controlling the wetting characteristics and increasing the adhesion between a metal and an oxide layer. By introducing a negatively-charged species to the surface of an oxide layer, layer-by-layer growth of metal deposited onto the oxide surface is promoted, increasing the adhesion strength of the metal-oxide interface. The negatively-charged species can either be deposited onto the oxide surface or a compound can be deposited that dissociates on, or reacts with, the surface to form the negatively-charged species. The deposited metal adatoms can thereby bond laterally to the negatively-charged species as well as vertically to the oxide surface as well as react with the negatively charged species, be oxidized, and incorporated on or into the surface of the oxide.

In Situ Atomic Scale Visualization Of Surface Kinetics Driven Dynamics Of Oxide Growth On A Ni–Cr Surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Langli; Zou, Lianfeng; Schreiber, Daniel K.

2016-01-20

We report in situ atomic-scale visualization of the dynamical three-dimensional (3D) growth of NiO during initial oxidation of Ni-10at%Cr using environmental transmission electron microscopy (ETEM). Despite the thermodynamic preference for Cr2O3 formation, cubic NiO oxides nucleated and grew epitaxially as the dominating oxide phase on the Ni-Cr (100) surface during initial oxidation. The growth of NiO islands proceeds through step-by-step adatom mechanism in 3D, which is sustained by surface diffusion of Ni and O atoms. Although the shapes of oxide islands are controlled by strain energy between oxide and alloy substrate, local surface kinetic variations can lead to the changemore » of surface planes of oxide islands. These results demonstrate that surface diffusion dominates initial oxidation of Ni-Cr in these test conditions.« less

Mapping the Iron Oxidation State in Martian Meteorites

NASA Technical Reports Server (NTRS)

Martin, A. M.; Treimann, A. H.; Righter, K.

2017-01-01

Several types of Martian igneous meteorites have been identified: clinopyroxenites (nakhlites), basaltic shergottites, peridotitic shergottites, dunites (chassignites) and orthopyroxenites [1,2]. In order to constrain the heterogeneity of the Martian mantle and crust, and their evolution through time, numerous studies have been performed on the iron oxidation state of these meteorites [3,4,5,6,7,8,9]. The calculated fO2 values all lie within the FMQ-5 to FMQ+0.5 range (FMQ representing the Fayalite = Magnetite + Quartz buffer); however, discrepancies appear between the various studies, which are either attributed to the choice of the minerals/melts used, or to the precision of the analytical/calculation method. The redox record in volcanic samples is primarily related to the oxidation state in the mantle source(s). However, it is also influenced by several deep processes: melting, crystallization, magma mixing [10], assimilation and degassing [11]. In addition, the oxidation state in Martian meteorites is potentially affected by several surface processes: assimilation of sediment/ crust during lava flowing at Mars' surface, low temperature micro-crystallization [10], weathering at the surface of Mars and low temperature reequilibration, impact processes (i.e. high pressure phase transitions, mechanical mixing, shock degassing and melting), space weathering, and weathering on Earth (at atmospheric conditions different from Mars). Decoding the redox record of Martian meteorites, therefore, requires large-scale quantitative analysis methods, as well as a perfect understanding of oxidation processes.

Fingerprinting Bacterial and Fungal Manganese Oxidation via Stable Oxygen Isotopes of Manganese Oxides

NASA Astrophysics Data System (ADS)

Sutherland, K. M.; Wankel, S. D.; Hansel, C. M.

2016-12-01

Manganese (Mn) oxides are a ubiquitous mineralogical component of surface Earth and Mars. Mn(III/IV) oxides are potent environmental sorbents and oxidants that play a crucial role in the fate of organic matter. The processes by which Mn(II) oxidation occurs in natural systems are poorly understood, but a number of studies have implicated microogranisms as the primary agents of Mn(II) oxidation in terrestrial and marine environments. The ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides transcends the boundaries of biological domain, with an abundance of well-characterized prokaryotes as well as eukaryotic fungi with the ability to oxidize Mn(II) to Mn(III/IV) oxides. Biological Mn(II) oxidation proceeds directly through enzymatic activity or indirectly through the production of reactive oxygen species. Building upon earlier research suggesting that stable oxygen isotope fractionation could be used to fingerprint unique Mn(II)-oxidizing organisms or distinct oxidation pathways, here we use culture-based studies of Mn(II)-oxidizing bacteria and fungi to determine the kinetic oxygen isotope effects associated with Mn(II) oxidation. Since the oxygen molecules in Mn(III/IV) oxides are comprised of oxygen from both precursor water and molecular oxygen, we used a two-fold approach to constrain isotope fractionation with respect to each oxygen source. We used open system oxidation experiments using oxygen-18 labeled water in parallel with closed system Rayleigh distillation oxidation experiments to fully constrain isotope fractionation associated with oxygen atom incorporation during Mn(II) oxidation. Our results suggest commonalities among fractionation factors from groups of Mn(II)-oxidizing organisms that have similar oxidation mechanisms. These results suggest that stable oxygen isotopes of Mn(III/IV) oxides have the potential to distinguish between Mn(II) oxidation pathways in nature, providing a way to determine which groups of Mn(II) oxidizers may be active in present and past surface Earth environments.

Improved blackwater disinfection using potentiodynamic methods with oxidized boron-doped diamond electrodes.

PubMed

Thostenson, J O; Mourouvin, R; Hawkins, B T; Ngaboyamahina, E; Sellgren, K L; Parker, C B; Deshusses, M A; Stoner, B R; Glass, J T

2018-09-01

Electrochemical disinfection (ECD) has become an important blackwater disinfection technology. ECD is a promising solution for the 2 billion people without access to conventional sanitation practices and in areas deficient in basic utilities (e.g., sewers, electricity, waste treatment). Here, we report on the disinfection of blackwater using potential cycling compared to potentiostatic treatment methods in chloride-containing and chloride-free solutions of blackwater (i.e., untreated wastewater containing feces, urine, and flushwater from a toilet). Potentiodynamic treatment is demonstrated to improve disinfection energy efficiency of blackwater by 24% and 124% compared to static oxidation and reduction methods, respectively. The result is shown to be caused by electrochemical advanced oxidation processes (EAOP) and regeneration of sp 2 -surface-bonded carbon functional groups that serve the dual purpose of catalysts and adsorption sites of oxidant intermediates. Following 24 h electrolysis in blackwater, electrode fouling is shown to be minimized by the potential cycling method when compared to equivalent potentiostatic methods. The potential cycling current density is 40% higher than both the static oxidative and reductive methods. This work enhances the understanding of oxygen reduction catalysts using functionalized carbon materials and electrochemical disinfection anodes, both of which have the potential to bring a cost-effective, energy efficient, and practical solution to the problem of disinfecting blackwater. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Nanotubular surface modification of metallic implants via electrochemical anodization technique.

PubMed

Wang, Lu-Ning; Jin, Ming; Zheng, Yudong; Guan, Yueping; Lu, Xin; Luo, Jing-Li

2014-01-01

Due to increased awareness and interest in the biomedical implant field as a result of an aging population, research in the field of implantable devices has grown rapidly in the last few decades. Among the biomedical implants, metallic implant materials have been widely used to replace disordered bony tissues in orthopedic and orthodontic surgeries. The clinical success of implants is closely related to their early osseointegration (ie, the direct structural and functional connection between living bone and the surface of a load-bearing artificial implant), which relies heavily on the surface condition of the implant. Electrochemical techniques for modifying biomedical implants are relatively simple, cost-effective, and appropriate for implants with complex shapes. Recently, metal oxide nanotubular arrays via electrochemical anodization have become an attractive technique to build up on metallic implants to enhance the biocompatibility and bioactivity. This article will thoroughly review the relevance of electrochemical anodization techniques for the modification of metallic implant surfaces in nanoscale, and cover the electrochemical anodization techniques used in the development of the types of nanotubular/nanoporous modification achievable via electrochemical approaches, which hold tremendous potential for bio-implant applications. In vitro and in vivo studies using metallic oxide nanotubes are also presented, revealing the potential of nanotubes in biomedical applications. Finally, an outlook of future growth of research in metallic oxide nanotubular arrays is provided. This article will therefore provide researchers with an in-depth understanding of electrochemical anodization modification and provide guidance regarding the design and tuning of new materials to achieve a desired performance and reliable biocompatibility.

Nanotubular surface modification of metallic implants via electrochemical anodization technique

PubMed Central

Wang, Lu-Ning; Jin, Ming; Zheng, Yudong; Guan, Yueping; Lu, Xin; Luo, Jing-Li

2014-01-01

Due to increased awareness and interest in the biomedical implant field as a result of an aging population, research in the field of implantable devices has grown rapidly in the last few decades. Among the biomedical implants, metallic implant materials have been widely used to replace disordered bony tissues in orthopedic and orthodontic surgeries. The clinical success of implants is closely related to their early osseointegration (ie, the direct structural and functional connection between living bone and the surface of a load-bearing artificial implant), which relies heavily on the surface condition of the implant. Electrochemical techniques for modifying biomedical implants are relatively simple, cost-effective, and appropriate for implants with complex shapes. Recently, metal oxide nanotubular arrays via electrochemical anodization have become an attractive technique to build up on metallic implants to enhance the biocompatibility and bioactivity. This article will thoroughly review the relevance of electrochemical anodization techniques for the modification of metallic implant surfaces in nanoscale, and cover the electrochemical anodization techniques used in the development of the types of nanotubular/nanoporous modification achievable via electrochemical approaches, which hold tremendous potential for bio-implant applications. In vitro and in vivo studies using metallic oxide nanotubes are also presented, revealing the potential of nanotubes in biomedical applications. Finally, an outlook of future growth of research in metallic oxide nanotubular arrays is provided. This article will therefore provide researchers with an in-depth understanding of electrochemical anodization modification and provide guidance regarding the design and tuning of new materials to achieve a desired performance and reliable biocompatibility. PMID:25258532

Undoped and Ni-doped CoO x surface modification of porous BiVO 4 photoelectrodes for water oxidation

DOE PAGES

Liu, Ya; Guo, Youhong; Schelhas, Laura T.; ...

2016-09-29

Surface modification of photoanodes with oxygen evolution reaction (OER) catalysts is an effective approach to enhance water oxidation kinetics, to reduce external bias, and to improve the energy harvesting efficiency of photoelectrochemical (PEC) water oxidation. Here, the surface of porous BiVO 4 photoanodes was modified by the deposition of undoped and Ni-doped CoO x via nitrogen flow assisted electrostatic spray pyrolysis. This newly developed atmospheric pressure deposition technique allows for surface coverage throughout the porous structure with thickness and composition control. PEC testing of modified BiVO 4 photoanodes shows that after deposition of an undoped CoO x surface layer, themore » onset potential shifts negatively by ca. 420 mV and the photocurrent density reaches 2.01 mA cm –2 at 1.23 vs V RHE under AM 1.5G illumination. Modification with Ni-doped CoO x produces even more effective OER catalysis and yields a photocurrent density of 2.62 mA cm –2 at 1.23 V RHE under AM 1.5G illumination. Furthermore, the valence band X-ray photoelectron spectroscopy and synchrotron-based X-ray absorption spectroscopy results show the Ni doping reduces the Fermi level of the CoO x layer; the increased surface band bending produced by this effect is partially responsible for the superior PEC performance.« less

Enriching acid rock drainage related microbial communities from surface-deposited oil sands tailings.

PubMed

Dean, Courtney; Xiao, Yeyuan; Roberts, Deborah J

2016-10-01

Little is known about the microbial communities native to surface-deposited pyritic oil sands tailings, an environment where acid rock drainage (ARD) could occur. The goal of this study was to enrich sulfur-oxidizing organisms from these tailings and determine whether different populations exist at pH levels 7, 4.5, and 2.5. Using growth-based methods provides model organisms for use in the future to predict potential activities and limitations of these organisms and to develop possible control methods. Thiosulfate-fed enrichment cultures were monitored for approximately 1 year. The results showed that the enrichments at pH 4.5 and 7 were established quicker than at pH 2.5. Different microbial community structures were found among the 3 pH environments. The sulfur-oxidizing microorganisms identified were most closely related to Halothiobacillus neapolitanus, Achromobacter spp., and Curtobacterium spp. While microorganisms related to Chitinophagaceae and Acidocella spp. were identified as the only possible iron-oxidizing and -reducing microbes. These results contribute to the general knowledge of the relatively understudied microbial communities that exist in pyritic oil sands tailings and indicate these communities may have a potential role in ARD generation, which may have implications for future tailings management.

Effects of ozone and ozone/peroxide on trace organic contaminants and NDMA in drinking water and water reuse applications.

PubMed

Pisarenko, Aleksey N; Stanford, Benjamin D; Yan, Dongxu; Gerrity, Daniel; Snyder, Shane A

2012-02-01

An ozone and ozone/peroxide oxidation process was evaluated at pilot scale for trace organic contaminant (TOrC) mitigation and NDMA formation in both drinking water and water reuse applications. A reverse osmosis (RO) pilot was also evaluated as part of the water reuse treatment train. Ozone/peroxide showed lower electrical energy per order of removal (EEO) values for TOrCs in surface water treatment, but the addition of hydrogen peroxide increased EEO values during wastewater treatment. TOrC oxidation was correlated to changes in UV(254) absorbance and fluorescence offering a surrogate model for predicting contaminant removal. A decrease in N-nitrosodimethylamine (NDMA) formation potential (after chloramination) was observed after treatment with ozone and ozone/peroxide. However, during spiking experiments with surface water, ozone/peroxide achieved limited destruction of NDMA, while in wastewaters net direct formation of NDMA of 6-33 ng/L was observed after either ozone or ozone/peroxide treatment. Once formed during ozonation, NDMA passed through the subsequent RO membranes, which highlights the significance of the potential for direct NDMA formation during oxidation in reuse applications. Copyright © 2011 Elsevier Ltd. All rights reserved.

Bio-Reduction of Graphene Oxide Using Sulfate-Reducing Bacteria and Its Implication on Anti-Biocorrosion.

PubMed

Song, Tian-Shun; Tan, Wei-Min; Xie, Jingjing

2018-08-01

In this paper, we developed an environmental friendly, cost effective, simple and green approach to reduce graphene oxide (GO) by a sulfate-reducing bacterium Desulfovibrio desulfuricans. The D. desulfuricans reduces exfoliated GO to reduced graphene oxide (rGO) at 25 °C in an aqueous solution without any toxic and environmentally harmful reducing agents. The rGO was characterized with X-ray Diffraction, Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy, Transmission Electron Microscope, X-ray Photoelectron Spectroscopy and Raman Spectroscopy. The analysis results showed that rGO had excellent properties and multi-layer graphene sheets structure. Furthermore, we demonstrated that D. desulfuricans, one of the primary bacteria responsible for the biocorrosion of various metals, might reduce GO to rGO on the surface of copper and prevented the corrosion of copper, which confirmed that electrophoretic deposition of GO on the surface of metals had great potential on the anti-biocorrosion applications.

The Effect of Surface Site Ensembles on the Activity and Selectivity of Ethanol Electrooxidation by Octahedral PtNiRh Nanoparticles.

PubMed

Erini, Nina; Beermann, Vera; Gocyla, Martin; Gliech, Manuel; Heggen, Marc; Dunin-Borkowski, Rafal E; Strasser, Peter

2017-06-01

Direct ethanol fuel cells are attractive power sources based on a biorenewable, high energy-density fuel. Their efficiency is limited by the lack of active anode materials which catalyze the breaking of the C-C bond coupled to the 12-electron oxidation to CO 2 . We report shape-controlled PtNiRh octahedral ethanol oxidation electrocatalysts with excellent activity and previously unachieved low onset potentials as low as 0.1 V vs. RHE, while being highly selective to complete oxidation to CO 2 . Our comprehensive characterization and in situ electrochemical ATR studies suggest that the formation of a ternary surface site ensemble around the octahedral Pt 3 Ni 1 Rh x nanoparticles plays a crucial mechanistic role for this behavior. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water flow in carbon-based nanoporous membranes impacted by interactions between hydrated ions and aromatic rings.

PubMed

Liu, Jian; Shi, Guosheng; Fang, Haiping

2017-02-24

Carbon-based nanoporous membranes, such as carbon nanotubes (CNTs), graphene/graphene oxide and graphyne, have shown great potential in water desalination and purification, gas and ion separation, biosensors, and lithium-based batteries, etc. A deep understanding of the interaction between hydrated ions in an aqueous solution and the graphitic surface in systems composed of water, ions and a graphitic surface is essential for applications with carbon-based nanoporous membrane platforms. In this review, we describe the recent progress of the interaction between hydrated ions and aromatic ring structures on the carbon-based surface and its applications in the water flow in a carbon nanotube. We expect that these works can be extended to the understanding of water flow in other nanoporous membranes, such as nanoporous graphene, graphyne and stacked sheets of graphene oxide.

Buffer-eliminated, charge-neutral epitaxial graphene on oxidized 4H-SiC (0001) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sirikumara, Hansika I., E-mail: hansi.sirikumara@siu.edu; Jayasekera, Thushari, E-mail: thushari@siu.edu

Buffer-eliminated, charge-neutral epitaxial graphene (EG) is important to enhance its potential in device applications. Using the first principles Density Functional Theory calculations, we investigated the effect of oxidation on the electronic and structural properties of EG on 4H-SiC (0001) surface. Our investigation reveals that the buffer layer decouples from the substrate in the presence of both silicate and silicon oxy-nitride at the interface, and the resultant monolayer EG is charge-neutral in both cases. The interface at 4H-SiC/silicate/EG is characterized by surface dangling electrons, which opens up another route for further engineering EG on 4H-SiC. Dangling electron-free 4H-SiC/silicon oxy-nitride/EG is idealmore » for achieving charge-neutral EG.« less

Oxidation Induced Doping of Nanoparticles Revealed by in Situ X-ray Absorption Studies.

PubMed

Kwon, Soon Gu; Chattopadhyay, Soma; Koo, Bonil; Dos Santos Claro, Paula Cecilia; Shibata, Tomohiro; Requejo, Félix G; Giovanetti, Lisandro J; Liu, Yuzi; Johnson, Christopher; Prakapenka, Vitali; Lee, Byeongdu; Shevchenko, Elena V

2016-06-08

Doping is a well-known approach to modulate the electronic and optical properties of nanoparticles (NPs). However, doping at nanoscale is still very challenging, and the reasons for that are not well understood. We studied the formation and doping process of iron and iron oxide NPs in real time by in situ synchrotron X-ray absorption spectroscopy. Our study revealed that the mass flow of the iron triggered by oxidation is responsible for the internalization of the dopant (molybdenum) adsorbed at the surface of the host iron NPs. The oxidation induced doping allows controlling the doping levels by varying the amount of dopant precursor. Our in situ studies also revealed that the dopant precursor substantially changes the reaction kinetics of formation of iron and iron oxide NPs. Thus, in the presence of dopant precursor we observed significantly faster decomposition rate of iron precursors and substantially higher stability of iron NPs against oxidation. The same doping mechanism and higher stability of host metal NPs against oxidation was observed for cobalt-based systems. Since the internalization of the adsorbed dopant at the surface of the host NPs is driven by the mass transport of the host, this mechanism can be potentially applied to introduce dopants into different oxidized forms of metal and metal alloy NPs providing the extra degree of compositional control in material design.

Identification of Surface-Exposed Protein Radicals and A Substrate Oxidation Site in A-Class Dye-Decolorizing Peroxidase from Thermomonospora curvata

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shrestha, Ruben; Chen, Xuejie; Ramyar, Kasra X.

Dye-decolorizing peroxidases (DyPs) are a family of heme peroxidases in which a catalytic distal aspartate is involved in H 2O 2 activation to catalyze oxidations under acidic conditions. They have received much attention due to their potential applications in lignin compound degradation and biofuel production from biomass. However, the mode of oxidation in bacterial DyPs remains unknown. We have recently reported that the bacterial TcDyP from Thermomonospora curvata is among the most active DyPs and shows activity toward phenolic lignin model compounds. On the basis of the X-ray crystal structure solved at 1.75 Å, sigmoidal steady-state kinetics with Reactive Bluemore » 19 (RB19), and formation of compound II like product in the absence of reducing substrates observed with stopped-flow spectroscopy and electron paramagnetic resonance (EPR), we hypothesized that the TcDyP catalyzes oxidation of large-size substrates via multiple surface-exposed protein radicals. Among 7 tryptophans and 3 tyrosines in TcDyP consisting of 376 residues for the matured protein, W263, W376, and Y332 were identified as surface-exposed protein radicals. Only the W263 was also characterized as one of the surface-exposed oxidation sites. SDS-PAGE and size-exclusion chromatography demonstrated that W376 represents an off-pathway destination for electron transfer, resulting in the cross-linking of proteins in the absence of substrates. Mutation of W376 improved compound I stability and overall catalytic efficiency toward RB19. While Y332 is highly conserved across all four classes of DyPs, its catalytic function in A-class TcDyP is minimal, possibly due to its extremely small solvent-accessible areas. Identification of surface-exposed protein radicals and substrate oxidation sites is important for understanding the DyP mechanism and modulating its catalytic functions for improved activity on phenolic lignin.« less

Effect of replacing a hydroxyl group with a methyl group on arsenic (V) species adsorption on goethite (alpha-FeOOH).

PubMed

Zhang, J S; Stanforth, R S; Pehkonen, S O

2007-02-01

Arsenate and methylated arsenicals, such as dimethylarsinate (DMA) and monomethylarsonate (MMA), are being found with increasing frequency in natural water systems. The mobility and bioavailability of these arsenic species in the environment are strongly influenced by their interactions with mineral surface, especially iron and aluminum oxides. Goethite (alpha-FeOOH), one of the most abundant ferric (hydr)oxides in natural systems, has a high retention capacity for arsenic species. Unfortunately, the sorption mechanism for the species is not completely understood, which limits our ability to model their behavior in natural systems. The purpose of this study is to investigate the effect of replacing a hydroxyl group with a methyl group on the adsorption behaviors of arsenic (V) species using adsorption edges, the influence of the background electrolyte on arsenic adsorption, and their effect on the zeta potential of goethite. The affinity of the three species to the goethite surface decreases in the order of AsO4=MMA>DMA. The uptake of DMA and MMA is independent of the concentration of background electrolyte, indicating that both species form inner-sphere complexes on the goethite surface and the most charge of adsorbed DMA and MMA locates at the surface plane. Arsenate uptake increases with increasing concentrations of background electrolyte at pH above 4, possibly due to that the charge of adsorbed arsenate is distributed between the surface plane and another electrostatic plane. DMA and lower concentrations of MMA have small effect on the zeta potential, whereas the zeta potential of goethite decreases in the presence of arsenate. The small effect on zeta potential of DMA or MMA adsorption suggests that the sorption sites for the anions is not important in controlling the surface charge. This observation is inconsistent with most adsorption models that postulate a singly coordinated hydroxyls contributing to both the adsorption and the surface charge, but supports the thesis that the charge on the goethite surface comes primarily from protonation of the triply bound oxygen atoms on the surface.

Etude Spectroscopique des Surfaces des Couches Minces de Silicium Amorphe Hydrogene

NASA Astrophysics Data System (ADS)

Bekkay, Touhami

In this work, we have studied the surface of hydrogenated a-Si and phosphorous doped a-Si:H,P. Due to the presence of unstable dangling bonds, these films are oxidized in the air after their preparation. XPS and UPS have been used to study these oxidized surfaces before and after plasma sputtering and wet chemical cleaning. We used deconvolution technique for the analysis of the spectra. First, the composition of a-Si:H films, prepared by plasma deposition at various power levels, has been determined by XPS. It has been found that films deposited using 5 W power contain SiH_4 molecules. This is confirmed by IR measurements. These molecules have not been seen in films prepared with a plasma power above 5 W. The XPS spectra of the surface oxide, before and after 3 keV sputtering by argon show that is impossible to completely remove these surface oxide ions. During sputtering, some oxygen atoms are forward scattered into the silicon substrat and form new oxidation states. UPS has been used to study the valence bands of the oxidized surfaces before and after HF cleaning. Prior to a chemical etch, the valence band analysis of the native SiO_2 indicates the presence of three O(2p) orbitals, in agreement with theory. Two are non-bonding orbitals and the third is associated with weak bonding to Si(3p). Two other orbitals have been identified at 10 eV and 11.8 eV. They correspond to O(2p)-Si(3p) and O(2p)-Si(3s) bonds respectively. A residual film containing -SiH, -SiO, SiOH and non-bonding orbitals has been found, after HF cleaning. A series of a-Si:H films have been doped with phosphine (PH_3). Their corresponding XPS spectra around 130 eV are dominated by the surface and bulk plasmon peaks. Numerical filtering has been used to distinguish between the phosphorous P(2p) peak located at 129.5 eV and the phosphorous oxide peak located at 134 eV. The increase in the intensity of these peaks as the (PH_3) increases indicates that a certain proportion of phosphorous is incorporated into the Si matrix and that the rest is oxidized. The shifts of the bulk Fermi level, E_{rm F}, and the surface Fermi level, E _{rm FS}, vary linearly with (PH_3). The difference between these two straight lines give the potential responsible for the bulk band bending. Close to the surface, the band bending is deduced by varying the detection angle in XPS measurements; a maximum value of 0.2 eV has been found in a depth range of 38 A to 105 A.

Surface reactivity of mercury on the oxygen-terminated hematite(0001) surface: a first-principle study

NASA Astrophysics Data System (ADS)

Jung, J. E.; Wilcox, J.

2016-12-01

Hematite (α-Fe2O3) is a common mineral found in Earth's near-surface environment. Due to its nontoxicity, corrosion-resistance, and high thermal stability, α-Fe2O3 has attracted attentions as materials for various applications such as photocatalysts, gas sensors, as well as for the removal of heavy metals. In this study, α-Fe2O3 is chosen for potential mercury (Hg) sorbent in order to remove Hg from coal-fired power plants. Specifically, theoretical approaches using density functional theory (DFT) is used to understand surface reactivity of Hg on oxygen (O) terminated α-Fe2O3(0001) surface. The most probable adsorption sites of Hg, chlorine (Cl), and mercury chloride (HgCl) on the α-Fe2O3 surface are found based on adsorption energy calculations, and the oxidation states of the adsorbates are determined by Bader charge analysis. Additionally, projected density of states (PDOS) analysis characterizes the surface-adsorbate bonding mechanism. The results of adsorption energy calculation proposes that Hg physisorbs to the α-Fe2O3(0001) surface with adsorption energy of -0.278 eV, and the subsequent Bader charge analysis confirms that Hg is slightly oxidized. In addition, Cl introduced to the Hg-adsorbed surface strengthens Hg stability on the α-Fe2O3(0001) surface as evidenced by a shortened Hg-surface equilibrium distance. The PDOS analysis also suggests that Cl enhances the chemical bonding between the surface and the adsorbate, thereby increasing adsorption strength. In summary, α-Fe2O3 has ability to adsorb and oxidize Hg, and this reactivity is enhanced in the presence of Cl.

Electrochemically enhanced antibody immobilization on polydopamine thin film for sensitive surface plasmon resonance immunoassay.

PubMed

Chen, Daqun; Mei, Yihong; Hu, Weihua; Li, Chang Ming

2018-05-15

For sensitive immunoassay, it is essentially important to immobilize antibody on a surface with high density and full retention of their recognition activity. Bio-inspired polydopamine (PDA) thin film has been widely utilized as a reactive coating to immobilize antibody on various surfaces. We herein report that the antibody immobilization capacity of PDA thin film is electrochemically enhanced by applying an oxidative potential to convert the surface catechol group to reactive quinone group. Quantitative surface plasmon resonance (SPR) investigation unveils that upon proper electrochemical oxidization, the antibody loading capacity of PDA film is significantly improved (up to 27%) and is very close to the theoretically maximal capacity of a planar surface if concentrated antibody solution is used. Using prostate-specific antigen (PSA) as a model target, it is further demonstrated that the SPR immunoassay sensitivity is greatly enhanced due to the improved antibody immobilization. This work offers an efficient strategy to enhance the reactivity of PDA film towards nucleophiles, and may also facilitate its immunoassay application among others. Copyright © 2018 Elsevier B.V. All rights reserved.

Adsorption of uranium(VI) to manganese oxides: X-ray absorption spectroscopy and surface complexation modeling.

PubMed

Wang, Zimeng; Lee, Sung-Woo; Catalano, Jeffrey G; Lezama-Pacheco, Juan S; Bargar, John R; Tebo, Bradley M; Giammar, Daniel E

2013-01-15

The mobility of hexavalent uranium in soil and groundwater is strongly governed by adsorption to mineral surfaces. As strong naturally occurring adsorbents, manganese oxides may significantly influence the fate and transport of uranium. Models for U(VI) adsorption over a broad range of chemical conditions can improve predictive capabilities for uranium transport in the subsurface. This study integrated batch experiments of U(VI) adsorption to synthetic and biogenic MnO(2), surface complexation modeling, ζ-potential analysis, and molecular-scale characterization of adsorbed U(VI) with extended X-ray absorption fine structure (EXAFS) spectroscopy. The surface complexation model included inner-sphere monodentate and bidentate surface complexes and a ternary uranyl-carbonato surface complex, which was consistent with the EXAFS analysis. The model could successfully simulate adsorption results over a broad range of pH and dissolved inorganic carbon concentrations. U(VI) adsorption to synthetic δ-MnO(2) appears to be stronger than to biogenic MnO(2), and the differences in adsorption affinity and capacity are not associated with any substantial difference in U(VI) coordination.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao, Franklin

Two main categories of heterogeneous catalysts are metal and metal oxide which catalyze 80% chemical reactions at solid-gas and solid-liquid interfaces. Metal oxide catalysts are much more complicated than metal catalysts. The reason is that the cations of the metal atoms could exhibit a few different oxidation states on surface of the same catalyst particle such as Co 3O 4 or change of their oxidation states under different reactive environments. For a metal catalyst, there is only one oxidation state typically. In addition, surface of a metal oxide can be terminated with multiple surface functionalities including O atoms with differentmore » binding configurations and OH group. For metal, only metal atoms are exposed typically. Obviously, the complication of surface chemistry and structure of a metal oxide makes studies of surface of an oxide catalyst very challenging. Due to the complication of surface of a meal oxide, the electronic and geometric structures of surface of a metal oxide and the exposed species have received enormous attention since oxide catalysts catalyze at least 1/3 chemical reactions in chemical and energy industries. Understanding of catalytic reactions on early transition metal oxide-based catalysts is fundamentally intriguing and of great practical interest in energy- and environment-related catalysis. Exploration of surface chemistry of oxide-based catalysts at molecular level during catalysis has remained challenging though it is critical in deeply understanding catalysis on oxide-based catalysts and developing oxide-based catalysts with high activity and selectivity. Thus, the overall objective of this project is to explore surface chemistry and structure of early transition metal oxide-based catalysts through in-situ characterization of surface of catalysts, measurements of catalytic performances, and then build an intrinsic correlation of surface chemistry and structure with their catalytic performances in a few important catalytic reactions, and essentially fundamentally understand catalytic mechanism. Furthermore, this correlation will guide the design of catalysts with high activity and selectivity.« less

Relative sliding durability of two candidate high temperature oxide fiber seal materials

NASA Technical Reports Server (NTRS)

Dellacorte, Christopher; Steinetz, Bruce M.

1991-01-01

A test program to determine the relative sliding durability of two candidate ceramic fibers for high temperature sliding seal applications is described. Pin on disk tests were used to evaluate potential seal materials. Friction during the tests and fiber wear, indicated by the extent of fibers broken in a test bundle or yarn, was measured at the end of a test. In general, friction and wear increase with test temperature. This may be due to a reduction in fiber strength, a change in the surface chemistry at the fiber/counterface interface due to oxidation, adsorption and/or desorption of surface species and, to a lesser extent, an increase in counterface surface roughness due to oxidation at elevated temperatures. The relative fiber durability correlates with tensile strength indicating that tensile data, which is more readily available than sliding durability data, may be useful in predicting fiber wear behavior under various conditions. A simple model developed using dimensional analysis shows that the fiber durability is related to a dimensionless parameter which represents the ratio of the fiber strength to the fiber stresses imposed by sliding.

Use of anionic surfactants for selective polishing of silicon dioxide over silicon nitride films using colloidal silica-based slurries

NASA Astrophysics Data System (ADS)

Penta, Naresh K.; Amanapu, H. P.; Peethala, B. C.; Babu, S. V.

2013-10-01

Four different anionic surfactants, sodium dodecyl sulfate, dodecyl benzene sulfonic acid (DBSA), dodecyl phosphate and Sodium lauroyl sarcosine, selected from the sulfate, phosphate, and carboxylic family, were investigated as additives in silica dispersions for selective polishing of silicon dioxide over silicon nitride films. We found that all these anionic surfactants suppress the nitride removal rates (RR) for pH ≤4 while more or less maintaining the oxide RRs, resulting in high oxide-to-nitride RR selectivity. The RR data obtained as a function of pH were explained based on pH dependent distributions of surfactant species, change in the zeta potentials of oxide and nitride surfaces, and thermogravimetric data. It appears that the negatively charged surfactant species preferentially adsorb on the positively charged nitride surface below IEP through its electrostatic interactions and form a bilayer adsorption, resulting in the suppression of nitride RRs. In contrast to the surfactants, K2SO4 interacts only weakly with the nitride surface and hence cannot suppress its RR.

Surface-oxidized cobalt phosphide used as high efficient electrocatalyst in activated carbon air-cathode microbial fuel cell

NASA Astrophysics Data System (ADS)

Yang, Tingting; Wang, Zhong; Li, Kexun; Liu, Yi; Liu, Di; Wang, Junjie

2017-09-01

Herein, we report a simplistic method to fabricate the surface-oxidized cobalt phosphide (CoP) nanocrystals (NCs), which is used as electrocatalyst for oxygen reduction reaction (ORR) in microbial fuel cell (MFC) for the first time. The corallite-like CoP NCs are successfully prepared by a hydrothermal reaction following a phosphating treatment in N2 atmosphere. When used as an ORR catalyst, cobalt phosphide shows comparable onset potential, inferior resistance, as well as a small Tafel slope with long-term stability in neutral media. The maximum power density of MFC embellished with 10% CoP reached 1914.4 ± 59.7 mW m-2, which is 108.5% higher than the control. The four-electron pathway, observed by the RDE, plays a crucial role in electrochemical catalytic activity. In addition, material characterizations indicate that the surface oxide layer (CoOx) around the metallic CoP core is important and beneficial for ORR. Accordingly, it can be expected that the as-synthesized CoP will be a promising candidate of the non-precious metal ORR electrocatalysts for electrochemical energy applications.

Oxide surfaces and metal/oxide interfaces studied by grazing incidence X-ray scattering

NASA Astrophysics Data System (ADS)

Renaud, Gilles

Experimental determinations of the atomic structure of insulating oxide surfaces and metal/oxide interfaces are scarce, because surface science techniques are often limited by the insulating character of the substrate. Grazing incidence X-ray scattering (GIXS), which is not subject to charge effects, can provide very precise information on the atomic structure of oxide surfaces: roughness, relaxation and reconstruction. It is also well adapted to analyze the atomic structure, the registry, the misfit relaxation, elastic or plastic, the growth mode and the morphology of metal/oxide interfaces during their growth, performed in situ. GIXS also allows the analysis of thin films and buried interfaces, in a non-destructive way, yielding the epitaxial relationships, and, by variation of the grazing incidence angle, the lattice parameter relaxation along the growth direction. On semi-coherent interfaces, the existence of an ordered network of interfacial misfit dislocations can be demonstrated, its Burger's vector determined, its ordering during in situ annealing cycles followed, and sometimes even its atomic structure can be addressed. Careful analysis during growth allows the modeling of the dislocation nucleation process. This review emphasizes the new information that GIXS can bring to oxide surfaces and metal/oxide interfaces by comparison with other surface science techniques. The principles of X-ray diffraction by surfaces and interfaces are recalled, together with the advantages and properties of grazing angles. The specific experimental requirements are discussed. Recent results are presented on the determination of the atomic structure of relaxed or reconstructed oxide surfaces. A description of results obtained during the in situ growth of metal on oxide surfaces is also given, as well as investigations of thick metal films on oxide surfaces, with lattice parameter misfit relaxed by an array of dislocations. Recent work performed on oxide thin films having important physical properties such as superconductivity or magnetism is also briefly reviewed. The strengths and limitations of the technique, such as the need for single crystals and surfaces of high crystalline quality are discussed. Finally, an outlook of future prospects in the field is given, such as the study of more complex oxide surfaces, vicinal surfaces, reactive metal/oxide interfaces, metal oxidation processes, the use of surfactants to promote wetting of a metal deposited on an oxide surface or the study of oxide/liquid interfaces in a non-UHV environment.

Modeling the Acid-Base Properties of Montmorillonite Edge Surfaces.

PubMed

Tournassat, Christophe; Davis, James A; Chiaberge, Christophe; Grangeon, Sylvain; Bourg, Ian C

2016-12-20

The surface reactivity of clay minerals remains challenging to characterize because of a duality of adsorption surfaces and mechanisms that does not exist in the case of simple oxide surfaces: edge surfaces of clay minerals have a variable proton surface charge arising from hydroxyl functional groups, whereas basal surfaces have a permanent negative charge arising from isomorphic substitutions. Hence, the relationship between surface charge and surface potential on edge surfaces cannot be described using the Gouy-Chapman relation, because of a spillover of negative electrostatic potential from the basal surface onto the edge surface. While surface complexation models can be modified to account for these features, a predictive fit of experimental data was not possible until recently, because of uncertainty regarding the densities and intrinsic pK a values of edge functional groups. Here, we reexamine this problem in light of new knowledge on intrinsic pK a values obtained over the past decade using ab initio molecular dynamics simulations, and we propose a new formalism to describe edge functional groups. Our simulation results yield reasonable predictions of the best available experimental acid-base titration data.

SERS as a tool for in vitro toxicology.

PubMed

Fisher, Kate M; McLeish, Jennifer A; Jamieson, Lauren E; Jiang, Jing; Hopgood, James R; McLaughlin, Stephen; Donaldson, Ken; Campbell, Colin J

2016-06-23

Measuring markers of stress such as pH and redox potential are important when studying toxicology in in vitro models because they are markers of oxidative stress, apoptosis and viability. While surface enhanced Raman spectroscopy is ideally suited to the measurement of redox potential and pH in live cells, the time-intensive nature and perceived difficulty in signal analysis and interpretation can be a barrier to its broad uptake by the biological community. In this paper we detail the development of signal processing and analysis algorithms that allow SERS spectra to be automatically processed so that the output of the processing is a pH or redox potential value. By automating signal processing we were able to carry out a comparative evaluation of the toxicology of silver and zinc oxide nanoparticles and correlate our findings with qPCR analysis. The combination of these two analytical techniques sheds light on the differences in toxicology between these two materials from the perspective of oxidative stress.

Apparatus for sensing patterns of electrical field variations across a surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Warren, William L.; Devine, Roderick A. B.

An array of nonvolatile field effect transistors used to sense electric potential variations. The transistors owe their nonvolatility to the movement of protons within the oxide layer that occurs only in response to an externally applied electric potential between the gate on one side of the oxide and the source/drain on the other side. The position of the protons within the oxide layer either creates or destroys a conducting channel in the adjacent source/channel/drain layer below it, the current in the channel being measured as the state of the nonvolatile memory. The protons can also be moved by potentials createdmore » by other instrumentalities, such as charges on fingerprints or styluses above the gates, pressure on a piezoelectric layer above the gates, light shining upon a photoconductive layer above the gates. The invention allows sensing of fingerprints, handwriting, and optical images, which are converted into digitized images thereof in a nonvolatile format.« less

Old Faithful Model for Radiolytic Gas-Driven Cryovolcanism at Enceladus

NASA Technical Reports Server (NTRS)

Cooper, John F.; Cooper, Paul D.; Sittler, Edward; Sturner, Steven J.; Rymer, Abigail M.

2009-01-01

A new model is presented on how chemically driven cryovolcanism might contribute to episodic outgassing at the icy moon Enceladus and potentially elsewhere including Europa and Kuiper Belt Objects. Exposed water ices can become oxidized from radiolytic chemical alteration of near-surface water ice by space environment irradiation. In contact with primordially abundant reductants such as NH3, CH4, and other hydrocarbons, the product oxidants can react exothermically to produce volatile gases driving cryovolcanism via gas-piston forces on any subsurface liquid reservoirs. Radiolytic oxidants such as H2O2 and O2 can continuously accumulate deep in icy regoliths and be conveyed by rheological flows to subsurface chemical reaction zones over million-year time scales indicated by cratering ages for active regions of Enceladus and Europa. Surface blanketing with cryovolcanic plume ejecta would further accelerate regolith burial of radiolytic oxidants. Episodic heating from transient gravitational tides, radioisotope decay, impacts, or other geologic events might occasionally accelerate chemical reaction rates and ignite the exothermic release of cumulative radiolytic oxidant energy. The time history for the suggested "Old Faithful" model of radiolytic gas-driven cryovolcanism at Enceladus and elsewhere therefore consists of long periods of chemical energy accumulation punctuated by much briefer episodes of cryovolcanic activity. The most probable sequence for detection of activity in the current epoch is a long evolutionary phase of slow but continuous oxidant accumulation over billions of years followed by continuous but variable high activity over the past 10(exp 7)-10(exp 8) years. Detectable cryovolcanic activity could then later decline due to near-total oxidation of the rheologically accessible ice crust and depletion the accessible reductant abundances, as may have already occurred for Europa in the more intense radiation environment of Jupiter's magnetosphere. Astrobiological potential of Enceladus could correspondingly be higher than at Europa due to a less extreme state of oxidation and greater residual abundance of organics.

Roles of Mo Surface Dopants in Enhancing the ORR Performance of Octahedral PtNi Nanoparticles

DOE PAGES

Jia, Qingying; Zhao, Zipeng; Cao, Liang; ...

2017-12-22

Doping with a transition metal was recently shown to greatly boost the activity and durability of PtNi/C octahedral nanoparticles (NPs) for the oxygen reduction reaction (ORR), but its specific roles remain unclear. By combining electrochemistry, ex situ and in situ spectroscopic techniques, density functional theory calculations, and a newly developed kinetic Monte Carlo model, we showed that Mo atoms are preferentially located on the vertex and edge sites of Mo–PtNi/C in the form of oxides, which are stable within the wide potential window of the electrochemical cycle. These surface Mo oxides stabilize adjacent Pt sites, hereby stabilizing the octahedral shapemore » enriched with (111) facets, and lead to increased concentration of Ni in subsurface layers where they are protected against acid dissolution. Consequently, the favorable Pt 3Ni(111) structure for the ORR is stabilized on the surface of PtNi/C NPs in acid against voltage cycling. Significantly, the unusual potential-dependent oxygen coverage trend on Mo-doped PtNi/C NPs as revealed by the surface-sensitive Δμ analysis suggests that the Mo dopants may also improve the ORR kinetics by modifying the coordination environments of Pt atoms on the surface. Lastly, our studies point out a possible way to stabilize the favorable shape and composition established on conceptual catalytic models in practical nanoscale catalysts.« less

Roles of Mo Surface Dopants in Enhancing the ORR Performance of Octahedral PtNi Nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jia, Qingying; Zhao, Zipeng; Cao, Liang

Doping with a transition metal was recently shown to greatly boost the activity and durability of PtNi/C octahedral nanoparticles (NPs) for the oxygen reduction reaction (ORR), but its specific roles remain unclear. By combining electrochemistry, ex situ and in situ spectroscopic techniques, density functional theory calculations, and a newly developed kinetic Monte Carlo model, we showed that Mo atoms are preferentially located on the vertex and edge sites of Mo–PtNi/C in the form of oxides, which are stable within the wide potential window of the electrochemical cycle. These surface Mo oxides stabilize adjacent Pt sites, hereby stabilizing the octahedral shapemore » enriched with (111) facets, and lead to increased concentration of Ni in subsurface layers where they are protected against acid dissolution. Consequently, the favorable Pt 3Ni(111) structure for the ORR is stabilized on the surface of PtNi/C NPs in acid against voltage cycling. Significantly, the unusual potential-dependent oxygen coverage trend on Mo-doped PtNi/C NPs as revealed by the surface-sensitive Δμ analysis suggests that the Mo dopants may also improve the ORR kinetics by modifying the coordination environments of Pt atoms on the surface. Lastly, our studies point out a possible way to stabilize the favorable shape and composition established on conceptual catalytic models in practical nanoscale catalysts.« less

TEMPO-oxidized cellulose nanofibers

NASA Astrophysics Data System (ADS)

Isogai, Akira; Saito, Tsuguyuki; Fukuzumi, Hayaka

2011-01-01

Native wood celluloses can be converted to individual nanofibers 3-4 nm wide that are at least several microns in length, i.e. with aspect ratios >100, by TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical)-mediated oxidation and successive mild disintegration in water. Preparation methods and fundamental characteristics of TEMPO-oxidized cellulose nanofibers (TOCN) are reviewed in this paper. Significant amounts of C6 carboxylate groups are selectively formed on each cellulose microfibril surface by TEMPO-mediated oxidation without any changes to the original crystallinity (~74%) or crystal width of wood celluloses. Electrostatic repulsion and/or osmotic effects working between anionically-charged cellulose microfibrils, the ζ-potentials of which are approximately -75 mV in water, cause the formation of completely individualized TOCN dispersed in water by gentle mechanical disintegration treatment of TEMPO-oxidized wood cellulose fibers. Self-standing TOCN films are transparent and flexible, with high tensile strengths of 200-300 MPa and elastic moduli of 6-7 GPa. Moreover, TOCN-coated poly(lactic acid) films have extremely low oxygen permeability. The new cellulose-based nanofibers formed by size reduction process of native cellulose fibers by TEMPO-mediated oxidation have potential application as environmentally friendly and new bio-based nanomaterials in high-tech fields.

Facile fabrication of Ag dendrite-integrated anodic aluminum oxide membrane as effective three-dimensional SERS substrate

NASA Astrophysics Data System (ADS)

Zhang, Cong-yun; Lu, Ya; Zhao, Bin; Hao, Yao-wu; Liu, Ya-qing

2016-07-01

A novel surface enhanced Raman scattering (SERS)-active substrate has been successfully developed, where Ag-dendrites are assembled on the surface and embedded in the channels of anodic aluminum oxide (AAO) membrane, via electrodeposition in AgNO3/PVP aqueous system. Reaction conditions were systematically investigated to attain the best Raman enhancement. The growth mechanism of Ag dendritic nanostructures has been proposed. The Ag dendrite-integrated AAO membrane with unique hierarchical structures exhibits high SERS activity for detecting rhodamine 6G with a detection limit as low as 1 × 10-11 M. Furthermore, the three-dimensional (3D) substrates display a good reproducibility with the average intensity variations at the major Raman peak less than 12%. Most importantly, the 3D SERS substrates without any surface modification show an outstanding SERS response for the molecules with weak affinity for noble metal surfaces. The potential application for the detection of polycyclic aromatic hydrocarbons (PAHs) was evaluated with fluoranthene as Raman target molecule and a sensitive SERS detection with a limit down to 10-8 M was reached. The 3D SERS-active substrate shows promising potential for rapid detection of trace organic pollutants even weak affinity molecules in the environment.

Adsorption of polycyclic aromatic hydrocarbons by graphene and graphene oxide nanosheets.

PubMed

Wang, Jun; Chen, Zaiming; Chen, Baoliang

2014-05-06

The adsorption of naphthalene, phenanthrene, and pyrene onto graphene (GNS) and graphene oxide (GO) nanosheets was investigated to probe the potential adsorptive sites and molecular mechanisms. The microstructure and morphology of GNS and GO were characterized by elemental analysis, XPS, FTIR, Raman, SEM, and TEM. Graphene displayed high affinity to the polycyclic aromatic hydrocarbons (PAHs), whereas GO adsorption was significantly reduced after oxygen-containing groups were attached to GNS surfaces. An unexpected peak was found in the curve of adsorption coefficients (Kd) with the PAH equilibrium concentrations. The hydrophobic properties and molecular sizes of the PAHs affected the adsorption of G and GO. The high affinities of the PAHs to GNS are dominated by π-π interactions to the flat surface and the sieving effect of the powerful groove regions formed by wrinkles on GNS surfaces. In contrast, the adsorptive sites of GO changed to the carboxyl groups attaching to the edges of GO because the groove regions disappeared and the polar nanosheet surfaces limited the π-π interactions. The TEM and SEM images initially revealed that after loading with PAH, the conformation and aggregation of GNS and GO nanosheets dramatically changed, which explained the observations that the potential adsorption sites of GNS and GO were unusually altered during the adsorption process.

In Situ Investigation of Electrochemically Mediated Surface-Initiated Atom Transfer Radical Polymerization by Electrochemical Surface Plasmon Resonance.

PubMed

Chen, Daqun; Hu, Weihua

2017-04-18

Electrochemically mediated atom transfer radical polymerization (eATRP) initiates/controls the controlled/living ATRP chain propagation process by electrochemically generating (regenerating) the activator (lower-oxidation-state metal complex) from deactivator (higher-oxidation-state metal complex). Despite successful demonstrations in both of the homogeneous polymerization and heterogeneous systems (namely, surface-initiated ATRP, SI-ATRP), the eATRP process itself has never been in situ investigated, and important information regarding this process remains unrevealed. In this work, we report the first investigation of the electrochemically mediated SI-ATRP (eSI-ATRP) by rationally combining the electrochemical technique with real-time surface plasmon resonance (SPR). In the experiment, the potential of a SPR gold chip modified by the self-assembled monolayer of the ATRP initiator was controlled to electrochemically reduce the deactivator to activator to initiate the SI-ATRP, and the whole process was simultaneously monitored by SPR with a high time resolution of 0.1 s. It is found that it is feasible to electrochemically trigger/control the SI-ATRP and the polymerization rate is correlated to the potential applied to the gold chip. This work reveals important kinetic information for eSI-ATRP and offers a powerful platform for in situ investigation of such complicated processes.

The surface characterization and passive behavior of Type 316L stainless steel in H2S-containing conditions

NASA Astrophysics Data System (ADS)

Wang, Zhu; Zhang, Lei; Tang, Xian; Zhang, Ziru; Lu, Minxu

2017-11-01

The protectiveness and characterization of passive films formed at various potentials in H2S-containing environments were studied using electrochemical measurements and surface analysis method. The corrosion resistance of 316L in H2S-containing environment decreases with the applied potential. The Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) results indicate that Ni participates in the film formation, which results in the corresponding enrichment in the passive film. The oxidization degree analysis indicates that metallic elements are present in the passive film. Sulfide ions are significantly favored in the passive film at higher potentials, which is responsible for the breakdown of passive film.

Chemical and isotope compositions of shallow groundwater in areas impacted by hydraulic fracturing and surface mining in the Central Appalachian Basin, Eastern United States

DOE Office of Scientific and Technical Information (OSTI.GOV)

LeDoux, St. Thomas M.; Szynkiewicz, Anna; Faiia, Anthony M.

Here, hydraulic fracturing of shale deposits has greatly increased the productivity of the natural gas industry by allowing it to exploit previously inaccessible reservoirs. Previous research has demonstrated that this practice has the potential to contaminate shallow aquifers with methane (CH 4) from deeper formations. This study compares concentrations and isotopic compositions of CH 4 sampled from domestic groundwater wells in Letcher County, Eastern Kentucky in order to characterize its occurrence and origins in relation to both neighboring hydraulically fractured natural gas wells and surface coal mines. The studied groundwater showed concentrations of CH 4 ranging from 0.05 mg/L tomore » 10 mg/L, thus, no immediate remediation is required. The δ 13C values of CH 4 ranged from 66‰ to 16‰, and δ 2H values ranged from –286‰ to –86‰, suggesting an immature thermogenic and mixed biogenic/thermogenic origin. The occurrence of CH 4 was not correlated with proximity to hydraulically fractured natural gas wells. Generally, CH 4 occurrence corresponded with groundwater abundant in Na +, Cl –, and HCO 3 – , and with low concentrations of SO 4 –2. The CH 4 and SO 4 –2 concentrations were best predicted by the oxidation/reduction potential of the studied groundwater. CH 4 was abundant in more reducing waters, and SO 4 –2 was abundant in more oxidizing waters. Additionally, groundwater in greater proximity to surface mining was more likely to be oxidized. This, in turn, might have increased the likelihood of CH 4 oxidation in shallow groundwater.« less

Chemical and isotope compositions of shallow groundwater in areas impacted by hydraulic fracturing and surface mining in the Central Appalachian Basin, Eastern United States

DOE PAGES

LeDoux, St. Thomas M.; Szynkiewicz, Anna; Faiia, Anthony M.; ...

2016-05-17

Here, hydraulic fracturing of shale deposits has greatly increased the productivity of the natural gas industry by allowing it to exploit previously inaccessible reservoirs. Previous research has demonstrated that this practice has the potential to contaminate shallow aquifers with methane (CH 4) from deeper formations. This study compares concentrations and isotopic compositions of CH 4 sampled from domestic groundwater wells in Letcher County, Eastern Kentucky in order to characterize its occurrence and origins in relation to both neighboring hydraulically fractured natural gas wells and surface coal mines. The studied groundwater showed concentrations of CH 4 ranging from 0.05 mg/L tomore » 10 mg/L, thus, no immediate remediation is required. The δ 13C values of CH 4 ranged from 66‰ to 16‰, and δ 2H values ranged from –286‰ to –86‰, suggesting an immature thermogenic and mixed biogenic/thermogenic origin. The occurrence of CH 4 was not correlated with proximity to hydraulically fractured natural gas wells. Generally, CH 4 occurrence corresponded with groundwater abundant in Na +, Cl –, and HCO 3 – , and with low concentrations of SO 4 –2. The CH 4 and SO 4 –2 concentrations were best predicted by the oxidation/reduction potential of the studied groundwater. CH 4 was abundant in more reducing waters, and SO 4 –2 was abundant in more oxidizing waters. Additionally, groundwater in greater proximity to surface mining was more likely to be oxidized. This, in turn, might have increased the likelihood of CH 4 oxidation in shallow groundwater.« less

Isothiocyanate from Moringa oleifera seeds mitigates hydrogen peroxide-induced cytotoxicity and preserved morphological features of human neuronal cells

PubMed Central

Shaari, Khozirah; Rosli, Rozita

2018-01-01

Reactive oxygen species are well known for induction of oxidative stress conditions through oxidation of vital biomarkers leading to cellular death via apoptosis and other process, thereby causing devastative effects on the host organs. This effect is believed to be linked with pathological alterations seen in several neurodegenerative disease conditions. Many phytochemical compounds proved to have robust antioxidant activities that deterred cells against cytotoxic stress environment, thus protect apoptotic cell death. In view of that we studied the potential of glucomoringin-isothiocyanate (GMG-ITC) or moringin to mitigate the process that lead to neurodegeneration in various ways. Neuroprotective effect of GMG-ITC was performed on retinoic acid (RA) induced differentiated neuroblastoma cells (SHSY5Y) via cell viability assay, flow cytometry analysis and fluorescence microscopy by means of acridine orange and propidium iodide double staining, to evaluate the anti-apoptotic activity and morphology conservation ability of the compound. Additionally, neurite surface integrity and ultrastructural analysis were carried out by means of scanning and transmission electron microscopy to assess the orientation of surface and internal features of the treated neuronal cells. GMG-ITC pre-treated neuron cells showed significant resistance to H2O2-induced apoptotic cell death, revealing high level of protection by the compound. Increase of intracellular oxidative stress induced by H2O2 was mitigated by GMG-ITC. Thus, pre-treatment with the compound conferred significant protection to cytoskeleton and cytoplasmic inclusion coupled with conservation of surface morphological features and general integrity of neuronal cells. Therefore, the collective findings in the presence study indicated the potentials of GMG-ITC to protect the integrity of neuron cells against induced oxidative-stress related cytotoxic processes, the hallmark of neurodegenerative diseases. PMID:29723199

Isothiocyanate from Moringa oleifera seeds mitigates hydrogen peroxide-induced cytotoxicity and preserved morphological features of human neuronal cells.

PubMed

Jaafaru, Mohammed Sani; Nordin, Norshariza; Shaari, Khozirah; Rosli, Rozita; Abdull Razis, Ahmad Faizal

2018-01-01

Reactive oxygen species are well known for induction of oxidative stress conditions through oxidation of vital biomarkers leading to cellular death via apoptosis and other process, thereby causing devastative effects on the host organs. This effect is believed to be linked with pathological alterations seen in several neurodegenerative disease conditions. Many phytochemical compounds proved to have robust antioxidant activities that deterred cells against cytotoxic stress environment, thus protect apoptotic cell death. In view of that we studied the potential of glucomoringin-isothiocyanate (GMG-ITC) or moringin to mitigate the process that lead to neurodegeneration in various ways. Neuroprotective effect of GMG-ITC was performed on retinoic acid (RA) induced differentiated neuroblastoma cells (SHSY5Y) via cell viability assay, flow cytometry analysis and fluorescence microscopy by means of acridine orange and propidium iodide double staining, to evaluate the anti-apoptotic activity and morphology conservation ability of the compound. Additionally, neurite surface integrity and ultrastructural analysis were carried out by means of scanning and transmission electron microscopy to assess the orientation of surface and internal features of the treated neuronal cells. GMG-ITC pre-treated neuron cells showed significant resistance to H2O2-induced apoptotic cell death, revealing high level of protection by the compound. Increase of intracellular oxidative stress induced by H2O2 was mitigated by GMG-ITC. Thus, pre-treatment with the compound conferred significant protection to cytoskeleton and cytoplasmic inclusion coupled with conservation of surface morphological features and general integrity of neuronal cells. Therefore, the collective findings in the presence study indicated the potentials of GMG-ITC to protect the integrity of neuron cells against induced oxidative-stress related cytotoxic processes, the hallmark of neurodegenerative diseases.

A two dimensional analytical modeling of surface potential in triple metal gate (TMG) fully-depleted Recessed-Source/Drain (Re-S/D) SOI MOSFET

NASA Astrophysics Data System (ADS)

Priya, Anjali; Mishra, Ram Awadh

2016-04-01

In this paper, analytical modeling of surface potential is proposed for new Triple Metal Gate (TMG) fully depleted Recessed-Source/Dain Silicon On Insulator (SOI) Metal Oxide Semiconductor Field Effect Transistor (MOSFET). The metal with the highest work function is arranged near the source region and the lowest one near the drain. Since Recessed-Source/Drain SOI MOSFET has higher drain current as compared to conventional SOI MOSFET due to large source and drain region. The surface potential model developed by 2D Poisson's equation is verified by comparison to the simulation result of 2-dimensional ATLAS simulator. The model is compared with DMG and SMG devices and analysed for different device parameters. The ratio of metal gate length is varied to optimize the result.

New oxidation treatment of NiTi shape memory alloys to obtain Ni-free surfaces and to improve biocompatibility.

PubMed

Michiardi, A; Aparicio, C; Planell, J A; Gil, F J

2006-05-01

Various oxidation treatments were applied to nearly equiatomic NiTi alloys so as to form a Ni-free protective oxide on the surface. Sample surfaces were analyzed by X-ray Photoelectron Spectroscopy, and NiTi transformation temperatures were determined by differential scanning calorimetry (DSC) before and after the surface treatment. An ion release experiment was carried out up to one month of immersion in SBF for both oxidized and untreated surfaces. The results show that oxidation treatment in a low-oxygen pressure atmosphere leads to a high surface Ti/Ni ratio, a very low Ni surface concentration and a thick oxide layer. This oxidation treatment does not significantly affect the shape memory properties of the alloy. Moreover, the oxide formed significantly decreases Ni release into exterior medium comparing with untreated surfaces. As a consequence, this new oxidation treatment could be of great interest for biomedical applications, as it could minimize sensitization and allergies and improve biocompatibility and corrosion resistance of NiTi shape memory alloys. (c) 2005 Wiley Periodicals, Inc.

Hydrothermal plume mapping as a prospecting tool for seafloor sulfide deposits: a case study at the Zouyu-1 and Zouyu-2 hydrothermal fields in the southern Mid-Atlantic Ridge

NASA Astrophysics Data System (ADS)

Tao, Chunhui; Chen, Sheng; Baker, Edward T.; Li, Huaiming; Liang, Jin; Liao, Shili; Chen, Yongshun John; Deng, Xianming; Zhang, Guoyin; Gu, Chunhua; Wu, Jialin

2017-06-01

Seafloor hydrothermal polymetallic sulfide deposits are a new type of resource, with great potential economic value and good prospect development. This paper discusses turbidity, oxidation-reduction potential, and temperature anomalies of hydrothermal plumes from the Zouyu-1 and Zouyu-2 hydrothermal fields on the southern Mid-Atlantic Ridge. We use the known location of these vent fields and plume data collected in multiple years (2009, 2011, 2013) to demonstrate how real-time plume exploration can be used to locate active vent fields, and thus associated sulfide deposits. Turbidity anomalies can be detected 10 s of km from an active source, but the location precision is no better than a few kilometers because fine-grained particles are quasi-conservative over periods of many days. Temperature and oxidation-reduction potential anomalies provide location precision of a few hundred meters. Temperature anomalies are generally weak and difficult to reliably detect, except by chance encounters of a buoyant plume. Oxidation-reduction potential is highly sensitive (nmol concentrations of reduced hydrothermal chemicals) to discharges of all temperatures and responds immediately to a plume encounter. Real-time surveys using continuous tows of turbidity and oxidation-reduction potential sensors offer the most efficient and precise surface ship exploration presently possible.

A charge optimized many-body potential for titanium nitride (TiN).

PubMed

Cheng, Y-T; Liang, T; Martinez, J A; Phillpot, S R; Sinnott, S B

2014-07-02

This work presents a new empirical, variable charge potential for TiN systems in the charge-optimized many-body potential framework. The potential parameters were determined by fitting them to experimental data for the enthalpy of formation, lattice parameters, and elastic constants of rocksalt structured TiN. The potential does a good job of describing the fundamental physical properties (defect formation and surface energies) of TiN relative to the predictions of first-principles calculations. This potential is used in classical molecular dynamics simulations to examine the interface of fcc-Ti(0 0 1)/TiN(0 0 1) and to characterize the adsorption of oxygen atoms and molecules on the TiN(0 0 1) surface. The results indicate that the potential is well suited to model TiN thin films and to explore the chemistry associated with their oxidation.

Fundamental Factors Impacting the Stability of Phosphonate-Derivatized Ruthenium Polypyridyl Sensitizers Adsorbed on Metal Oxide Surfaces.

PubMed

Raber, McKenzie; Brady, Matthew David; Troian-Gautier, Ludovic; Dickenson, John; Marquard, Seth L; Hyde, Jacob; Lopez, Santiago; Meyer, Gerald J; Meyer, Thomas J; Harrison, Daniel P

2018-06-08

A series of 18 ruthenium(II) polypyridyl complexes were synthesized and evaluated under electrochemically oxidative conditions, which generates the Ru(III) oxidation state and mimics the harsh conditions experienced during the kinetically-limited regime that can occur in dye-sensitized solar cells (DSSCs) and dye-sensitized photoelectrosynthesis cells (DSPECs), to further develop fundamental insights into the factors governing molecular sensitizer surface stability in aqueous 0.1 M HClO4 (aq). Both desorption and oxidatively induced ligand substitution were observed on planar fluorine doped tin oxide, FTO, electrodes, with a dependence on the E1/2 Ru(III/II) redox potential dictating the comparative ratios of the processes. Complexes such as RuP4OMe (E1/2 = 0.91 vs Ag/AgCl) displayed virtually only desorption, while complexes such as RuPbpz (E1/2 > 1.62 V vs Ag/AgCl) displayed only chemical decomposition. Comparing isomers of 4,4'- and 5,5-disubstituted-2,2'-bipyridine ancillary polypyridyl ligands, a dramatic increase in the rate of desorption of the Ru(III) complexes was observed for the 5,5'-ligands. Nanoscopic indium doped tin oxide thin films, nanoITO, were also sensitized and analyzed with cyclic voltammetry, UV-Vis absorption spectroscopy, and XPS, allowing for further distinction of desorption versus ligand substitution processes. Desorption loss to bulk solution associated with the planar surface of FTO is essentially non-existent on nanoITO, where both desorption and ligand substitution are shut down with RuP4OMe. These results revealed that minimizing time spent in the oxidized form, incorporating electron donating groups, maximizing hydrophobicity, and minimizing molecular bulk near the adsorbed ligand are critical to optimizing the performance of ruthenium(II) polypyridyl complexes in dye-sensitized solar cell devices.

Atomic and molecular layer deposition for surface modification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vähä-Nissi, Mika, E-mail: mika.vaha-nissi@vtt.fi; Sievänen, Jenni; Salo, Erkki

2014-06-01

Atomic and molecular layer deposition (ALD and MLD, respectively) techniques are based on repeated cycles of gas–solid surface reactions. A partial monolayer of atoms or molecules is deposited to the surface during a single deposition cycle, enabling tailored film composition in principle down to molecular resolution on ideal surfaces. Typically ALD/MLD has been used for applications where uniform and pinhole free thin film is a necessity even on 3D surfaces. However, thin – even non-uniform – atomic and molecular deposited layers can also be used to tailor the surface characteristics of different non-ideal substrates. For example, print quality of inkjetmore » printing on polymer films and penetration of water into porous nonwovens can be adjusted with low-temperature deposited metal oxide. In addition, adhesion of extrusion coated biopolymer to inorganic oxides can be improved with a hybrid layer based on lactic acid. - Graphical abstract: Print quality of a polylactide film surface modified with atomic layer deposition prior to inkjet printing (360 dpi) with an aqueous ink. Number of printed dots illustrated as a function of 0, 5, 15 and 25 deposition cycles of trimethylaluminum and water. - Highlights: • ALD/MLD can be used to adjust surface characteristics of films and fiber materials. • Hydrophobicity after few deposition cycles of Al{sub 2}O{sub 3} due to e.g. complex formation. • Same effect on cellulosic fabrics observed with low temperature deposited TiO{sub 2}. • Different film growth and oxidation potential with different precursors. • Hybrid layer on inorganic layer can be used to improve adhesion of polymer melt.« less

Interfacial Energy Alignment at the ITO/Ultra-Thin Electron Selective Dielectric Layer Interface and Its Effect on the Efficiency of Bulk-Heterojunction Organic Solar Cells.

PubMed

Itoh, Eiji; Goto, Yoshinori; Saka, Yusuke; Fukuda, Katsutoshi

2016-04-01

We have investigated the photovoltaic properties of an inverted bulk heterojunction (BHJ) cell in a device with an indium-tin-oxide (ITO)/electron selective layer (ESL)/P3HT:PCBM active layer/MoOx/Ag multilayered structure. The insertion of only single layer of poly(diallyl-dimethyl-ammonium chloride) (PDDA) cationic polymer film (or poly(ethyleneimine) (PEI) polymeric interfacial dipole layer) and titanium oxide nanosheet (TN) films as an ESL effectively improved cell performance. Abnormal S-shaped curves were observed in the inverted BHJ cells owing to the contact resistance across the ITO/active layer interface and the ITO/PDDA/TN/active layer interface. The series resistance across the ITO/ESL interface in the inverted BHJ cell was successfully reduced using an interfacial layer with a positively charged surface potential with respect to ITO base electrode. The positive dipole in PEI and the electronic charge phenomena at the electrophoretic deposited TN (ED-TN) films on ITO contributed to the reduction of the contact resistance at the electrode interface. The surface potential measurement revealed that the energy alignment by the transfer of electronic charges from the ED-TN to the base electrodes. The insertion of the ESL with a large positive surface potential reduced the potential barrier for the electron injection at ITO/TN interface and it improved the photovoltaic properties of the inverted cell with an ITO/TN/active layer/MoOx/Ag structure.

Reactor vessel using metal oxide ceramic membranes

DOEpatents

Anderson, Marc A.; Zeltner, Walter A.

1992-08-11

A reaction vessel for use in photoelectrochemical reactions includes as its reactive surface a metal oxide porous ceramic membrane of a catalytic metal such as titanium. The reaction vessel includes a light source and a counter electrode. A provision for applying an electrical bias between the membrane and the counter electrode permits the Fermi levels of potential reaction to be favored so that certain reactions may be favored in the vessel. The electrical biasing is also useful for the cleaning of the catalytic membrane.

Electrocatalysis of borohydride oxidation: a review of density functional theory approach combined with experimental validation.

PubMed

Escaño, Mary Clare Sison; Arevalo, Ryan Lacdao; Gyenge, Elod; Kasai, Hideaki

2014-09-03

The electrocatalysis of borohydride oxidation is a complex, up-to-eight-electron transfer process, which is essential for development of efficient direct borohydride fuel cells. Here we review the progress achieved by density functional theory (DFT) calculations in explaining the adsorption of BH4(-) on various catalyst surfaces, with implications for electrocatalyst screening and selection. Wherever possible, we correlate the theoretical predictions with experimental findings, in order to validate the proposed models and to identify potential directions for further advancements.

Electrocatalysis of borohydride oxidation: a review of density functional theory approach combined with experimental validation

NASA Astrophysics Data System (ADS)

Sison Escaño, Mary Clare; Lacdao Arevalo, Ryan; Gyenge, Elod; Kasai, Hideaki

2014-09-01

The electrocatalysis of borohydride oxidation is a complex, up-to-eight-electron transfer process, which is essential for development of efficient direct borohydride fuel cells. Here we review the progress achieved by density functional theory (DFT) calculations in explaining the adsorption of BH4- on various catalyst surfaces, with implications for electrocatalyst screening and selection. Wherever possible, we correlate the theoretical predictions with experimental findings, in order to validate the proposed models and to identify potential directions for further advancements.

The Impact and Oxidation Survival of Selected Meteoritic Compounds: Signatures of Asteroid Organic Material on Planetary Surfaces

NASA Technical Reports Server (NTRS)

Cooper, George; Horz, Fred; Oleary, Alanna; Chang, Sherwood

2013-01-01

Polar, non-volatile organic compounds may be present on the surfaces (or near surfaces) of multiple Solar System bodies. If found, by current or future missions, it would be desirable to determine the origin(s) of such compounds, e.g., asteroidal or in situ. To test the possible survival of meteoritic compounds both during impacts with planetary surfaces and under subsequent (possibly) harsh ambient conditions, we subjected known meteoritic compounds to relatively high impact-shock pressures and/or to varying oxidizing/corrosive conditions. Tested compounds include sulfonic and phosphonic acids (S&P), polyaromatic hydrocarbons (PAHs) amino acids, keto acids, dicarboxylic acids, deoxy sugar acids, and hydroxy tricarboxylic acids (Table 1). Meteoritic sulfonic acids were found to be relatively abundant in the Murchison meteorite and to possess unusual S-33 isotope anomalies (non mass-dependent isotope fractionations). Combined with distinctive C-S and C-P bonds, the S&P are potential signatures of asteroidal organic material.

Effects of electrolyzed oxidizing water on reducing Listeria monocytogenes contamination on seafood processing surfaces.

PubMed

Liu, Chengchu; Duan, Jingyun; Su, Yi-Cheng

2006-02-15

The effects of electrolyzed oxidizing (EO) water on reducing Listeria monocytogenes contamination on seafood processing surfaces were studied. Chips (5 x 5 cm(2)) of stainless steel sheet (SS), ceramic tile (CT), and floor tile (FT) with and without crabmeat residue on the surface were inoculated with L. monocytogenes and soaked in tap or EO water for 5 min. Viable cells of L. monocytogenes were detected on all chip surfaces with or without crabmeat residue after being held at room temperature for 1 h. Soaking contaminated chips in tap water resulted in small-degree reductions of the organism (0.40-0.66 log cfu/chip on clean surfaces and 0.78-1.33 log cfu/chip on dirty surfaces). Treatments of EO water significantly (p<0.05) reduced L. monocytogenes on clean surfaces (3.73 log on SS, 4.24 log on CT, and 5.12 log on FT). Presence of crabmeat residue on chip surfaces reduced the effectiveness of EO water on inactivating Listeria cells. However, treatments of EO water also resulted in significant reductions of L. monocytogenes on dirty surfaces (2.33 log on SS and CT and 1.52 log on FT) when compared with tap water treatments. The antimicrobial activity of EO water was positively correlated with its chlorine content. High oxidation-reduction potential (ORP) of EO water also contributed significantly to its antimicrobial activity against L. monocytogenes. EO water was more effective than chlorine water on inactivating L. monocytogenes on surfaces and could be used as a chlorine alternative for sanitation purpose. Application of EO water following a thorough cleaning process could greatly reduce L. monocytogenes contamination in seafood processing environments.

Pure and Oxidized Copper Materials as Potential Antimicrobial Surfaces for Spaceflight Activities

NASA Astrophysics Data System (ADS)

Hahn, C.; Hans, M.; Hein, C.; Mancinelli, R. L.; Mücklich, F.; Wirth, R.; Rettberg, P.; Hellweg, C. E.; Moeller, R.

2017-12-01

Microbial biofilms can lead to persistent infections and degrade a variety of materials, and they are notorious for their persistence and resistance to eradication. During long-duration space missions, microbial biofilms present a danger to crew health and spacecraft integrity. The use of antimicrobial surfaces provides an alternative strategy for inhibiting microbial growth and biofilm formation to conventional cleaning procedures and the use of disinfectants. Antimicrobial surfaces contain organic or inorganic compounds, such as antimicrobial peptides or copper and silver, that inhibit microbial growth. The efficacy of wetted oxidized copper layers and pure copper surfaces as antimicrobial agents was tested by applying cultures of Escherichia coli and Staphylococcus cohnii to these metallic surfaces. Stainless steel surfaces were used as non-inhibitory control surfaces. The production of reactive oxygen species and membrane damage increased rapidly within 1 h of exposure on pure copper surfaces, but the effect on cell survival was negligible even after 2 h of exposure. However, longer exposure times of up to 4 h led to a rapid decrease in cell survival, whereby the survival of cells was additionally dependent on the exposed cell density. Finally, the release of metal ions was determined to identify a possible correlation between copper ions in suspension and cell survival. These measurements indicated a steady increase of free copper ions, which were released indirectly by cells presumably through excreted complexing agents. These data indicate that the application of antimicrobial surfaces in spaceflight facilities could improve crew health and mitigate material damage caused by microbial contamination and biofilm formation. Furthermore, the results of this study indicate that cuprous oxide layers were superior to pure copper surfaces related to the antimicrobial effect and that cell density is a significant factor that influences the time dependence of antimicrobial activity.

Mechanistic investigation of Fe(III) oxide reduction by low molecular weight organic sulfur species

NASA Astrophysics Data System (ADS)

Eitel, Eryn M.; Taillefert, Martial

2017-10-01

Low molecular weight organic sulfur species, often referred to as thiols, are known to be ubiquitous in aquatic environments and represent important chemical reductants of Fe(III) oxides. Thiols are excellent electron shuttles used during dissimilatory iron reduction, and in this capacity could indirectly affect the redox state of sediments, release adsorbed contaminants via reductive dissolution, and influence the carbon cycle through alteration of bacterial respiration processes. Interestingly, the reduction of Fe(III) oxides by thiols has not been previously investigated in environmentally relevant conditions, likely due to analytical limitations associated with the detection of thiols and their oxidized products. In this study, a novel electrochemical method was developed to simultaneously determine thiol/disulfide pair concentrations in situ during the reduction of ferrihydrite in batch reactors. First order rate laws with respect to initial thiol concentration were confirmed for Fe(III) oxyhydroxide reduction by four common thiols: cysteine, homocysteine, cysteamine, and glutathione. Zero order was determined for both Fe(III) oxyhydroxide and proton concentration at circumneutral pH. A kinetic model detailing the molecular mechanism of the reaction was optimized with proposed intermediate surface structures. Although metal oxide overall reduction rate constants were inversely proportional to the complexity of the thiol structure, the extent of metal reduction increased with structure complexity, indicating that surface complexes play a significant role in the ability of these thiols to reduce iron. Taken together, these results demonstrate the importance of considering the molecular reaction mechanism at the iron oxide surface when investigating the potential for thiols to act as electron shuttles during dissimilatory iron reduction in natural environments.

Binary Oxide p-n Heterojunction Piezoelectric Nanogenerators with an Electrochemically Deposited High p-Type Cu2O Layer.

PubMed

Baek, Seung Ki; Kwak, Sung Soo; Kim, Joo Sung; Kim, Sang Woo; Cho, Hyung Koun

2016-08-31

The high performance of ZnO-based piezoelectric nanogenerators (NGs) has been limited due to the potential screening from intrinsic electron carriers in ZnO. We have demonstrated a novel approach to greatly improve piezoelectric power generation by electrodepositing a high-quality p-type Cu2O layer between the piezoelectric semiconducting film and the metal electrode. The p-n heterojunction using only oxides suppresses the screening effect by forming an intrinsic depletion region, and thus sufficiently enhances the piezoelectric potential, compared to the pristine ZnO piezoelectric NG. Interestingly, a Sb-doped Cu2O layer has high mobility and low surface trap states. Thus, this doped layer is an attractive p-type material to significantly improve piezoelectric performance. Our results revealed that p-n junction NGs consisting of Au/ZnO/Cu2O/indium tin oxide with a Cu2O:Sb (cuprous oxide with a small amount of antimony) layer of sufficient thickness (3 μm) exhibit an extraordinarily high piezoelectric potential of 0.9 V and a maximum output current density of 3.1 μA/cm(2).

Analysis of Wear Behavior of Graphene OXIDE — Polyamide Gears for Engineering Applications

NASA Astrophysics Data System (ADS)

Rajamani, Geetha; Paulraj, Jawahar; Krishnan, Kanny

Recent advances in polymer nanocomposites open a wide range of applications in various industrial sectors. Due to their high potential properties, these materials are replacing the usage of metals for many heavier components in automobile industries. In this experimental work, the tribological performance of Graphene oxide (GO) — Polyamide is investigated against pristine polyamide by fabricating gears for the usage in engineering applications. A gear test rig was developed in-house for analysis to study the specific wear rate and temperature gradient at different conditions of load and speeds. The wear resistance of the polyamide gears with the addition of 0.03wt.% of graphene oxide is better than the pristine polyamide gears and the specific wear rate is reduced significantly. The reduced specific wear rate of these polymer nanocomposite gears is attributed to the superior properties of graphene oxide such as High specific surface area, good adhesion properties and enhanced glass transition temperatures. The GO nanocomposite gear seems to be a potential alternative against conventional gears for engineering applications. Finally, the wear mechanisms and the potential of GO-based polyamide nanocomposite gears were proposed tentatively in the development of transmission gears for engineering applications.

Biodegradation potential of chlorinated solvents in ground water at the Naval Surface Warfare Center, Louisville, Kentucky, July 1999 to February 2000

USGS Publications Warehouse

Vroblesky, Don A.; Bradley, Paul M.; Petkewich, Matthew D.; Casey, Clifton C.

2001-01-01

The U.S. Geological Survey, in cooperation with the U.S. Department of the Navy, Southern Division Naval Facilities Engineering Command, investigated the potential for biodegradation of chlorinated solvents in ground water at the Naval Surface Warfare Center (also known as the Naval Ordnance Station, or the station), Louisville, Kentucky. The subsurface down to at least 100 feet at the station is characterized, from shallowest to deepest, by overburden deposits, a shale layer, and limestone. In general, all of the strata are poorly permeable. The permeable zones of the overburden and the limestone make up the overburden aquifer and the bedrock aquifer, respectively. Observed concentrations of redox-sensitive solutes suggest that the predominant anaerobic terminal electron accepting process in the overburden aquifer can shift between iron reduction and sulfate reduction, possibly as a result of rainfall-induced oxidation events. Daughter-product concentrations and laboratory experiments indicate that a variety of mechanisms, including reductive dechlorination and cometabolic oxidation, appear to be actively

The potential for biologically catalyzed anaerobic methane oxidation on ancient Mars.

PubMed

Marlow, Jeffrey J; Larowe, Douglas E; Ehlmann, Bethany L; Amend, Jan P; Orphan, Victoria J

2014-04-01

This study examines the potential for the biologically mediated anaerobic oxidation of methane (AOM) coupled to sulfate reduction on ancient Mars. Seven distinct fluids representative of putative martian groundwater were used to calculate Gibbs energy values in the presence of dissolved methane under a range of atmospheric CO2 partial pressures. In all scenarios, AOM is exergonic, ranging from -31 to -135 kJ/mol CH4. A reaction transport model was constructed to examine how environmentally relevant parameters such as advection velocity, reactant concentrations, and biomass production rate affect the spatial and temporal dependences of AOM reaction rates. Two geologically supported models for ancient martian AOM are presented: a sulfate-rich groundwater with methane produced from serpentinization by-products, and acid-sulfate fluids with methane from basalt alteration. The simulations presented in this study indicate that AOM could have been a feasible metabolism on ancient Mars, and fossil or isotopic evidence of this metabolic pathway may persist beneath the surface and in surface exposures of eroded ancient terrains.

Two-color vibrational, femtosecond, fully resonant electronically enhanced CARS (FREE-CARS) of gas-phase nitric oxide.

PubMed

Stauffer, Hans U; Roy, Sukesh; Schmidt, Jacob B; Wrzesinski, Paul J; Gord, James R

2016-09-28

A resonantly enhanced, two-color, femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) approach is demonstrated and used to explore the nature of the frequency- and time-dependent signals produced by gas-phase nitric oxide (NO). Through careful selection of the input pulse wavelengths, this fully resonant electronically enhanced CARS (FREE-CARS) scheme allows rovibronic-state-resolved observation of time-dependent rovibrational wavepackets propagating on the vibrationally excited ground-state potential energy surface of this diatomic species. Despite the use of broadband, ultrafast time-resolved input pulses, high spectral resolution of gas-phase rovibronic transitions is observed in the FREE-CARS signal, dictated by the electronic dephasing timescales of these states. Analysis and computational simulation of the time-dependent spectra observed as a function of pump-Stokes and Stokes-probe delays provide insight into the rotationally resolved wavepacket motion observed on the excited-state and vibrationally excited ground-state potential energy surfaces of NO, respectively.

The Morning NO x maximum in the forest atmosphere boundary layer

NASA Astrophysics Data System (ADS)

Alaghmand, M.; Shepson, P. B.; Starn, T. K.; Jobson, B. T.; Wallace, H. W.; Carroll, M. A.; Bertman, S. B.; Lamb, B.; Edburg, S. L.; Zhou, X.; Apel, E.; Riemer, D.; Stevens, P.; Keutsch, F.

2011-10-01

During the 1998, 2000, 2001, 2008, and 2009 summer intensives of the Program for Research on Oxidants: PHotochemistry, Emissions and Transport (PROPHET), ambient measurement of nitrogen oxides (NO + NO2 = NOx) were conducted. NO and NOx mole fractions displayed a diurnal pattern with NOx frequently highest in early morning. This pattern has often been observed in other rural areas. In this paper, we discuss the potential sources and contributing factors of the frequently observed morning pulse of NOx. Of the possible potential contributing factors to the observed morning pulse of NO and NOx, we find that surface-layer transport and slow upward mixing from soil emissions, related to the thermodynamic stability in the nocturnal boundary layer (NBL) before its morning breakup are the largest contributors. The morning NOx peak can significantly impact boundary layer chemistry, e.g. through production of HONO on surfaces, and by increasing the importance of NO3 chemistry in the morning boundary layer.

Polypyrrole-coated samarium oxide nanobelts: fabrication, characterization, and application in supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Peng; Wang, Yunjiao; Wang, Xue; Yang, Chao; Yi, Yanfeng

2012-11-01

Polypyrrole-coated samarium oxide nanobelts were synthesized by the in situ chemical oxidative surface polymerization technique based on the self-assembly of pyrrole on the surface of the amine-functionalized Sm2O3 nanobelts. The morphologies of the polypyrrole/samarium oxide (PPy/Sm2O3) nanocomposites were characterized using transmission electron microscope. The UV-vis absorbance of these samples was also investigated, and the remarkable enhancement was clearly observed. The electrochemical behaviors of the PPy/Sm2O3 composites were investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge-discharge. The results indicated that the PPy/Sm2O3 composite electrode was fully reversible and achieved a very fast Faradaic reaction. After being corrected into the weight percentage of the PPy/Sm2O3 composite at a current density of 20 mA cm-2 in a 1.0 M NaNO3 electrolyte solution, a maximum discharge capacity of 771 F g-1 was achieved in a half-cell setup configuration for the PPy/Sm2O3 composites electrode with the potential application to electrode materials for electrochemical capacitors.

Influence of anodizing conditions on generation of internal cracks in anodic porous tin oxide films grown in NaOH electrolyte

NASA Astrophysics Data System (ADS)

Zaraska, Leszek; Gawlak, Karolina; Gurgul, Magdalena; Dziurka, Magdalena; Nowak, Marlena; Gilek, Dominika; Sulka, Grzegorz D.

2018-05-01

Nanoporous tin oxide layers were synthesized via simple one-step anodic oxidation of a low-purity Sn foil (98.8%) in sodium hydroxide electrolyte. The process of pore formation at the early stage of anodization was discussed on the basis of concepts of oxygen bubble mould effect and viscous flow of oxide. The effect of anodizing conditions on the generation of internal cracks and fractures within the anodic film was investigated in detail. It was confirmed that crack-free tin oxide films can be obtained if the anodization is carried out at the potential of 4 V independently of the electrolyte concentration. On the other hand, the porous anodic film with a totally stacked internal morphology is obtained at the potential of 5 V in 0.1 M NaOH electrolyte. The generation of internal cracks and voids can be attributed to a much lower surface porosity and local trapping of O2 inside the pores of the oxide layer. However, increasing electrolyte concentration allows for obtaining less cracked porous films due to effective and uniform liberation of oxygen bubbles from the channels through completely open pore mouths. Furthermore, it was confirmed that uniformity of the anodic tin oxide layers can be significantly improved by vigorous electrolyte stirring. Finally, we observed that the addition of ethanol to the electrolyte can reduce anodic current density and the oxide growth rate. In consequence, less cracked anodic film can be formed even at the potential of 6 V. The generation of oxygen at the pore bottoms, together with the open pore mouths were found to be critical factors responsible for the anodic formation of crack-free porous tin oxide films.

Alkali Potassium Induced HCl/CO2 Selectivity Enhancement and Chlorination Reaction Inhibition for Catalytic Oxidation of Chloroaromatics.

PubMed

Sun, Pengfei; Wang, Wanglong; Weng, Xiaole; Dai, Xiaoxia; Wu, Zhongbiao

2018-06-05

Industrial combustion of chloroaromatics is likely to generate unintentional biphenyls (PCBs), polychlorinated dibenzo- p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs). This process involves a surface-mediated reaction and can be accelerated in the presence of a catalyst. In the past decade, the effect of surface nature of applied catalysts on the conversion of chloroaromatics to PCBs/PCDD/PCDF has been well explored. However, studies on how the flue gas interferent components affect such a conversion process remain insufficient. In this article, a critical flue gas interferent component, alkali potassium, was investigated to reveal its effect on the chloroaromatics oxidation at a typical solid acid-base catalyst, Mn x Ce 1- x O 2 /HZSM-5. The loading of alkali potassium was found to improve the Lewis acidity of the catalyst (by increasing the amounts of surface Mn 4+ after calcination), which thus promoted the CO 2 selectivity for catalytic chlorobenzene (CB) oxidation. The KOH with a high hydrophilicity has favored the adsorption/activation of H 2 O molecules that provided sufficient hydroxyl groups and possibly induced a hydrolysis process to promote the formation of HCl. The K ion also served as a potential sink for chorine ions immobilization (via forming KCl). Both of these inhibited the formation of phenyl polychloride byproducts, thereby blocking the conversion of CB to chlorophenol and then PCDDs/PCDFs, and potentially ensuring a durable operation and less secondary pollution for the catalytic chloroaromatics combustion in industry.

The influence of poly(ethylene oxide) and illumination on the copper electrodeposition process onto n-Si(100).

PubMed

Muñoz, Eduardo C; Schrebler, Ricardo S; Cury, Paula K; Suarez, Claudio A; Córdova, Ricardo A; Gómez, Carlos H; Marotti, Ricardo E; Dalchiele, Enrique A

2006-10-26

In this study, we examined the influence of illumination and the presence of poly(ethylene oxide) (PEO) as an additive for the copper electrodeposition process onto n-Si(100). The study was carried out by means of cyclic voltammetry (CV) and the potential steps method, from which the corresponding nucleation and growth mechanism (NGM) were determined. Likewise, a morphologic analysis of the deposits obtained at different potential values by means of atomic force microscopy (AFM) was carried out. In a first stage, Mott-Schottky measurements so as to characterize the energetics of the semiconductor/electrolyte interface were made. Also, parallel capacity measurements were carried out in order to determine the surface state density of the substrate. It was found that when PEO concentration is increased, the number of these surface states decreases. The CV results indicated that the presence of PEO inhibits the photoelectrochemical reaction of oxide formation on the surface of the semiconductor. This allows a decrease in the overpotential associated with the electrodeposition process. The analysis of the j/t transients shows that the NGM corresponds to progressive three-dimensional (3D) diffusional controlled (PN3D(Diff)), which was confirmed by the AFM technique. Neither illumination nor the presence of PEO changes the mechanisms. Their influence is in that they diminish the size of the nuclei and the speed with which these are formed, which produces a more homogeneous electrodeposit.