In Situ X-Ray Photoelectron Spectroscopy of Model Catalysts: At the Edge of the Gap

NASA Astrophysics Data System (ADS)

Blomberg, S.; Hoffmann, M. J.; Gustafson, J.; Martin, N. M.; Fernandes, V. R.; Borg, A.; Liu, Z.; Chang, R.; Matera, S.; Reuter, K.; Lundgren, E.

2013-03-01

We present high-pressure x-ray photoelectron spectroscopy (HP-XPS) and first-principles kinetic Monte Carlo study addressing the nature of the active surface in CO oxidation over Pd(100). Simultaneously measuring the chemical composition at the surface and in the near-surface gas phase, we reveal both O-covered pristine Pd(100) and a surface oxide as stable, highly active phases in the near-ambient regime accessible to HP-XPS. Surprisingly, no adsorbed CO can be detected during high CO2 production rates, which can be explained by a combination of a remarkably short residence time of the CO molecule on the surface and mass-transfer limitations in the present setup.

A recyclable Au(I) catalyst for selective homocoupling of arylboronic acids: significant enhancement of nano-surface binding for stability and catalytic activity.

PubMed

Zhang, Xin; Zhao, Haitao; Wang, Jianhui

2010-08-01

Au nanoparticles stabilized by polystyrene-co-polymethacrylic acid microspheres (PS-co-PMAA) were prepared and characterized via X-ray diffraction (XRD), and transmission electron microscope (TEM). The Au nanoparticles supported on the microspheres showed highly selective catalytic activity for homo-coupling reactions of arylboronic acids in a system of aryl-halides and arylboronic acids. X-ray photoelectron spectroscopy (XPS) spectra of the catalyst shows large amounts of Au(I) complexes band to the surface of the Au nanoparticles, which contributes to the selective homocoupling of the arylboronic acids. More importantly, this supported Au complex is a highly recyclable catalyst. The supported Au catalyst can be recycled and reused at least 6 times for a phenylboronic acid reactant, whereas the parent complex shows very low catalytic activity for this compound. The high catalytic activity of this material is attributed to: (1) the high surface to volume ratio which leads to more active sites being exposed to reactants; (2) the strong surface binding of the Au nanoparticle to the Au(I) complexes, which enhances both the stability and the catalytic activity of these complexes.

Adaptation of an Antarctic lichen to Martian niche conditions can occur within 34 days

NASA Astrophysics Data System (ADS)

de Vera, Jean-Pierre; Schulze-Makuch, Dirk; Khan, Afshin; Lorek, Andreas; Koncz, Alexander; Möhlmann, Diedrich; Spohn, Tilman

2014-08-01

Stresses occurring on the Martian surface were simulated in a Mars Simulation Chamber (MSC) and included high UV fluxes (Zarnecki and Catling, 2002), low temperatures, low water activity, high atmospheric CO2 concentrations, and an atmospheric pressure of about 800 Pa (Kasting, 1991; Head et al., 2003). The lichen Pleopsidium chlorophanum is an extremophile that lives in very cold, dry, high-altitude habitats, which are Earth's best approximation of the Martian surface. Samples with P. chlorophanum were exposed uninterruptedly to simulated conditions of the unprotected Martian surface (i.e. 6344 kJ m-2) and protected niche conditions (269 kJ m-2) for 34 days. Under unprotected Martian surface conditions the fungal symbiont decreases its metabolic activity and it was unclear if the algal symbiont of the lichen was still actively photosynthesizing. However, under "protected site" conditions, the entire lichen not only survived and remained photosynthetically active, it even adapted physiologically by increasing its photosynthetic activity over 34 days.

Surface oxidation of GaN(0001): Nitrogen plasma-assisted cleaning for ultrahigh vacuum applications

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

Gangopadhyay, Subhashis; Schmidt, Thomas, E-mail: tschmidt@ifp.uni-bremen.de; Kruse, Carsten

The cleaning of metal-organic vapor-phase epitaxial GaN(0001) template layers grown on sapphire has been investigated. Different procedures, performed under ultrahigh vacuum conditions, including degassing and exposure to active nitrogen from a radio frequency nitrogen plasma source have been compared. For this purpose, x-ray photoelectron spectroscopy, reflection high-energy electron diffraction, and scanning tunneling microscopy have been employed in order to assess chemical as well as structural and morphological surface properties. Initial degassing at 600 °C under ultrahigh vacuum conditions only partially eliminates the surface contaminants. In contrast to plasma assisted nitrogen cleaning at temperatures as low as 300 °C, active-nitrogen exposure at temperaturesmore » as high as 700 °C removes the majority of oxide species from the surface. However, extended high-temperature active-nitrogen cleaning leads to severe surface roughening. Optimum results regarding both the removal of surface oxides as well as the surface structural and morphological quality have been achieved for a combination of initial low-temperature plasma-assisted cleaning, followed by a rapid nitrogen plasma-assisted cleaning at high temperature.« less

Laboratory Activity Worksheet to Train High Order Thinking Skill of Student on Surface Chemistry Lecture

NASA Astrophysics Data System (ADS)

Yonata, B.; Nasrudin, H.

2018-01-01

A worksheet has to be a set with activity which is help students to arrange their own experiments. For this reason, this research is focused on how to train students’ higher order thinking skills in laboratory activity by developing laboratory activity worksheet on surface chemistry lecture. To ensure that the laboratory activity worksheet already contains aspects of the higher order thinking skill, it requires theoretical and empirical validation. From the data analysis results, it shows that the developed worksheet worth to use. The worksheet is worthy of theoretical and empirical feasibility. This conclusion is based on the findings: 1) Assessment from the validators about the theoretical feasibility aspects in the category is very feasible with an assessment range of 95.24% to 97.92%. 2) students’ higher thinking skill from N Gain values ranges from 0.50 (enough) to 1.00 (high) so it can be concluded that the laboratory activity worksheet on surface chemistry lecture is empirical in terms of worth. The empirical feasibility is supported by the responses of the students in very reasonable categories. It is expected that the laboratory activity worksheet on surface chemistry lecture can train students’ high order thinking skills for students who program surface chemistry lecture.

Geothermic analysis of high temperature hydrothermal activities area in Western plateau of Sichuan province, China

NASA Astrophysics Data System (ADS)

Zhang, J.

2016-12-01

There is a high temperature hydrothermal activity area in the western plateau of Sichuan. More than 200 hot springs points have been found in the region, including 11 hot spring water temperature above local boiling point. Most of these distribute along Jinshajjiang fracture, Dege-Xiangcheng fracture, Ganzi-Litang fracture as well as Xianshuihe fracture, and form three high-temperature hydrothermal activity strips in the NW-SE direction. Using gravity, magnetic, seismic and helium isotope data, this paper analyzed the crust-mantle heat flow structure, crustal heat source distribution and water heating system. The results show that the geothermal activity mainly controlled by the "hot" crust. The ratio of crustal heat flow and surface heat flow is higher than 60%. In the high temperature hydrothermal activities area, there is lower S wave velocity zone with Vs<3.2 km/s in 15 30 km depth in middle and lower crust. Basing on the S wave velocity inversion temperature of crust-mantle, it has been found that there is a high temperature layer with 850 1000 ° in 20 40 km depth. It is the main heat source of high temperature hydrothermal activity area of western Sichuan. Our argument is that atmospheric precipitation, surface water infiltrated along the fault fracture into the crustal deep, heating by crustal hot source, and circulation to surface become high temperature hot water. Geothermal water mainly reserve in the Triassic strata of the containing water good carbonate rocks, and in the intrusive granite which is along the fault zone. The thermal energy of Surface heat thermal activities mainly comes from the high-temperature hot source which is located in the middle and lower crust. Being in the deep crustal fracture, the groundwater infiltrated to the deep crust and absorbed heat, then, quickly got back to the surface and formed high hot springs.

A facile reflux procedure to increase active surface sites form highly active and durable supported palladium@platinum bimetallic nanodendrites

NASA Astrophysics Data System (ADS)

Wang, Qin; Li, Yingjun; Liu, Baocang; Xu, Guangran; Zhang, Geng; Zhao, Qi; Zhang, Jun

2015-11-01

A series of well-dispersed bimetallic Pd@Pt nanodendrites uniformly supported on XC-72 carbon black are fabricated by using different capping agents. These capping agents are essential for the branched morphology control. However, the surfactant adsorbed on the nanodendrites surface blocks the access of reactant molecules to the active surface sites, and the catalytic activities of these bimetallic nanodendrites are significantly restricted. Herein, a facile reflux procedure to effectively remove the capping agent molecules without significantly affecting their sizes is reported for activating supported nanocatalysts. More significantly, the structure and morphology of the nanodendrites can also be retained, enhancing the numbers of active surface sites, catalytic activity and stability toward methanol and ethanol electro-oxidation reactions. The as-obtained hot water reflux-treated Pd@Pt/C catalyst manifests superior catalytic activity and stability both in terms of surface and mass specific activities, as compared to the untreated catalysts and the commercial Pt/C and Pd/C catalysts. We anticipate that this effective and facile removal method has more general applicability to highly active nanocatalysts prepared with various surfactants, and should lead to improvements in environmental protection and energy production.

Activated carbon derived from waste coffee grounds for stable methane storage.

PubMed

Kemp, K Christian; Baek, Seung Bin; Lee, Wang-Geun; Meyyappan, M; Kim, Kwang S

2015-09-25

An activated carbon material derived from waste coffee grounds is shown to be an effective and stable medium for methane storage. The sample activated at 900 °C displays a surface area of 1040.3 m(2) g(-1) and a micropore volume of 0.574 cm(3) g(-1) and exhibits a stable CH4 adsorption capacity of ∼4.2 mmol g(-1) at 3.0 MPa and a temperature range of 298 ± 10 K. The same material exhibits an impressive hydrogen storage capacity of 1.75 wt% as well at 77 K and 100 kPa. Here, we also propose a mechanism for the formation of activated carbon from spent coffee grounds. At low temperatures, the material has two distinct types with low and high surface areas; however, activation at elevated temperatures drives off the low surface area carbon, leaving behind the porous high surface area activated carbon.

Activated carbon derived from waste coffee grounds for stable methane storage

NASA Astrophysics Data System (ADS)

Kemp, K. Christian; Baek, Seung Bin; Lee, Wang-Geun; Meyyappan, M.; Kim, Kwang S.

2015-09-01

An activated carbon material derived from waste coffee grounds is shown to be an effective and stable medium for methane storage. The sample activated at 900 °C displays a surface area of 1040.3 m2 g-1 and a micropore volume of 0.574 cm3 g-1 and exhibits a stable CH4 adsorption capacity of ˜4.2 mmol g-1 at 3.0 MPa and a temperature range of 298 ± 10 K. The same material exhibits an impressive hydrogen storage capacity of 1.75 wt% as well at 77 K and 100 kPa. Here, we also propose a mechanism for the formation of activated carbon from spent coffee grounds. At low temperatures, the material has two distinct types with low and high surface areas; however, activation at elevated temperatures drives off the low surface area carbon, leaving behind the porous high surface area activated carbon.

Dynamic pesticide removal with activated carbon fibers.

PubMed

Martín-Gullón, I; Font, R

2001-02-01

Rapid small-scale minicolumn tests were carried out to simulate the atrazine adsorption in water phase with three pelletized pitch-based activated carbon fibers (ACF) and one commercial granular activated carbon (GAC). Initial atrazine solutions were prepared with pretreated ground water. Minicolumn tests showed that the performance of highly activated carbon fibers (surface area of 1700 m2/g) is around 7 times better than the commercial GAC (with surface area at around 1100 m2/g), whereas carbon fibers with medium activation degree (surface area of 1500 m2/g) had a removal efficiency worse than the commercial carbon. The high removal efficiency of the highly activated ACF is due to the wide-opened microstructure of the material, with an appreciable contribution of the low size mesopores, maintaining at these conditions a fast kinetic adsorption rate rather than a selective adsorbent for micropollutants vs. natural organic matter.

Selection of pecan shell-based activated carbons for removal of organic and inorganic impurities from water.

PubMed

Niandou, Mohamed A S; Novak, Jeffrey M; Bansode, Rishipal R; Yu, Jianmei; Rehrah, Djaafar; Ahmedna, Mohamed

2013-01-01

Activated carbons are a byproduct from pyrolysis and have value as a purifying agent. The effectiveness of activated carbons is dependent on feedstock selection and pyrolysis conditions that modify their surface properties. Therefore, pecan shell-based activated carbons (PSACs) were prepared by soaking shells in 50% (v/v) HPO or 25 to 50% of KOH-NaHCO followed by pyrolysis at 400 to 700°C under a N atmosphere. Physically activated PSACs were produced by pyrolysis at 700°C under N followed by activation with steam or CO at 700 to 900°C. Physicochemical, surface, and adsorption properties of the PSACs were compared with two commercially available activated carbons. The average mass yield of PSACs with respect to the initial mass of the biomass was about 20 and 34% for physically activated and chemically activated carbons, respectively. Acid-activated carbons exhibited higher surface area, higher bulk density, and lower ash content compared with steam- or CO-activated carbons and the two commercial products. Base activation led to the development of biochar with moderate to high surface area with surface charges suitable for adsorption of anionic species. Regardless of the activation method, PSACs had high total surface area ranging from 400 to 1000 m g, better pore size distribution, and more surface charges than commercial samples. Our results also showed that PSACs were effective in removing inorganic contaminants such as Cu and NO as well as organic contaminants such as atrazine and metolachlor. This study showed that pyrolysis conditions and activation had a large influence on the PSAC's surface characteristics, which can limit its effectiveness as a custom sorbent for targeted water contaminants. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Mass-produced multi-walled carbon nanotubes as catalyst supports for direct methanol fuel cells.

PubMed

Jang, In Young; Park, Ki Chul; Jung, Yong Chae; Lee, Sun Hyung; Song, Sung Moo; Muramatsu, Hiroyuki; Kim, Yong Jung; Endo, Morinobu

2011-01-01

Commercially mass-produced multi-walled carbon nanotubes, i.e., VGNF (Showa Denko Co.), were applied to support materials for platinum-ruthenium (PtRu) nanoparticles as anode catalysts for direct methanol fuel cells. The original VGNFs are composed of high-crystalline graphitic shells, which hinder the favorable surface deposition of the PtRu nanoparticles that are formed via borohydride reduction. The chemical treatment of VGNFs with potassium hydroxide (KOH), however, enables highly dispersed and dense deposition of PtRu nanoparticles on the VGNF surface. This capability becomes more remarkable depending on the KOH amount. The electrochemical evaluation of the PtRu-deposited VGNF catalysts showed enhanced active surface areas and methanol oxidation, due to the high dispersion and dense deposition of the PtRu nanoparticles. The improvement of the surface deposition states of the PtRu nanoparticles was significantly due to the high surface area and mesorporous surface structure of the KOH-activated VGNFs.

Micropore-free surface-activated carbon for the analysis of polychlorinated dibenzo-p-dioxins-dibenzofurans and non-ortho-substituted polychlorinated biphenyls in environmental samples.

PubMed

Kemmochi, Yukio; Tsutsumi, Kaori; Arikawa, Akihiro; Nakazawa, Hiroyuki

2002-11-22

2,3,7,8-Substituted polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/Fs) and non-ortho-substituted polychlorinated biphenyls (PCBs) account for almost all of the total toxic equivalents (TEQ) in environmental samples. Activated carbon columns are used to fractionate the samples for GC-MS analysis or bioassay. Micropore-free surface-activated carbon is highly selective for PCDD/Fs and non-ortho-PCBs and can improve the conventional activated carbon column clean-up. Along with sulfuric acid-coated diatomaceous earth columns, micropore-free surface-activated carbon provides a rapid, robust, and high-throughput sample preparation method for PCDD/Fs and non-ortho-PCBs analysis.

Characterization of surface active materials derived from farm products

USDA-ARS?s Scientific Manuscript database

Surface active materials obtained by chemical modification of plant protein isolates (lupin, barley, oat), corn starches (dextrin, normal, high amylose, and waxy) and soybean oil (soybean oil based polysoaps, SOPS) were investigated for their surface and interfacial properties using axisymmetric dro...

Factors affecting the behavior of unburned carbon upon steam activation

NASA Astrophysics Data System (ADS)

Lu, Zhe

The main objective of this study is to investigate the factors that could affect the behavior of unburned carbon samples upon steam activation. Through this work, the relationships among the factors that could influence the carbon-steam reaction with the surface area of the produced activated carbon were explored. Statistical analysis was used to relate the chemical and physical properties of the unburned carbon to the surface area of the activated carbon. Six unburned carbons were selected as feedstocks for activated carbon, and marked as UCA through UCF. The unburned carbons were activated using steam at 850°C for 90 minutes, and the surface areas of their activated counterparts were measured using N2 adsorption isotherms at 77K. The activated carbons produced from different unburned carbon precursors presented different surface areas at similar carbon burn-off levels. Moreover, in different carbon burn-off regions, the sequences for surface area of activated carbons from different unburned carbon samples were different. The factors that may affect the carbon-steam gasification reactions, including the concentration of carbon active sites, the crystallite size of the carbon, the intrinsic porous structure of carbon, and the inorganic impurities, were investigated. All unburned carbons investigated in this study were similar in that they showed the very broad (002) and (10 ) carbon peaks, which are characteristic of highly disordered carbonaceous materials. In this study, the unburned carbon samples contained about 17--48% of inorganic impurities. Compared to coals, the unburned carbon samples contain a larger amount of inorganic impurities as a result of the burn-off, or at lease part, of the carbon during the combustion process. These inorganic particles were divided into two groups in terms of the way they are associated with carbon particles: free single particles, and particles combined with carbon particles. As indicated from the present work, unburned carbons with one of the following properties will produce activated carbons with high surface areas. These properties include: (a) large amount of O2 chemisorption capacity; (b) high concentration of surface C-O complex; and (c) small crystallite diameter; (d) high concentration of Na+K particles that are combined with carbon; (e) high concentration of isotropic carbon. (Abstract shortened by UMI.)

Electrospinning Fabrication of SrTiO3 Nanofibers and Their Photocatalytic Activity

NASA Astrophysics Data System (ADS)

Xu, Lei; Zhao, Yiping; Wang, Wei; Liu, Hao; Wang, Rui

2018-06-01

SrTiO3 nanofibers were fabricated by an electrospinning process. The phase, microstructure and photocatalytic activity of the obtained SrTiO3 nanofibers were investigated. The XRD patterns and the SEM images suggest that SrTiO3 nanofibers with perovskite phase and rough surface have been fabricated in the current work. The SrTiO3 nanofibers show a high efficiency decomposition of RhB under ultraviolet light irradiation. The high photocatalytic activity of SrTiO3 nanofibers results from the large specific surface area. The large specific surface area provides more surface active sits and makes an easier charge carrier transport. On the basis of the photocatalytic performance of SrTiO3 nanofibers, the possible photocatalysis mechanism was proposed.

Innate resistance to sporicides and potential failure to decontaminate.

PubMed

Maillard, J-Y

2011-03-01

Bacterial spores are frequently intrinsically resistant to biocides and only a number of alkylating and oxidising biocides are sporicidal under certain conditions. Activity against spores is affected by several key factors such as concentration, exposure time, soiling, and the types of surface to be treated. Sporicidal efficacy is usually achieved after an exposure time of several minutes with a high concentration of a biocide. Failure to understand these factors will result in decreased sporicide activity and spore survival. Sporicides in healthcare settings are used for surface disinfection and for the high level disinfection of certain medical devices (e.g. endoscopes). With efficacy data in mind, sporicidal activity should be achieved for the disinfection of medical devices where both high concentration and long exposure time occur. However, for the disinfection of environmental surfaces, high concentration is not recommended, nor is long exposure time achievable. In this case, sporicidal activity is severely reduced and spore survival following treatment is to be expected and contributes to the explanation of spore persistence on surfaces. Copyright © 2010 The Hospital Infection Society. Published by Elsevier Ltd. All rights reserved.

[Adsorption behavior and influence factors of p-nitroaniline on high surface area activated carbons prepared from plant stems].

PubMed

Li, Kun-quan; Zheng, Zheng; Luo, Xing-zhang

2010-08-01

Low-cost and high surface area microporous activated carbons were prepared from Spartina alternilora and cotton stalk with KOH activation under the conditions of impregnation ratio of 3.0, activation temperature at 800 degrees C and activation time of 1.5 h. The adsorption behavior of p-nitroaniline on the activated carbons was investigated by batch sorption experiments. The influences of solution pH value, adsorbent dose and temperature were investigated. The adsorption isotherm and thermodynamic characteristics were also discussed. The Spartina alterniflora activated carbon (SA-AC) has a high surface area of 2825 m2 x g(-1) and a micropore volume of 1.192 cm3 x g(-1). The BET surface area and micropore volume of the cotton stalk activated carbon (CS-AC) are 2135 m2 x g(-1) and 1.011 cm3 x g(-1), respectively. The sorption experiments show that both the activated carbons have high sorption capacity for p-nitroaniline. The Langmuir maximum sorption amount was found to be 719 mg x g(-1) for SA-AC and 716 mg x g(-1) for CS-AC, respectively. The sorption was found to depend on solution pH, adsorbent dose, and temperature. The optimum pH for the removal of p-nitroaniline was found to be 7.0. The Freundlich model and Redlich-Peterson model can describe the experimental data effectively. The negative changes in free energy (delta G0) and enthalpy (delta H0) indicate that the sorption is a spontaneous and exothermic procedure. The negative values of the adsorption entropy delta S0 indicate that the mobility of p-nitroaniline on the carbon surface becomes more restricted as compared with that of those in solution.

Preparation of activated carbon from cherry stones by chemical activation with ZnCl 2

NASA Astrophysics Data System (ADS)

Olivares-Marín, M.; Fernández-González, C.; Macías-García, A.; Gómez-Serrano, V.

2006-06-01

Cherry stones (CS), an industrial product generated abundantly in the Valle del Jerte (Cáceres province, Spain), were used as precursor in the preparation of activated carbon by chemical activation with ZnCl 2. The influence of process variables such as the carbonisation temperature and the ZnCl 2:CS ratio (impregnation ratio) on textural and chemical-surface properties of the products obtained was studied. Such products were characterised texturally by adsorption of N 2 at -196 °C, mercury porosimetry and density measurements. Information on the surface functional groups and structures of the carbons was provided by FT-IR spectroscopy. Activated carbon with a high development of surface area and porosity is prepared. When using the 4:1 impregnation ratio, the specific surface area (BET) of the resultant carbon is as high as 1971 m 2 g -1. The effect of the increase in the impregnation ratio on the porous structure of activated carbon is stronger than that of the rise in the carbonisation temperature, whereas the opposite applies to the effect on the surface functional groups and structures.

Highly porous activated carbons from resource-recovered Leucaena leucocephala wood as capacitive deionization electrodes.

PubMed

Hou, Chia-Hung; Liu, Nei-Ling; Hsi, Hsing-Cheng

2015-12-01

Highly porous activated carbons were resource-recovered from Leucaena leucocephala (Lam.) de Wit. wood through combined chemical and physical activation (i.e., KOH etching followed by CO2 activation). This invasive species, which has severely damaged the ecological economics of Taiwan, was used as the precursor for producing high-quality carbonaceous electrodes for capacitive deionization (CDI). Carbonization and activation conditions strongly influenced the structure of chars and activated carbons. The total surface area and pore volume of activated carbons increased with increasing KOH/char ratio and activation time. Overgasification induced a substantial amount of mesopores in the activated carbons. In addition, the electrochemical properties and CDI electrosorptive performance of the activated carbons were evaluated; cyclic voltammetry and galvanostatic charge/discharge measurements revealed a typical capacitive behavior and electrical double layer formation, confirming ion electrosorption in the porous structure. The activated-carbon electrode, which possessed high surface area and both mesopores and micropores, exhibited improved capacitor characteristics and high electrosorptive performance. Highly porous activated carbons derived from waste L. leucocephala were demonstrated to be suitable CDI electrode materials. Copyright © 2015 Elsevier Ltd. All rights reserved.

pH-Induced interfacial properties of Chaplin E from Streptomyces coelicolor.

PubMed

Dokouhaki, Mina; Hung, Andrew; Prime, Emma L; Qiao, Greg G; Day, Li; Gras, Sally L

2017-12-01

Chaplin E, or Chp E, is a surface active peptide secreted by Streptomyces coelicolor that adopts different structures depending on solution pH but the effect of these structures on the interfacial properties of Chp E is not known. In experiments paired with simulations, Chp E was found to display pH-dependent interfacial assembly and surface activity. At pH 3.0, Chp E formed an ordered non-amyloidal interfacial film with high surface activity; while at pH 10.0, Chp E self-assembled into a heterogeneous film containing randomly arranged fibrils at the interface that was less surface active compared to the film formed at pH 3.0. In simulations at pH 10.0, Chp E molecules showed a higher propensity for dimerization within the solution phase, lower rate of adsorption to the interface and tighter inter-molecular associations at the interface, consistent with the lower surface activity and smaller interfacial area coverage per molecule measured at this pH compared to at pH 3.0. A model is presented for the role of Chp E in the developmental differentiation of Streptomyces coelicolor, where Chp E contributes to changes in surface tension at low pH and the formation of fibrils on the surface of aerial hyphae at high pH. Our data also suggest Chp E could be a promising surface active agent with functional activity that can be controlled by pH. Copyright © 2017 Elsevier B.V. All rights reserved.

Structure Design and Performance Tuning of Nanomaterials for Electrochemical Energy Conversion and Storage.

PubMed

Sheng, Tian; Xu, Yue-Feng; Jiang, Yan-Xia; Huang, Ling; Tian, Na; Zhou, Zhi-You; Broadwell, Ian; Sun, Shi-Gang

2016-11-15

The performance of nanomaterials in electrochemical energy conversion (fuel cells) and storage (secondary batteries) strongly depends on the nature of their surfaces. Designing the structure of electrode materials is the key approach to achieving better performance. Metal or metal oxide nanocrystals (NCs) with high-energy surfaces and open surface structures have attained significant attention in the past decade since such features possess intrinsically exceptional properties. However, they are thermodynamically metastable, resulting in a huge challenge in their shape-controlled synthesis. The tuning of material structure, design, and performance on the nanoscale for electrochemical energy conversion and storage has attracted extended attention over the past few years. In this Account, recent progress made in shape-controlled synthesis of nanomaterials with high-energy surfaces and open surface structures using both electrochemical methods and surfactant-based wet chemical route are reviewed. In fuel cells, the most important catalytic materials are Pt and Pd and their NCs with high-energy surfaces of convex or concave morphology. These exhibit remarkable activity toward electrooxidation of small organic molecules, such as formic acid, methanol, and ethanol and so on. In practical applications, the successful synthesis of Pt NCs with high-energy surfaces of small sizes (sub-10 nm) realized a superior high mass activity. The electrocatalytic performances have been further boosted by synergetic effects in bimetallic systems, either through surface decoration using foreign metal atoms or by alloying in which the high-index facet structure is preserved and the electronic structure of the NCs is altered. The intrinsic relationship of high electrocatalytic performance dependent on open structure and high-energy surface is also valid for (metal) oxide nanomaterials used in Li ion batteries (LIB). It is essential for the anode nanomaterials to have optimized structures to keep them more stable during the charge/discharge processes for reducing damaging volume expansion via intercalation and subsequent reduced battery lifetime. In the case of cathodes, tuning the surface structure of nanomaterials should be one of the most beneficial strategies to enhance the capacity and rate performance. In addition, metal oxides with unique defective structure of high catalytic activity and carbon materials of porous structure for facilitating fast Li + diffusion paths and efficiently trapping polysulfide are most important approached and employed in Li-O 2 battery and Li-S battery, respectively. In summary, significant progress has already been made in the electrocatalytic field, and likely emerging techniques based on NCs enclosed with high-energy surfaces and high-index facets could provide a promising platform to investigate the surface structure-catalytic functionality at nanoscale, thus shedding light on the rational design of practical catalysts with high activity, selectivity, and durability for energy conversion and storage.

Passivation of phosphorus diffused silicon surfaces with Al{sub 2}O{sub 3}: Influence of surface doping concentration and thermal activation treatments

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

Richter, Armin, E-mail: armin.richter@ise.fraunhofer.de; Benick, Jan; Kimmerle, Achim

2014-12-28

Thin layers of Al{sub 2}O{sub 3} are well known for the excellent passivation of p-type c-Si surfaces including highly doped p{sup +} emitters, due to a high density of fixed negative charges. Recent results indicate that Al{sub 2}O{sub 3} can also provide a good passivation of certain phosphorus-diffused n{sup +} c-Si surfaces. In this work, we studied the recombination at Al{sub 2}O{sub 3} passivated n{sup +} surfaces theoretically with device simulations and experimentally for Al{sub 2}O{sub 3} deposited with atomic layer deposition. The simulation results indicate that there is a certain surface doping concentration, where the recombination is maximal duemore » to depletion or weak inversion of the charge carriers at the c-Si/Al{sub 2}O{sub 3} interface. This pronounced maximum was also observed experimentally for n{sup +} surfaces passivated either with Al{sub 2}O{sub 3} single layers or stacks of Al{sub 2}O{sub 3} capped by SiN{sub x}, when activated with a low temperature anneal (425 °C). In contrast, for Al{sub 2}O{sub 3}/SiN{sub x} stacks activated with a short high-temperature firing process (800 °C) a significant lower surface recombination was observed for most n{sup +} diffusion profiles without such a pronounced maximum. Based on experimentally determined interface properties and simulation results, we attribute this superior passivation quality after firing to a better chemical surface passivation, quantified by a lower interface defect density, in combination with a lower density of negative fixed charges. These experimental results reveal that Al{sub 2}O{sub 3}/SiN{sub x} stacks can provide not only excellent passivation on p{sup +} surfaces but also on n{sup +} surfaces for a wide range of surface doping concentrations when activated with short high-temperature treatments.« less

Aloe vera Derived Activated High-Surface-Area Carbon for Flexible and High-Energy Supercapacitors.

PubMed

Karnan, M; Subramani, K; Sudhan, N; Ilayaraja, N; Sathish, M

2016-12-28

Materials which possess high specific capacitance in device configuration with low cost are essential for viable application in supercapacitors. Herein, a flexible high-energy supercapacitor device was fabricated using porous activated high-surface-area carbon derived from aloe leaf (Aloe vera) as a precursor. The A. vera derived activated carbon showed mesoporous nature with high specific surface area of ∼1890 m 2 /g. A high specific capacitance of 410 and 306 F/g was achieved in three-electrode and symmetric two-electrode system configurations in aqueous electrolyte, respectively. The fabricated all-solid-state device showed a high specific capacitance of 244 F/g with an energy density of 8.6 Wh/kg. In an ionic liquid electrolyte, the fabricated device showed a high specific capacitance of 126 F/g and a wide potential window up to 3 V, which results in a high energy density of 40 Wh/kg. Furthermore, it was observed that the activation temperature has significant role in the electrochemical performance, as the activated sample at 700 °C showed best activity than the samples activated at 600 and 800 °C. The electron microscopic images (FE-SEM and HR-TEM) confirmed the formation of pores by the chemical activation. A fabricated supercapacitor device in ionic liquid with 3 V could power up a red LED for 30 min upon charging for 20s. Also, it is shown that the operation voltage and capacitance of flexible all-solid-state symmetric supercapacitors fabricated using aloe-derived activated carbon could be easily tuned by series and parallel combinations. The performance of fabricated supercapacitor devices using A. vera derived activated carbon in all-solid-state and ionic liquid indicates their viable applications in flexible devices and energy storage.

Platelet Surface-Associated Activation and Secretion-Mediated Inhibition of Coagulation Factor XII

PubMed Central

Zakharova, Natalia V.; Artemenko, Elena O.; Podoplelova, Nadezhda A.; Sveshnikova, Anastasia N.; Demina, Irina A.; Ataullakhanov, Fazly I.; Panteleev, Mikhail A.

2015-01-01

Coagulation factor XII (fXII) is important for arterial thrombosis, but its physiological activation mechanisms are unclear. In this study, we elucidated the role of platelets and platelet-derived material in fXII activation. FXII activation was only observed upon potent platelet stimulation (with thrombin, collagen-related peptide, or calcium ionophore, but not ADP) accompanied by phosphatidylserine exposure and was localised to the platelet surface. Platelets from three patients with grey platelet syndrome did not activate fXII, which suggests that platelet-associated fXII-activating material might be released from α-granules. FXII was preferentially bound by phosphotidylserine-positive platelets and annexin V abrogated platelet-dependent fXII activation; however, artificial phosphotidylserine/phosphatidylcholine microvesicles did not support fXII activation under the conditions herein. Confocal microscopy using DAPI as a poly-phosphate marker did not reveal poly-phosphates associated with an activated platelet surface. Experimental data for fXII activation indicates an auto-inhibition mechanism (k i/k a = 180 molecules/platelet). Unlike surface-associated fXII activation, platelet secretion inhibited activated fXII (fXIIa), particularly due to a released C1-inhibitor. Platelet surface-associated fXIIa formation triggered contact pathway-dependent clotting in recalcified plasma. Computer modelling suggests that fXIIa inactivation was greatly decreased in thrombi under high blood flow due to inhibitor washout. Combined, the surface-associated fXII activation and its inhibition in solution herein may be regarded as a flow-sensitive regulator that can shift the balance between surface-associated clotting and plasma-dependent inhibition, which may explain the role of fXII at high shear and why fXII is important for thrombosis but negligible in haemostasis. PMID:25688860

Predicting Catalytic Activity of Nanoparticles by a DFT-Aided Machine-Learning Algorithm.

PubMed

Jinnouchi, Ryosuke; Asahi, Ryoji

2017-09-07

Catalytic activities are often dominated by a few specific surface sites, and designing active sites is the key to realize high-performance heterogeneous catalysts. The great triumphs of modern surface science lead to reproduce catalytic reaction rates by modeling the arrangement of surface atoms with well-defined single-crystal surfaces. However, this method has limitations in the case for highly inhomogeneous atomic configurations such as on alloy nanoparticles with atomic-scale defects, where the arrangement cannot be decomposed into single crystals. Here, we propose a universal machine-learning scheme using a local similarity kernel, which allows interrogation of catalytic activities based on local atomic configurations. We then apply it to direct NO decomposition on RhAu alloy nanoparticles. The proposed method can efficiently predict energetics of catalytic reactions on nanoparticles using DFT data on single crystals, and its combination with kinetic analysis can provide detailed information on structures of active sites and size- and composition-dependent catalytic activities.

MO-Co@N-Doped Carbon (M = Zn or Co): Vital Roles of Inactive Zn and Highly Efficient Activity toward Oxygen Reduction/Evolution Reactions for Rechargeable Zn-Air Battery

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

Chen, Biaohua; He, Xiaobo; Yin, Fengxiang

A highly efficient bifunctional oxygen catalyst is required for practical applications of fuel cells and metal-air batteries, as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are their core electrode reactions. Here, the MO-Co@ N-doped carbon (NC, M = Zn or Co) is developed as a highly active ORR/OER bifunctional catalyst via pyrolysis of a bimetal metal-organic framework containing Zn and Co, i.e., precursor (CoZn). The vital roles of inactive Zn in developing highly active bifunctional oxygen catalysts are unraveled. When the precursors include Zn, the surface contents of pyridinic N for ORR and the surface contents of Co-N-xmore » and Co3+/Co2+ ratios for OER are enhanced, while the high specific surface areas, high porosity, and high electrochemical active surface areas are also achieved. Furthermore, the synergistic effects between Zn-based and Co-based species can promote the well growth of multiwalled carbon nanotubes (MWCNTs) at high pyrolysis temperatures (>= 700 degrees C), which is favorable for charge transfer. The optimized CoZn-NC-700 shows the highly bifunctional ORR/OER activity and the excellent durability during the ORR/OER processes, even better than 20 wt% Pt/C (for ORR) and IrO2 (for OER). CoZn-NC-700 also exhibits the prominent Zn-air battery performance and even outperforms the mixture of 20 wt% Pt/C and IrO2.« less

Physiochemical Control of Composition and Location for Fundamental Studies of Biofouling Resistant, High Fouling Release Surfaces

DTIC Science & Technology

2016-06-22

with increased legislation on toxicity requirements, the research community has been actively exploring and developing new, robust, and...with a brominated end functionality. The presence of active radical species only at locations where light interacts with the catalyst affords...i.e., the burying of the reactive bromo chain ends due to the high surface activity of the fluorinated repeat units, which imposes additional steric

Atmospheric-pressure plasma activation and surface characterization on polyethylene membrane separator

NASA Astrophysics Data System (ADS)

Tseng, Yu-Chien; Li, Hsiao-Ling; Huang, Chun

2017-01-01

The surface hydrophilic activation of a polyethylene membrane separator was achieved using an atmospheric-pressure plasma jet. The surface of the atmospheric-pressure-plasma-treated membrane separator was found to be highly hydrophilic realized by adjusting the plasma power input. The variations in membrane separator chemical structure were confirmed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Chemical analysis showed newly formed carbonyl-containing groups and high surface concentrations of oxygen-containing species on the atmospheric-pressure-plasma-treated polymeric separator surface. It also showed that surface hydrophilicity primarily increased from the polar component after atmospheric-pressure plasma treatment. The surface and pore structures of the polyethylene membrane separator were examined by scanning electron microscopy, revealing a slight alteration in the pore structure. As a result of the incorporation of polar functionalities by atmospheric-pressure plasma activation, the electrolyte uptake and electrochemical impedance of the atmospheric-pressure-plasma-treated membrane separator improved. The investigational results show that the separator surface can be controlled by atmospheric-pressure plasma surface treatment to tailor the hydrophilicity and enhance the electrochemical performance of lithium ion batteries.

Porous silicon structures with high surface area/specific pore size

DOEpatents

Northrup, M.A.; Yu, C.M.; Raley, N.F.

1999-03-16

Fabrication and use of porous silicon structures to increase surface area of heated reaction chambers, electrophoresis devices, and thermopneumatic sensor-actuators, chemical preconcentrates, and filtering or control flow devices. In particular, such high surface area or specific pore size porous silicon structures will be useful in significantly augmenting the adsorption, vaporization, desorption, condensation and flow of liquids and gases in applications that use such processes on a miniature scale. Examples that will benefit from a high surface area, porous silicon structure include sample preconcentrators that are designed to adsorb and subsequently desorb specific chemical species from a sample background; chemical reaction chambers with enhanced surface reaction rates; and sensor-actuator chamber devices with increased pressure for thermopneumatic actuation of integrated membranes. Examples that benefit from specific pore sized porous silicon are chemical/biological filters and thermally-activated flow devices with active or adjacent surfaces such as electrodes or heaters. 9 figs.

Porous silicon structures with high surface area/specific pore size

DOEpatents

Northrup, M. Allen; Yu, Conrad M.; Raley, Norman F.

1999-01-01

Fabrication and use of porous silicon structures to increase surface area of heated reaction chambers, electrophoresis devices, and thermopneumatic sensor-actuators, chemical preconcentrates, and filtering or control flow devices. In particular, such high surface area or specific pore size porous silicon structures will be useful in significantly augmenting the adsorption, vaporization, desorption, condensation and flow of liquids and gasses in applications that use such processes on a miniature scale. Examples that will benefit from a high surface area, porous silicon structure include sample preconcentrators that are designed to adsorb and subsequently desorb specific chemical species from a sample background; chemical reaction chambers with enhanced surface reaction rates; and sensor-actuator chamber devices with increased pressure for thermopneumatic actuation of integrated membranes. Examples that benefit from specific pore sized porous silicon are chemical/biological filters and thermally-activated flow devices with active or adjacent surfaces such as electrodes or heaters.

Electrodeposition of Highly Porous Pt Nanoparticles Studied by Quantitative 3D Electron Tomography: Influence of Growth Mechanisms and Potential Cycling on the Active Surface Area.

PubMed

Ustarroz, Jon; Geboes, Bart; Vanrompay, Hans; Sentosun, Kadir; Bals, Sara; Breugelmans, Tom; Hubin, Annick

2017-05-17

Nanoporous Pt nanoparticles (NPs) are promising fuel cell catalysts due to their large surface area and increased electrocatalytic activity toward the oxygen reduction reaction (ORR). Herein, we report on the influence of the growth mechanisms on the surface properties of electrodeposited Pt dendritic NPs with large surface areas. The electrochemically active surface was studied by hydrogen underpotential deposition (H UPD) and compared for the first time to high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) quantitative 3D electron tomography of individual nanoparticles. Large nucleation overpotential leads to a large surface coverage of roughened spheroids, which provide a large roughness factor (R f ) but low mass-specific electrochemically active surface area (EASA). Lowering the nucleation overpotential leads to highly porous Pt NPs with pores stretching to the center of the structure. At the expense of smaller R f , the obtained EASA values of these structures are in the range of those of large surface area supported fuel cell catalysts. The active surface area of the Pt dendritic NPs was measured by electron tomography, and it was found that the potential cycling in the H adsorption/desorption and Pt oxidation/reduction region, which is generally performed to determine the EASA, leads to a significant reduction of that surface area due to a partial collapse of their dendritic and porous morphology. Interestingly, the extrapolation of the microscopic tomography results in macroscopic electrochemical parameters indicates that the surface properties measured by H UPD are comparable to the values measured on individual NPs by electron tomography after the degradation caused by the H UPD measurement. These results highlight that the combination of electrochemical and quantitative 3D surface analysis techniques is essential to provide insights into the surface properties, the electrochemical stability, and, hence, the applicability of these materials. Moreover, it indicates that care must be taken with widely used electrochemical methods of surface area determination, especially in the case of large surface area and possibly unstable nanostructures, since the measured surface can be strongly affected by the measurement itself.

Metal sponge for cryosorption pumping applications

DOEpatents

Myneni, Ganapati R.; Kneisel, Peter

1995-01-01

A system has been developed for adsorbing gases at high vacuum in a closed area. The system utilizes large surface clean anodized metal surfaces at low temperatures to adsorb the gases. The large surface clean anodized metal is referred to as a metal sponge. The metal sponge generates or maintains the high vacuum by increasing the available active cryosorbing surface area.

UV activation of polymeric high aspect ratio microstructures: ramifications in antibody surface loading for circulating tumor cell selection.

PubMed

Jackson, Joshua M; Witek, Małgorzata A; Hupert, Mateusz L; Brady, Charles; Pullagurla, Swathi; Kamande, Joyce; Aufforth, Rachel D; Tignanelli, Christopher J; Torphy, Robert J; Yeh, Jen Jen; Soper, Steven A

2014-01-07

The need to activate thermoplastic surfaces using robust and efficient methods has been driven by the fact that replication techniques can be used to produce microfluidic devices in a high production mode and at low cost, making polymer microfluidics invaluable for in vitro diagnostics, such as circulating tumor cell (CTC) analysis, where device disposability is critical to mitigate artifacts associated with sample carryover. Modifying the surface chemistry of thermoplastic devices through activation techniques can be used to increase the wettability of the surface or to produce functional scaffolds to allow for the covalent attachment of biologics, such as antibodies for CTC recognition. Extensive surface characterization tools were used to investigate UV activation of various surfaces to produce uniform and high surface coverage of functional groups, such as carboxylic acids in microchannels of different aspect ratios. We found that the efficiency of the UV activation process is highly dependent on the microchannel aspect ratio and the identity of the thermoplastic substrate. Colorimetric assays and fluorescence imaging of UV-activated microchannels following EDC/NHS coupling of Cy3-labeled oligonucleotides indicated that UV-activation of a PMMA microchannel with an aspect ratio of ~3 was significantly less efficient toward the bottom of the channel compared to the upper sections. This effect was a consequence of the bulk polymer's damping of the modifying UV radiation due to absorption artifacts. In contrast, this effect was less pronounced for COC. Moreover, we observed that after thermal fusion bonding of the device's cover plate to the substrate, many of the generated functional groups buried into the bulk rendering them inaccessible. The propensity of this surface reorganization was found to be higher for PMMA compared to COC. As an example of the effects of material and microchannel aspect ratios on device functionality, thermoplastic devices for the selection of CTCs from whole blood were evaluated, which required the immobilization of monoclonal antibodies to channel walls. From our results, we concluded the CTC yield and purity of isolated CTCs were dependent on the substrate material with COC producing the highest clinical yields for CTCs as well as better purities compared to PMMA.

Isolation, screening, and characterization of surface-active agent-producing, oil-degrading marine bacteria of Mumbai Harbor.

PubMed

Mohanram, Rajamani; Jagtap, Chandrakant; Kumar, Pradeep

2016-04-15

Diverse marine bacterial species predominantly found in oil-polluted seawater produce diverse surface-active agents. Surface-active agents produced by bacteria are classified into two groups based on their molecular weights, namely biosurfactants and bioemulsifiers. In this study, surface-active agent-producing, oil-degrading marine bacteria were isolated using a modified Bushnell-Haas medium with high-speed diesel as a carbon source from three oil-polluted sites of Mumbai Harbor. Surface-active agent-producing bacterial strains were screened using nine widely used methods. The nineteen bacterial strains showed positive results for more than four surface-active agent screening methods; further, these strains were characterized using biochemical and nucleic acid sequencing methods. Based on the results, the organisms belonged to the genera Acinetobacter, Alcanivorax, Bacillus, Comamonas, Chryseomicrobium, Halomonas, Marinobacter, Nesterenkonia, Pseudomonas, and Serratia. The present study confirmed the prevalence of surface-active agent-producing bacteria in the oil-polluted waters of Mumbai Harbor. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Nanoscale electrochemical patterning reveals the active sites for catechol oxidation at graphite surfaces.

PubMed

Patel, Anisha N; McKelvey, Kim; Unwin, Patrick R

2012-12-19

Graphite-based electrodes (graphite, graphene, and nanotubes) are used widely in electrochemistry, and there is a long-standing view that graphite step edges are needed to catalyze many reactions, with the basal surface considered to be inert. In the present work, this model was tested directly for the first time using scanning electrochemical cell microscopy reactive patterning and shown to be incorrect. For the electro-oxidation of dopamine as a model process, the reaction rate was measured at high spatial resolution across a surface of highly oriented pyrolytic graphite. Oxidation products left behind in a pattern defined by the scanned electrochemical cell served as surface-site markers, allowing the electrochemical activity to be correlated directly with the graphite structure on the nanoscale. This process produced tens of thousands of electrochemical measurements at different locations across the basal surface, unambiguously revealing it to be highly electrochemically active, with step edges providing no enhanced activity. This new model of graphite electrodes has significant implications for the design of carbon-based biosensors, and the results are additionally important for understanding electrochemical processes on related sp(2)-hybridized materials such as pristine graphene and nanotubes.

Atomic Scale Analysis of the Enhanced Electro- and Photo-Catalytic Activity in High-Index Faceted Porous NiO Nanowires

NASA Astrophysics Data System (ADS)

Shen, Meng; Han, Ali; Wang, Xijun; Ro, Yun Goo; Kargar, Alireza; Lin, Yue; Guo, Hua; Du, Pingwu; Jiang, Jun; Zhang, Jingyu; Dayeh, Shadi A.; Xiang, Bin

2015-02-01

Catalysts play a significant role in clean renewable hydrogen fuel generation through water splitting reaction as the surface of most semiconductors proper for water splitting has poor performance for hydrogen gas evolution. The catalytic performance strongly depends on the atomic arrangement at the surface, which necessitates the correlation of the surface structure to the catalytic activity in well-controlled catalyst surfaces. Herein, we report a novel catalytic performance of simple-synthesized porous NiO nanowires (NWs) as catalyst/co-catalyst for the hydrogen evolution reaction (HER). The correlation of catalytic activity and atomic/surface structure is investigated by detailed high resolution transmission electron microscopy (HRTEM) exhibiting a strong dependence of NiO NW photo- and electrocatalytic HER performance on the density of exposed high-index-facet (HIF) atoms, which corroborates with theoretical calculations. Significantly, the optimized porous NiO NWs offer long-term electrocatalytic stability of over one day and 45 times higher photocatalytic hydrogen production compared to commercial NiO nanoparticles. Our results open new perspectives in the search for the development of structurally stable and chemically active semiconductor-based catalysts for cost-effective and efficient hydrogen fuel production at large scale.

Decoupling the Effects of High Crystallinity and Surface Area on the Photocatalytic Overall Water Splitting over β-Ga2 O3 Nanoparticles by Chemical Vapor Synthesis.

PubMed

Lukic, Sasa; Menze, Jasper; Weide, Philipp; Busser, G Wilma; Winterer, Markus; Muhler, Martin

2017-09-11

Chemical vapor synthesis (CVS) is a unique method to prepare well-defined photocatalyst materials with both large specific surface area and a high degree of crystallinity. The obtained β-Ga 2 O 3 nanoparticles were optimized for photocatalysis by reductive photodeposition of the Rh/CrO x co-catalyst system. The influence of the degree of crystallinity and the specific surface area on photocatalytic aqueous methanol reforming and overall water splitting (OWS) was investigated by synthesizing β-Ga 2 O 3 samples in the temperature range from 1000 °C to 1500 °C. With increasing temperature, the specific surface area and the microstrain were found to decrease, whereas the degree of crystallinity and the crystallite size increased. Whereas the photocatalyst with the highest specific surface area showed the highest aqueous methanol reforming activity, the highest OWS activity was that for the sample with an optimum ratio between high degree of crystallinity and specific surface area. Thus, it was possible to show that the facile aqueous methanol reforming and the demanding OWS have different requirements for high photocatalytic activity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Tam, M.S.; Antal, M.J. Jr.

A novel, three-step process for the production of high-quality activated carbons from macadamia nut shell and coconut shell charcoals is described. In this process the charcoal is (1) heated to a high temperature (carbonized), (2) oxidized in air following a stepwise heating program from low (ca. 450 K) to high (ca. 660 K) temperatures (oxygenated), and (3) heated again in an inert environment to a high temperature (activated). By use of this procedure, activated carbons with surface areas greater than 1,000 m{sub 2}/g are manufactured with an overall yield of 15% (based on the dry shell feed). Removal of carbonmore » mass by the development of mesopores and macropores is largely responsible for increases in the surface area of the carbons above 600 m{sub 2}/g. Thus, the surface area per gram of activated carbon can be represented by an inverse function of the yield for burnoffs between 15 and 60%. These findings are supported by mass-transfer calculations and pore-size distribution measurements. A kinetic model for gasification of carbon by oxygen, which provides for an Eley-Rideal type reaction of a surface oxide with oxygen in air, fits the measured gasification rates reasonably well over the temperature range of 550--660 K.« less

Photo-induced self-cleaning and sterilizing activity of Sm3+ doped ZnO nanomaterials.

PubMed

Saif, M; Hafez, H; Nabeel, A I

2013-01-01

Highly active samarium doped zinc oxide self-cleaning and biocidal surfaces (x mol% Sm(3+)/ZnO where x=0, 1, 2 and 4 mol%) with crystalline porous structures were synthesized by hydrothermal method. Sm(3+)/ZnO thin films were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), energy dispersive spectroscopic (EDS), UV-visible diffuse reflectance and fluorescence (FL) spectroscopy. The combination between doping and hydrothermal treatments significantly altered the morphology of ZnO into rod and plate-like nanoshapes structure and enhanced its absorption and emission of ultraviolet radiation. The photo-activity in term of quantitative determination of the active oxidative species (()OH) produced on the thin film surfaces was evaluated using fluorescent probe method. The results showed that, the hydrothermally treated 2.0 mol% Sm(3+)/ZnO film (S2) is the highly active one. The optical, structural, morphology and photo-activity properties of the highly active thin film (S2) make it promising surface for self-cleaning and sterilizing applications. Copyright © 2012 Elsevier Ltd. All rights reserved.

Solvothermal synthesis of hierarchical TiO2 nanostructures with tunable morphology and enhanced photocatalytic activity

NASA Astrophysics Data System (ADS)

Fan, Zhenghua; Meng, Fanming; Zhang, Miao; Wu, Zhenyu; Sun, Zhaoqi; Li, Aixia

2016-01-01

This paper presents controllable growth and photocatalytic activity of TiO2 hierarchical nanostructures by solvothermal method at different temperatures. It is revealed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) that the morphology of TiO2 can be effectively controlled as rose-like, chrysanthemum-like and sea-urchin-like only changing solvothermal temperature. BET surface area analysis confirms the presence of a mesoporous network in all the nanostructures, and shows high surface area at relatively high temperature. The photocatalytic activities of the photocatalysts are evaluated by the photodegradation of RhB under UV light irradiation. The TiO2 samples exhibit high activity on the photodegradation of RhB, which is higher than that of the commercial P25. The enhancement in photocatalytic performance can be attributed to the synergetic effect of the surface area, crystallinity, band gap and crystalline size.

The Soil Moisture Active Passive (SMAP) Radar: Measurements at High Latitudes and of Surface Freeze/Thaw State

NASA Technical Reports Server (NTRS)

Spencer, Michael; Dunbar, Scott; Chen, Curtis

2013-01-01

The Soil Moisture Active/Passive (SMAP) mission is scheduled for a late 2014 launch date. The mission will use both active radar and passive radiometer instruments at L-Band in order to achieve the science objectives of measuring soil moisture and land surface freeze-thaw state. To achieve requirements for a wide swath at sufficiently high resolution for both active and passive channels, an instrument architecture that uses a large rotating reflector is employed. In this paper, focus will be placed on the radar design. The radar will employ synthetic-aperture processing to achieve a "moderate" resolution dual-pol product over a 1000 km swath. Because the radar is operating continuously, very frequent temporal coverage will be achieved at high latitudes. This data will be used to produce a surface freeze/thaw state data product.

Metal sponge for cryosorption pumping applications

DOEpatents

Myneni, G.R.; Kneisel, P.

1995-12-26

A system has been developed for adsorbing gases at high vacuum in a closed area. The system utilizes large surface clean anodized metal surfaces at low temperatures to adsorb the gases. The large surface clean anodized metal is referred to as a metal sponge. The metal sponge generates or maintains the high vacuum by increasing the available active cryosorbing surface area. 4 figs.

Immobilization of β-galactosidase from Kluyveromyces lactis onto polymeric membrane surfaces: effect of surface characteristics.

PubMed

Güleç, Hacı Ali

2013-04-01

The aim of this study was to investigate the effects of surface characteristics of plain and plasma modified cellulose acetate (CA) membranes on the immobilization yield of β-galactosidases from Kluyveromyces lactis (KLG) and its galacto-oligosaccharide (GOS) yield, respectively. Low pressure plasma treatments involving oxygen plasma activation, plasma polymerization (PlsP) of ethylenediamine (EDA) and PlsP of 2-mercaptoethanol were used to modify plain CA membrane surfaces. KLG enzyme was immobilized onto plain and oxygen plasma treated membrane surfaces by simple adsorption. Oxygen plasma activation increased the hydrophylicity of CA membrane surfaces and it improved the immobilization yield of the enzyme by 42%. KLG enzyme was also immobilized onto CA membrane surfaces through amino groups created by PlsP of EDA via covalent binding. Plasma action at 60W plasma power and 15 min. exposure time improved the amount of membrane bounded enzyme by 3.5-fold. The enrichment of the amount of amino groups via polyethyleneimine (PEI) addition enhanced this increase from 3.5-fold to 4.5-fold. Although high enzyme loading was achived (65-83%), both of the methods dramatically decreased the enzyme activity (11-12%) and GOS yield due to probably negative effects of active amino groups. KLG enzyme was more effectively immobilized onto thiolated CA membrane surface created by PlsP of 2-mercaptoethanol with high immobilization yield (70%) and especially high enzyme activity (46%). Immobilized enzymes on the CA membranes treated by PlsP were successively reutilized for 5-8 cycles at 25°C and enzymatic derivatives retained approximately 75-80% of their initial activites at the end of the reactions. Copyright © 2012 Elsevier B.V. All rights reserved.

Peroxide-assisted microwave activation of pyrolysis char for adsorption of dyes from wastewater.

PubMed

Nair, Vaishakh; Vinu, R

2016-09-01

In this study, mesoporous activated biochar with high surface area and controlled pore size was prepared from char obtained as a by-product of pyrolysis of Prosopis juliflora biomass. The activation was carried out by a simple process that involved H2O2 treatment followed by microwave pyrolysis. H2O2 impregnation time and microwave power were optimized to obtain biochar with high specific surface area and high adsorption capacity for commercial dyes such as Remazol Brilliant Blue and Methylene Blue. Adsorption parameters such as initial pH of the dye solution and adsorbent dosage were also optimized. Pore size distribution, surface morphology and elemental composition of activated biochar were thoroughly characterized. H2O2 impregnation time of 24h and microwave power of 600W produced nanostructured biochar with narrow and deep pores of 357m(2)g(-1) specific surface area. Langmuir and Langmuir-Freundlich isotherms described the adsorption equilibrium, while pseudo second order model described the kinetics of adsorption. Copyright © 2016 Elsevier Ltd. All rights reserved.

Acyl-gelatins for cell-hybrid biomaterials: preparation of gelatins with high melting point and affinity for hydrophobic surfaces.

PubMed

Miyamoto, Keiichi; Chinzei, Hiroko; Komai, Takashi

2002-12-01

In the development of cell-hybrid biomaterials, the functional activity of cells depends on the selective binding of cells to artificial ligands on the biomaterials. The extracellular matrix (ECM) is the most important ligand for cell activity. ECM is known to contain collagen, one of whose constituents is gelatin. Although natural gelatin has good cell attachment properties, the melting point of gelatin hydrogel is lower than body temperature. Thus, non-chemically cross-linked gelatin hydrogel is not a biomaterial that is used for prostheses. In the present study, we report the preparation of acyl-gelatin hydrogels with high melting point (>37 degrees C) and high affinity for hydrophobic surfaces for easy handling for transportation and adhesion activities on the hydrophobic surfaces. In addition, the doubling time of endothelial cells on the coated cell culture plate was faster than that of natural gelatin owing to the higher adhesion activity of acyl-gelatin. The results clearly demonstrated that the acyl-gelatin acted as an interface that enabled cell adhesion to artificial materials surfaces.

Coupling Binding to Catalysis: Using Yeast Cell Surface Display to Select Enzymatic Activities.

PubMed

Zhang, Keya; Bhuripanyo, Karan; Wang, Yiyang; Yin, Jun

2015-01-01

We find yeast cell surface display can be used to engineer enzymes by selecting the enzyme library for high affinity binding to reaction intermediates. Here we cover key steps of enzyme engineering on the yeast cell surface including library design, construction, and selection based on magnetic and fluorescence-activated cell sorting.

Nitrogen-doped hierarchical lamellar porous carbon synthesized from the fish scale as support material for platinum nanoparticle electrocatalyst toward the oxygen reduction reaction.

PubMed

Liu, Haijing; Cao, Yinliang; Wang, Feng; Huang, Yaqin

2014-01-22

Novel hierarchical lamellar porous carbon (HLPC) with high BET specific surface area of 2730 m(2) g(-1) and doped by nitrogen atoms has been synthesized from the fish scale without any post-synthesis treatment, and applied to support the platinum (Pt) nanoparticle (NP) catalysts (Pt/HLPC). The Pt NPs could be highly dispersed on the porous surface of HLPC with a narrow size distribution centered at ca. 2.0 nm. The results of the electrochemical analysis reveal that the electrochemical active surface area (ECSA) of Pt/HLPC is larger than the Pt NP electrocatalyst supported on the carbon black (Pt/Vulcan XC-72). Compared with the Pt/Vulcan XC-72, the Pt/HLPC exhibits larger current density, lower overpotential, and enhanced catalytic activity toward the oxygen reduction reaction (ORR) through the direct four-electron pathway. The improved catalytic activity is mainly attributed to the high BET specific surface area, hierarchical porous structures and the nitrogen-doped surface property of HLPC, indicating the superiority of HLPC as a promising support material for the ORR electrocatalysts.

A review of the fundamental studies of the copper activation mechanisms for selective flotation of the sulfide minerals, sphalerite and pyrite.

PubMed

Chandra, A P; Gerson, A R

2009-01-30

A review of the considerable, but often contradictory, literature examining the specific surface reactions associated with copper adsorption onto the common metal sulfide minerals sphalerite, (Zn,Fe)S, and pyrite (FeS(2)), and the effect of the co-location of the two minerals is presented. Copper "activation", involving the surface adsorption of copper species from solution onto mineral surfaces to activate the surface for hydrophobic collector attachment, is an important step in the flotation and separation of minerals in an ore. Due to the complexity of metal sulfide mineral containing systems this activation process and the emergence of activation products on the mineral surfaces are not fully understood for most sulfide minerals even after decades of research. Factors such as copper concentration, activation time, pH, surface charge, extent of pre-oxidation, water and surface contaminants, pulp potential and galvanic interactions are important factors affecting copper activation of sphalerite and pyrite. A high pH, the correct reagent concentration and activation time and a short time delay between reagent additions is favourable for separation of sphalerite from pyrite. Sufficient oxidation potential is also needed (through O(2) conditioning) to maintain effective galvanic interactions between sphalerite and pyrite. This ensures pyrite is sufficiently depressed while sphalerite floats. Good water quality with low concentrations of contaminant ions, such as Pb(2+)and Fe(2+), is also needed to limit inadvertent activation and flotation of pyrite into zinc concentrates. Selectivity can further be increased and reagent use minimised by opting for inert grinding and by carefully choosing selective pyrite depressants such as sulfoxy or cyanide reagents. Studies that approximate plant conditions are essential for the development of better separation techniques and methodologies. Improved experimental approaches and surface sensitive techniques with high spatial resolution are needed to precisely verify surface structures formed after copper activation. Sphalerite and pyrite surfaces are characterised by varying amounts of steps and defects, and this heterogeneity suggests co-existence of more than one copper-sulfide structure after activation.

Preparation of activated carbon hollow fibers from ramie at low temperature for electric double-layer capacitor applications.

PubMed

Du, Xuan; Zhao, Wei; Wang, Yi; Wang, Chengyang; Chen, Mingming; Qi, Tao; Hua, Chao; Ma, Mingguo

2013-12-01

Activated carbon hollow fibers (ACHFs) with high surface area were prepared from inexpensive, renewable ramie fibers (RFs) by a single-step activation method under lower temperature than that of other reports. The effects of activation conditions on the pore structure and turbostratic structure of ACHFs were investigated systematically. The results show that ACHFs surface area decreased but micropore volume and conductivity increased as the increase of activation temperature and activation time. The electrochemical measurements of supercapacitors fabricated from these ACHFs electrodes reveal that the electrochemical properties improved with the enhancing of activation degree. However, too high activation temperature can make the ion diffusion resistance increase. It suggests that pore structure and conductivity are as important as surface area to decide the electrochemical performances of ACHFs electrode materials. A maximum capacity of 287 F g(-1) at 50 mA g(-1) was obtained for the ACHFs electrode prepared under suitable conditions. Copyright © 2013 Elsevier Ltd. All rights reserved.

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

Mesoporous carbon-supported Pd nanoparticles with high specific surface area for cyclohexene hydrogenation: Outstanding catalytic activity of NaOH-treated catalysts

NASA Astrophysics Data System (ADS)

Puskás, R.; Varga, T.; Grósz, A.; Sápi, A.; Oszkó, A.; Kukovecz, Á.; Kónya, Z.

2016-06-01

Extremely high specific surface area mesoporous carbon-supported Pd nanoparticle catalysts were prepared with both impregnation and polyol-based sol methods. The silica template used for the synthesis of mesoporous carbon was removed by both NaOH and HF etching. Pd/mesoporous carbon catalysts synthesized with the impregnation method has as high specific surface area as 2250 m2/g. In case of NaOH-etched impregnated samples, the turnover frequency of cyclohexene hydrogenation to cyclohexane at 313 K was obtained 14 molecules • site- 1 • s- 1. The specific surface area of HF-etched samples was higher compared to NaOH-etched samples. However, catalytic activity was 3-6 times higher on NaOH-etched samples compared to HF-etched samples, which can be attributed to the presence of sodium and surface hydroxylgroups of the catalysts etched with NaOH solution.

Solid-support immobilization of a "swing" fusion protein for enhanced glucose oxidase catalytic activity.

PubMed

Takatsuji, Yoshiyuki; Yamasaki, Ryota; Iwanaga, Atsushi; Lienemann, Michael; Linder, Markus B; Haruyama, Tetsuya

2013-12-01

The strategic surface immobilization of a protein can add new functionality to a solid substrate; however, protein activity, e.g., enzymatic activity, can be drastically decreased on immobilization onto a solid surface. The concept of a designed and optimized "molecular interface" is herein introduced in order to address this problem. In this study, molecular interface was designed and constructed with the aim of attaining high enzymatic activity of a solid-surface-immobilized a using the hydrophobin HFBI protein in conjunction with a fusion protein of HFBI attached to glucose oxidase (GOx). The ability of HFBI to form a self-organized membrane on a solid surface in addition to its adhesion properties makes it an ideal candidate for immobilization. The developed fusion protein was also able to form an organized membrane, and its structure and immobilized state on a solid surface were investigated using QCM-D measurements. This method of immobilization showed retention of high enzymatic activity and the ability to control the density of the immobilized enzyme. In this study, we demonstrated the importance of the design and construction of molecular interface for numerous purposes. This method of protein immobilization could be utilized for preparation of high throughput products requiring structurally ordered molecular interfaces, in addition to many other applications. Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

Healing of Fatigue Crack by High-Density Electropulsing in Austenitic Stainless Steel Treated with the Surface-Activated Pre-Coating

PubMed Central

Hosoi, Atsushi; Kishi, Tomoya; Ju, Yang

2013-01-01

A technique to heal a fatigue crack in austenitic stainless steel SUS316 by applying a controlled, high-density pulsed current was developed. A surface-activated pre-coating (SAPC), which eliminates the oxide layer and coats a Ni film on the crack surface, was used to improve the adhesion between crack surfaces. Cracks were observed by scanning electron microscopy before and after the application of high-density electropulsing. To evaluate the healing effect of the SAPC during crack propagation, fatigue tests were conducted under a constant stress intensity factor. The fatigue crack treated with the SAPC was found to be effectively healed as a result of electropulsing, and also showed a slower rate of crack propagation. PMID:28788327

Assessment of trace element contamination of urban surface soil at informal industrial sites in a low-income country.

PubMed

Kanda, Artwell; Ncube, France; Hwende, Tamuka; Makumbe, Peter

2018-05-29

Trace elements released by human activity are ubiquitously detected in surface soil. The trace element contamination statuses of 20 sampling stations at two busy informal industrial sites of Harare city, Zimbabwe, were evaluated using geochemical indices. Spectrophotometric determinations of concentrations of trace elements in surface soil indicated generally higher values than the reference site and the average upper earth's crust. High contamination factors were observed for trace elements across sampling stations at Gazaland and Siyaso informal industrial sites. Concentrations exhibited heterogeneous distribution of trace elements in surface soil varying with the nature of activity at a sampling station. The pollution load index and degree of contamination suggested highly contaminated surface soil with Cd, Cu and Pb particularly where the following activities were done: (1) welding, (2) automobile maintenance and (3) waste dumping. These results may be very important to reduce soil contamination. Paving surfaces may help to reduce dispersal of trace elements deposited on surface soil to other stations and minimise human exposure via inhalation and contact.

Influence of the physico-chemical properties of CeO 2-ZrO 2 mixed oxides on the catalytic oxidation of NO to NO 2

NASA Astrophysics Data System (ADS)

Atribak, Idriss; Guillén-Hurtado, Noelia; Bueno-López, Agustín; García-García, Avelina

2010-10-01

Commercial and home-made Ce-Zr catalysts prepared by co-precipitation were characterised by XRD, Raman spectroscopy, N 2 adsorption at -196 °C and XPS, and were tested for NO oxidation to NO 2. Among the different physico-chemical properties characterised, the surface composition seems to be the most relevant one in order to explain the NO oxidation capacity of these Ce-Zr catalysts. As a general trend, Ce-Zr catalysts with a cerium-rich surface, that is, high XPS-measured Ce/Zr atomic surface ratios, are more active than those with a Zr-enriched surface. The decrease in catalytic activity of the Ce-Zr mixed oxided upon calcinations at 800 °C with regard to 500 °C is mainly attributed to the decrease in Ce/Zr surface ratio, that is, to the surface segregation of Zr. The phase composition (cubic or t'' for Ce-rich compositions) seems not to be a direct effect on the catalytic activity for NO oxidation in the range of compositions tested. However, the formation of a proper solid solution prevents important surface segregation of Zr upon calcinations at high temperature. The effect of the BET surface area in the catalytic activity for NO oxidation of Ce-Zr mixed oxides is minor in comparison with the effect of the Ce/Zr surface ratio.

Role of LiCoO 2 Surface Terminations in Oxygen Reduction and Evolution Kinetics

DOE PAGES

Han, Binghong; Qian, Danna; Risch, Marcel; ...

2015-03-22

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities of LiCoO 2 nanorods with sizes in the range from 9 to 40 nm were studied in alkaline solution. The sides of these nanorods were terminated with low-index surfaces such as (003) while the tips were terminated largely with high-index surfaces such as (104) as revealed by high-resolution transmission electron microscopy. Electron energy loss spectroscopy demonstrated that low-spin Co 3+ prevailed on the sides, while the tips exhibited predominantly high- or intermediate-spin Co 3+. We correlated the electronic and atomic structure to higher specific ORR and OER activities at themore » tips as compared to the sides, which was accompanied by more facile redox of Co 2+/3+ and higher charge transferred per unit area. These findings highlight the critical role of surface terminations and electronic structures of transition metal oxides on the ORR and OER activity.« less

In situ dynamic tracking of heterogeneous nanocatalytic processes by shell-isolated nanoparticle-enhanced Raman spectroscopy

PubMed Central

Zhang, Hua; Wang, Chen; Sun, Han-Lei; Fu, Gang; Chen, Shu; Zhang, Yue-Jiao; Chen, Bing-Hui; Anema, Jason R.; Yang, Zhi-Lin; Li, Jian-Feng; Tian, Zhong-Qun

2017-01-01

Surface molecular information acquired in situ from a catalytic process can greatly promote the rational design of highly efficient catalysts by revealing structure-activity relationships and reaction mechanisms. Raman spectroscopy can provide this rich structural information, but normal Raman is not sensitive enough to detect trace active species adsorbed on the surface of catalysts. Here we develop a general method for in situ monitoring of heterogeneous catalytic processes through shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) satellite nanocomposites (Au-core silica-shell nanocatalyst-satellite structures), which are stable and have extremely high surface Raman sensitivity. By combining operando SHINERS with density functional theory calculations, we identify the working mechanisms for CO oxidation over PtFe and Pd nanocatalysts, which are typical low- and high-temperature catalysts, respectively. Active species, such as surface oxides, superoxide/peroxide species and Pd–C/Pt–C bonds are directly observed during the reactions. We demonstrate that in situ SHINERS can provide a deep understanding of the fundamental concepts of catalysis. PMID:28537269

Single Silver Adatoms on Nanostructured Manganese Oxide Surfaces: Boosting Oxygen Activation for Benzene Abatement.

PubMed

Chen, Yaxin; Huang, Zhiwei; Zhou, Meijuan; Ma, Zhen; Chen, Jianmin; Tang, Xingfu

2017-02-21

The involvement of a great amount of active oxygen species is a crucial requirement for catalytic oxidation of benzene, because complete mineralization of one benzene molecule needs 15 oxygen atoms. Here, we disperse single silver adatoms on nanostructured hollandite manganese oxide (HMO) surfaces by using a thermal diffusion method. The single-atom silver catalyst (Ag 1 /HMO) shows high catalytic activity in benzene oxidation, and 100% conversion is achieved at 220 °C at a high space velocity of 23 000 h -1 . The Mars-van Krevelen mechanism is valid in our case as the reaction orders for both benzene and O 2 approach one, according to reaction kinetics data. Data from H 2 temperature-programmed reduction and O core-level X-ray photoelectron spectra (XPS) reveal that Ag 1 /HMO possesses a great amount of active surface lattice oxygen available for benzene oxidation. Valence-band XPS and density functional theoretical calculations demonstrate that the single Ag adatoms have the upshifted 4d orbitals, thus facilitating the activation of gaseous oxygen. Therefore, the excellent activation abilities of Ag 1 /HMO toward both surface lattice oxygen and gaseous oxygen account for its high catalytic activity in benzene oxidation. This work may assist with the rational design of efficient metal-oxide catalysts for the abatement of volatile organic compounds such as benzene.

Effective rate constants for nanostructured heterogeneous catalysts

NASA Astrophysics Data System (ADS)

Hendy, Shaun; Gaston, Nicola; Zhang, Philip; Lund, Nat

2012-02-01

There is currently a high level of interest in the use of nanostructured materials for catalysis. For instance, gold, which is largely inert in the bulk, can exhibit strong catalytic activity when in nanoparticle form. With precious metal catalysts such as Pt and Pd in high demand, the use of these materials in nanoparticle form can also substantially reduce costs by exposure of more surface area for the same volume of material. When reactants are plentiful, the effective activity of a nanoparticulate catalyst will increase roughly with its surface area. However, under diffusion-limited conditions, the reactant must diffuse to active sites on the catalyst, so a high surface area and a high density of active sites may bring diminishing returns if reactant is consumed faster than it arrives. Here we apply a mathematical homogenisation approach to derive simple expressions for the effective reactivity of a nanostructured catalyst under diffusion limited conditions that relate the intrinsic rate constants of the surfaces presented by the catalyst to an effective rate constant. When highly active catalytic sites, such as step edges or other defects are present, we show that distinct limiting cases emerge depending on the degree of overlap of the reactant depletion zone about each site. In gases, the size of this depletion zone is approximately the mean free path, so the effective reactivity will depend on the structure of the catalyst on that scale. We discuss implications for the optimal design of nanoparticle catalysts.

Surfaces of Fluorinated Pyridinium Block Copolymers with Enhanced Antibacterial Activity

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

Krishnan,S.; Ward, R.; Hexemer, A.

2006-01-01

Polystyrene-b-poly(4-vinylpyridine) copolymers were quaternized with 1-bromohexane and 6-perfluorooctyl-1-bromohexane. Surfaces prepared from these polymers were characterized by contact angle measurements, near-edge X-ray absorption fine structure spectroscopy and X-ray photoelectron spectroscopy. The fluorinated pyridinium surfaces showed enhanced antibacterial activity compared to their nonfluorinated counterparts. Even a polymer with a relatively low molecular weight pyridinium block showed high antimicrobial activity. The bactericidal effect was found to be related to the molecular composition and organization in the top 2-3 nm of the surface and increased with increasing hydrophilicity and pyridinium concentration of the surface.

Methane combustion reactivity during the metal→metallic oxide transformation of Pd-Pt catalysts: Effect of oxygen pressure

NASA Astrophysics Data System (ADS)

Qi, Wenjie; Ran, Jingyu; Zhang, Zhien; Niu, Juntian; Zhang, Peng; Fu, Lijuan; Hu, Bo; Li, Qilai

2018-03-01

Density functional theory combined with kinetic models were used to probe different kinetics consequences by which methane activation on different oxygen chemical potential surfaces as oxygen pressure increased. The metallic oxide → metal transformation temperature of Pd-Pt catalysts increased with the increase of the Pd content or/and O2 pressure. The methane conversion rate on Pt catalyst increased and then decreased to a constant value when increasing the O2 pressure, and Pd catalyst showed a poor activity performance in the case of low O2 pressure. Moreover, its activity increased as the oxygen chemical potential for O2 pressure increased in the range of 2.5-10 KPa. For metal clusters, the Csbnd H bond and Odbnd O bond activation steps occurred predominantly on *-* site pairs. The methane conversion rate was determined by O2 pressure because the adsorbed O atoms were rapidly consumed by other adsorbed species in this kinetic regime. As the O2 pressure increased, the metallic active sites for methane activation were decreased and there was no longer lack of adsorbed O atoms, resulting in the decrease of the methane conversion rate. Furthermore, when the metallic surfaces were completely covered by adsorbed oxygen atoms at higher oxygen chemical potentials, Pt catalyst showed a poor activity due to a high Csbnd H bond activation barrier on O*sbnd O*. In the case of high O2 pressure, Pd atoms preferred to segregate to the active surface of Pd-Pt catalysts, leading to the formation of PdO surfaces. The increase of Pd segregation promoted a subsequent increase in active sites and methane conversion rate. The PdO was much more active than metallic and O* saturated surfaces for methane activation, inferred from the theory and experimental study. Pd-rich bimetallic catalyst (75% molar Pd) showed a dual high methane combustion activity on O2-poor and O2-rich conditions.

Study on photoemission surface of varied doping GaN photocathode

NASA Astrophysics Data System (ADS)

Qiao, Jianliang; Du, Ruijuan; Ding, Huan; Gao, Youtang; Chang, Benkang

2014-09-01

For varied doping GaN photocathode, from bulk to surface the doping concentrations are distributed from high to low. The varied doping GaN photocathode may produce directional inside electric field within the material, so the higher quantum efficiency can be obtained. The photoemission surface of varied doping GaN photocathode is very important to the high quantum efficiency, but the forming process of the surface state after Cs activation or Cs/O activation has been not known completely. Encircling the photoemission mechanism of varied GaN photocathode, considering the experiment phenomena during the activation and the successful activation results, the varied GaN photocathode surface model [GaN(Mg):Cs]:O-Cs after activation with cesium and oxygen was given. According to GaN photocathode activation process and the change of electronic affinity, the comparatively ideal NEA property can be achieved by Cs or Cs/O activation, and higher quantum efficiency can be obtained. The results show: The effective NEA characteristic of GaN can be gotten only by Cs. [GaN(Mg):Cs] dipoles form the first dipole layer, the positive end is toward the vacuum side. In the activation processing with Cs/O, the second dipole layer is formed by O-Cs dipoles, A O-Cs dipole includes one oxygen atom and two Cs atoms, and the positive end is also toward the vacuum side thus the escape of electrons can be promoted.

The surface activity of purified ocular mucin at the air-liquid interface and interactions with meibomian lipids.

PubMed

Millar, Thomas J; Tragoulias, Sophia T; Anderton, Philip J; Ball, Malcolm S; Miano, Fausto; Dennis, Gary R; Mudgil, Poonam

2006-01-01

Ocular mucins are thought to contribute to the stability of the tear film by reducing surface tension. The purpose of this study was to compare the effect of different mucins and hyaluronic acid (HA) alone and mixed with meibomian lipids on the surface pressure at an air-liquid interface. A Langmuir trough and Wilhelmy balance were used to measure and compare the surface activity of bovine submaxillary gland mucin (BSM), purified BSM, purified bovine ocular mucin and HA, and mixtures of these with meibomian lipids, phosphatidylcholine, and phosphatidylglycerol. Their appearance at the surface of an air-buffer interface was examined using epifluorescence microscopy. Purified ocular mucin had no surface activity even at concentrations that were 100 times more than normally occur in tears. By contrast, commercial BSM caused changes to surface pressure that were concentration dependent. The surface pressure-area profiles showed surface activity with maximum surface pressures of 12.3-22.5 mN/m depending on the concentration. Purified BSM showed no surface activity at low concentrations, whereas higher concentrations reached a maximum surface pressure of 25 mN/m. HA showed no surface activity, at low or high concentrations. Epifluorescence showed that the mucins were located at the air-buffer interface and changed the appearance of lipid films. Purified bovine ocular mucin and HA have no surface activity. However, despite having no surface activity in their own right, ocular mucins are likely to be present at the surface of the tear film, where they cause an increase in surface pressure by causing a compression of the lipids (a reorganization of the lipids) and alter the viscoelastic properties at the surface.

Advanced Thermionic Technology Program

NASA Technical Reports Server (NTRS)

1977-01-01

Topics include surface studies (surface theory, basic surface experiments, and activation chamber experiments); plasma studies (converter theory and enhanced mode conversion experiments); and component development (low temperature conversion experiments, high efficiency conversion experiments, and hot shell development).

Zwitterionic sulfobetaine-grafted poly(vinylidene fluoride) membrane with highly effective blood compatibility via atmospheric plasma-induced surface copolymerization.

PubMed

Chang, Yung; Chang, Wan-Ju; Shih, Yu-Ju; Wei, Ta-Chin; Hsiue, Ging-Ho

2011-04-01

Development of nonfouling membranes to prevent nonspecific protein adsorption and platelet adhesion is critical for many biomedical applications. It is always a challenge to control the surface graft copolymerization of a highly polar monomer from the highly hydrophobic surface of a fluoropolymer membrane. In this work, the blood compatibility of poly(vinylidene fluoride) (PVDF) membranes with surface-grafted electrically neutral zwitterionic poly(sulfobetaine methacrylate) (PSBMA), from atmospheric plasma-induced surface copolymerization, was studied. The effect of surface composition and graft morphology, electrical neutrality, hydrophilicity and hydration capability on blood compatibility of the membranes were determined. Blood compatibility of the zwitterionic PVDF membranes was systematically evaluated by plasma protein adsorption, platelet adhesion, plasma-clotting time, and blood cell hemolysis. It was found that the nonfouling nature and hydration capability of grafted PSBMA polymers can be effectively controlled by regulating the grafting coverage and charge balance of the PSBMA layer on the PVDF membrane surface. Even a slight charge bias in the grafted zwitterionic PSBMA layer can induce electrostatic interactions between proteins and the membrane surfaces, leading to surface protein adsorption, platelet activation, plasma clotting and blood cell hemolysis. Thus, the optimized PSBMA surface graft layer in overall charge neutrality has a high hydration capability and the best antifouling, anticoagulant, and antihemolytic activities when comes into contact with human blood. © 2011 American Chemical Society

Improvement of oxygen-containing functional groups on olive stones activated carbon by ozone and nitric acid for heavy metals removal from aqueous phase.

PubMed

Bohli, Thouraya; Ouederni, Abdelmottaleb

2016-08-01

Recently, modification of surface structure of activated carbons in order to improve their adsorption performance toward especial pollutants has gained great interest. Oxygen-containing functional groups have been devoted as the main responsible for heavy metal binding on the activated carbon surface; their introduction or enhancement needs specific modification and impregnation methods. In the present work, olive stones activated carbon (COSAC) undergoes surface modifications in gaseous phase using ozone (O3) and in liquid phase using nitric acid (HNO3). The activated carbon samples were characterized using N2 adsorption-desorption isotherm, SEM, pHpzc, FTIR, and Boehm titration. The activated carbon parent (COSAC) has a high surface area of 1194 m(2)/g and shows a predominantly microporous structure. Oxidation treatments with nitric acid and ozone show a decrease in both specific surface area and micropore volumes, whereas these acidic treatments have led to a fixation of high amount of surface oxygen functional groups, thus making the carbon surface more hydrophilic. Activated carbon samples were used as an adsorbent matrix for the removal of Co(II), Ni(II), and Cu(II) heavy metal ions from aqueous solutions. Adsorption isotherms were obtained at 30 °C, and the data are well fitted to the Redlich-Peterson and Langmuir equation. Results show that oxidized COSACs, especially COSAC(HNO3), are capable to remove more Co(II), Cu(II), and Ni(II) from aqueous solution. Nitric acid-oxidized olive stones activated carbon was tested in its ability to remove metal ions from binary systems and results show an important maximum adsorbed amount as compared to single systems.

A molecular catalyst for water oxidation that binds to metal oxide surfaces

PubMed Central

Sheehan, Stafford W.; Thomsen, Julianne M.; Hintermair, Ulrich; Crabtree, Robert H.; Brudvig, Gary W.; Schmuttenmaer, Charles A.

2015-01-01

Molecular catalysts are known for their high activity and tunability, but their solubility and limited stability often restrict their use in practical applications. Here we describe how a molecular iridium catalyst for water oxidation directly and robustly binds to oxide surfaces without the need for any external stimulus or additional linking groups. On conductive electrode surfaces, this heterogenized molecular catalyst oxidizes water with low overpotential, high turnover frequency and minimal degradation. Spectroscopic and electrochemical studies show that it does not decompose into iridium oxide, thus preserving its molecular identity, and that it is capable of sustaining high activity towards water oxidation with stability comparable to state-of-the-art bulk metal oxide catalysts. PMID:25757425

Sulfur-doped nanoporous carbon spheres with ultrahigh specific surface area and high electrochemical activity for supercapacitor

NASA Astrophysics Data System (ADS)

Liu, Simin; Cai, Yijin; Zhao, Xiao; Liang, Yeru; Zheng, Mingtao; Hu, Hang; Dong, Hanwu; Jiang, Sanping; Liu, Yingliang; Xiao, Yong

2017-08-01

Development of facile and scalable synthesis process for the fabrication of nanoporous carbon materials with large specific surface areas, well-defined nanostructure, and high electrochemical activity is critical for the high performance energy storage applications. The key issue is the dedicated balance between the ultrahigh surface area and highly porous but interconnected nanostructure. Here, we demonstrate the fabrication of new sulfur doped nanoporous carbon sphere (S-NCS) with the ultrahigh surface area up to 3357 m2 g-1 via a high-temperature hydrothermal carbonization and subsequent KOH activation process. The as-prepared S-NCS which integrates the advantages of ultrahigh porous structure, well-defined nanospherical and modification of heteroatom displays excellent electrochemical performance. The best performance is obtained on S-NCS prepared by the hydrothermal carbonization of sublimed sulfur and glucose, S-NCS-4, reaching a high specific capacitance (405 F g-1 at a current density of 0.5 A g-1) and outstanding cycle stability. Moreover, the symmetric supercapacitor is assembled by S-NCS-4 displays a superior energy density of 53.5 Wh kg-1 at the power density of 74.2 W kg-1 in 1.0 M LiPF6 EC/DEC. The synthesis method is simple and scalable, providing a new route to prepare highly porous and heteroatom-doped nanoporous carbon spheres for high performance energy storage applications.

Graphene-based textured surface by pulsed laser deposition as a robust platform for surface enhanced Raman scattering applications

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

Tite, T.; Donnet, C.; Loir, A.-S.

We have developed a surface enhanced Raman scattering (SERS)-active substrate based on gold nanoparticles-decorated few-layer (fl) graphene grown by pulsed laser deposition. Diamond-Like Carbon film has been converted to fl-graphene after thermal annealing at low temperature. The formation of fl-graphene was confirmed by Raman spectroscopy, and surface morphology was highlighted by scanning electron microscopy. We found that textured fl-graphene film with nanoscale roughness was highly beneficial for SERS detection. Rhodamine 6G and p-aminothiophenol proposed as test molecules were detected with high sensitivity. The detection at low concentration of deltamethrin, an active molecule of a commercial pesticide was further demonstrated.

Mesoporous metallic rhodium nanoparticles

NASA Astrophysics Data System (ADS)

Jiang, Bo; Li, Cuiling; Dag, Ömer; Abe, Hideki; Takei, Toshiaki; Imai, Tsubasa; Hossain, Md. Shahriar A.; Islam, Md. Tofazzal; Wood, Kathleen; Henzie, Joel; Yamauchi, Yusuke

2017-05-01

Mesoporous noble metals are an emerging class of cutting-edge nanostructured catalysts due to their abundant exposed active sites and highly accessible surfaces. Although various noble metal (e.g. Pt, Pd and Au) structures have been synthesized by hard- and soft-templating methods, mesoporous rhodium (Rh) nanoparticles have never been generated via chemical reduction, in part due to the relatively high surface energy of rhodium (Rh) metal. Here we describe a simple, scalable route to generate mesoporous Rh by chemical reduction on polymeric micelle templates [poly(ethylene oxide)-b-poly(methyl methacrylate) (PEO-b-PMMA)]. The mesoporous Rh nanoparticles exhibited a ~2.6 times enhancement for the electrocatalytic oxidation of methanol compared to commercially available Rh catalyst. Surprisingly, the high surface area mesoporous structure of the Rh catalyst was thermally stable up to 400 °C. The combination of high surface area and thermal stability also enables superior catalytic activity for the remediation of nitric oxide (NO) in lean-burn exhaust containing high concentrations of O2.

Wrinkled substrate and Indium Tin Oxide-free transparent electrode making organic solar cells thinner in active layer

NASA Astrophysics Data System (ADS)

Liu, Kong; Lu, Shudi; Yue, Shizhong; Ren, Kuankuan; Azam, Muhammad; Tan, Furui; Wang, Zhijie; Qu, Shengchun; Wang, Zhanguo

2016-11-01

To enable organic solar cells with a competent charge transport efficiency, reducing the thickness of active layer without sacrificing light absorption efficiency turns out to be of high feasibility. Herein, organic solar cells on wrinkled metal surface are designed. The purposely wrinkled Al/Au film with a smooth surface provides a unique scaffold for constructing thin organic photovoltaic devices by avoiding pinholes and defects around sharp edges in conventional nanostructures. The corresponding surface light trapping effect enables the thin active layer (PTB7-Th:PC71BM) with a high absorption efficiency. With the innovative MoO3/Ag/ZnS film as the top transparent electrode, the resulting Indium Tin Oxide-free wrinkled devices show a power conversion efficiency as 7.57% (50 nm active layer), higher than the planner counterparts. Thus, this paper provides a new methodology to improve the performance of organic solar cells by balancing the mutual restraint factors to a high level.

Effects of O 2 plasma and UV-O 3 assisted surface activation on high sensitivity metal oxide functionalized multiwalled carbon nanotube CH 4 sensors

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

Humayun, Md Tanim; Sainato, Michela; Divan, Ralu

We present a comparative analysis of UV-O 3 (UVO) and O 2 plasma-based surface activation processes of multi-walled carbon nanotubes (MWCNTs) enabling highly effective functionalization with metal oxide nanocrystals (MONCs). Experimental results from transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy show that by forming COOH (carboxyl), C-OH (hydroxyl), and C=O (carbonyl) groups on the MWCNT surface that act as active nucleation sites, O 2 plasma and UVO-based dry pre-treatment techniques greatly enhance the affinity between MWCNT surface and the functionalizing MONCs. MONCs, such as ZnO and SnO 2, deposited by atomic layermore » deposition (ALD) technique, were implemented as the functionalizing material following UVO and O 2 plasma activation of MWCNTs. In conclusion, a comparative study on the relative resistance changes of O 2 plasma and UVO activated MWCNT functionalized with MONC in the presence of 10 ppm methane (CH 4) in air, is presented as well.« less

Photocatalytic activity of nanostructured ZnO-ZrO2 binary oxide using fluorometric method

NASA Astrophysics Data System (ADS)

Ibrahim, M. M.

2015-06-01

Evaluation of the photocatalytic activity of ZnO-ZrO2 nanomaterials using fluorescence based technique has rarely been reported. In the present work, ZnO-ZrO2 mixed oxides coupled with various ZnO dosages (0, 10, 30, 50, 70 wt%) were prepared by impregnation method. These nanomaterials were characterized by studying their structural, surface and optical properties. The photocatalytic activity in term of quantitative determination of the active oxidative species (radOH) produced on the surface of binary oxide was evaluated using fluorescent probe method. The interaction between ZnO and ZrO2 was affected on the photocatalytic efficiency of mixture. The results show that, the addition of ZnO to ZrO2 decreased the electron-hole recombination and increased the rate of radOH radicals formation. 50 wt% ZnO-ZrO2 photocatalyst exhibited much higher photocatalytic activity. The profound effect of binary oxide catalyst was generally considered due to the high surface area, small particle size, high monoclinic phase of ZrO2 content, low band gap and the presence of surface OH groups.

Effects of O 2 plasma and UV-O 3 assisted surface activation on high sensitivity metal oxide functionalized multiwalled carbon nanotube CH 4 sensors

DOE PAGES

Humayun, Md Tanim; Sainato, Michela; Divan, Ralu; ...

2017-07-28

We present a comparative analysis of UV-O 3 (UVO) and O 2 plasma-based surface activation processes of multi-walled carbon nanotubes (MWCNTs) enabling highly effective functionalization with metal oxide nanocrystals (MONCs). Experimental results from transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy show that by forming COOH (carboxyl), C-OH (hydroxyl), and C=O (carbonyl) groups on the MWCNT surface that act as active nucleation sites, O 2 plasma and UVO-based dry pre-treatment techniques greatly enhance the affinity between MWCNT surface and the functionalizing MONCs. MONCs, such as ZnO and SnO 2, deposited by atomic layermore » deposition (ALD) technique, were implemented as the functionalizing material following UVO and O 2 plasma activation of MWCNTs. In conclusion, a comparative study on the relative resistance changes of O 2 plasma and UVO activated MWCNT functionalized with MONC in the presence of 10 ppm methane (CH 4) in air, is presented as well.« less

Graphene incorporated, N doped activated carbon as catalytic electrode in redox active electrolyte mediated supercapacitor

NASA Astrophysics Data System (ADS)

Gao, Zhiyong; Liu, Xiao; Chang, Jiuli; Wu, Dapeng; Xu, Fang; Zhang, Lingcui; Du, Weimin; Jiang, Kai

2017-01-01

Graphene incorporated, N doped activated carbons (GNACs) are synthesized by alkali activation of graphene-polypyrrole composite (G-PPy) at different temperatures for application as electrode materials of supercapacitors. Under optimal activation temperature of 700 °C, the resultant samples, labeled as GNAC700, owns hierarchically porous texture with high specific surface area and efficient ions diffusion channels, N, O functionalized surface with apparent pseudocapacitance contribution and high wettability, thus can deliver a moderate capacitance, a high rate capability and a good cycleability when used as supercapacitor electrode. Additionally, the GNAC700 electrode demonstrates high catalytic activity for the redox reaction of pyrocatechol/o-quinone pair in H2SO4 electrolyte, thus enables a high pseudocapacitance from electrolyte. Under optimal pyrocatechol concentration in H2SO4 electrolyte, the electrode capacitance of GNAC700 increases by over 4 folds to 512 F g-1 at 1 A g-1, an excellent cycleability is also achieved simultaneously. Pyridinic- N is deemed to be responsible for the high catalytic activity. This work provides a promising strategy to ameliorate the capacitive performances of supercapacitors via the synergistic interaction between redox-active electrolyte and catalytic electrodes.

Laser-induced surface modification of biopolymers – micro/nanostructuring and functionalization

NASA Astrophysics Data System (ADS)

Stankova, N. E.; Atanasov, P. A.; Nedyalkov, N. N.; Tatchev, Dr; Kolev, K. N.; Valova, E. I.; Armyanov, St. A.; Grochowska, K.; Śliwiński, G.; Fukata, N.; Hirsch, D.; Rauschenbach, B.

2018-03-01

The medical-grade polydimethylsiloxane (PDMS) elastomer is a widely used biomaterial in medicine for preparation of high-tech devices because of its remarkable properties. In this paper, we present experimental results on surface modification of PDMS elastomer by using ultraviolet, visible, and near-infrared ns-laser system and investigation of the chemical composition and the morphological structure inside the treated area in dependence on the processing parameters – wavelength, laser fluence and number of pulses. Remarkable chemical transformations and changes of the morphological structure were observed, resulting in the formation of a highly catalytically active surface, which was successfully functionalized via electroless Ni and Pt deposition by a sensitizing-activation free process. The results obtained are very promising in view of applying the methods of laser-induced micro- and nano-structuring and activation of biopolymers’ surface and further electroless metal plating to the preparation of, e.g., multielectrode arrays (MEAs) devices in neural and muscular surface interfacing implantable systems.

γH2Ax Expression as a Potential Biomarker Differentiating between Low and High Grade Cervical Squamous Intraepithelial Lesions (SIL) and High Risk HPV Related SIL

PubMed Central

Kefala, Maria; Kottaridi, Christine; Spathis, Aris; Gouloumi, Alina-Roxani; Pouliakis, Abraham; Pappas, Asimakis; Sioulas, Vasileios; Chrelias, Charalambos; Karakitsos, Petros; Panayiotides, Ioannis

2017-01-01

Background γH2AX is a protein biomarker for double-stranded DNA breakage; its expression was studied in cervical squamous intraepithelial lesions and carcinomas. Methods Immunostaining for phospho-γH2AX was performed in sections from histologically confirmed cervical SIL and carcinomas, as well as from normal cervices used as controls. In total, 275 cases were included in the study: 112 low grade SIL (LGSIL), 99 high grade SIL (HGSIL), 24 squamous cell carcinoma (SCC), 12 adenocarcinoma and 28 cervical specimens with no essential lesions. Correlation of histological grading, high risk vs. low risk HPV virus presence, activated vs. non-activated status (by high risk HPV mRNA expression) and γH2AX expression in both basal and surface segments of the squamous epithelium was performed. Results Gradual increase of both basal and surface γH2AX expression was noted up from normal cervices to LGSIL harboring a low risk HPV type, to LGSIL harboring a high risk virus at a non-activated state (p<0.05). Thereafter, both basal and surface γH2AX expression dropped in LGSIL harboring a high risk virus at an activated state and in HGSIL. Conclusions γH2AX could serve as a potential biomarker discriminating between LGSIL and HGSIL, as well as between LGSIL harboring high risk HPV at an activated state. PMID:28118377

Poly(ethylene oxide) surfactant polymers.

PubMed

Vacheethasanee, Katanchalee; Wang, Shuwu; Qiu, Yongxing; Marchant, Roger E

2004-01-01

We report on a series of structurally well-defined surfactant polymers that undergo surface-induced self-assembly on hydrophobic biomaterial surfaces. The surfactant polymers consist of a poly(vinyl amine) backbone with poly(ethylene oxide) and hexanal pendant groups. The poly(vinyl amine) (PVAm) was synthesized by hydrolysis of poly(N-vinyl formamide) following free radical polymerization of N-vinyl formamide. Hexanal and aldehyde-terminated poly(ethylene oxide) (PEO) were simultaneously attached to PVAm via reductive amination. Surfactant polymers with different PEO:hexanal ratios and hydrophilic/hydrophobic balances were prepared, and characterized by FT-IR, 1H-NMR and XPS spectroscopies. Surface active properties at the air/water interface were determined by surface tension measurements. Surface activity at a solid surface/water interface was demonstrated by atomic force microscopy, showing epitaxially molecular alignment for surfactant polymers adsorbed on highly oriented pyrolytic graphite. The surfactant polymers described in this report can be adapted for simple non-covalent surface modification of biomaterials and hydrophobic surfaces to provide highly hydrated interfaces.

New reagent for extraction photomeric determination of anionic surface-active substances

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

Chernova, R.K.; Yastrebova, N.I.; Pankratov, A.N.

1995-02-01

The new reagent 2,6-diphenyl-4-(4-dimethylamino)styrylpyryl chloride is suggested for extraction photometric determination of anionic surface-active substances (SAS). This reagent possesses high sensitivity and selectivity, and can be used for the determination of both individual SAS of any kind and the total amount of anionic SAS. The reagent was used in analysis of highly mineralized statal waters and for the determination of sulfated products in polyoxyethylated alkylphenols.

Biosurfactant Production by Bacillus salmalaya for Lubricating Oil Solubilization and Biodegradation.

PubMed

Dadrasnia, Arezoo; Ismail, Salmah

2015-08-19

This study investigated the capability of a biosurfactant produced by a novel strain of Bacillus salmalaya to enhance the biodegradation rates and bioavailability of organic contaminants. The biosurfactant produced by cultured strain 139SI showed high physicochemical properties and surface activity in the selected medium. The biosurfactant exhibited a high emulsification index and a positive result in the drop collapse test, with the results demonstrating the wetting activity of the biosurfactant and its potential to produce surface-active molecules. Strain 139SI can significantly reduce the surface tension (ST) from 70.5 to 27 mN/m, with a critical micelle concentration of 0.4%. Moreover, lubricating oil at 2% (v/v) was degraded on Day 20 (71.5). Furthermore, the biosurfactant demonstrated high stability at different ranges of salinity, pH, and temperature. Overall, the results indicated the potential use of B. salmalaya 139SI in environmental remediation processes.

Formation of continuous activated carbon fibers for barrier fabrics

NASA Astrophysics Data System (ADS)

Liang, Ying

1997-08-01

Commercial protective suits made of active carbon granules or nonwoven fabrics are heavy, have low moisture vapor transport rate, and are uncomfortable. Inherent problems due to construction of barrier fabrics lead to severe heat stress when worn for even short time in warm environments. One proposed method to eliminate these problems is to facilitate the construction of a fabric made of continuous activated carbon fibers (CACF). This study is directed toward investigating the possibility of developing CAFC from two precursors: aramid and fibrillated PAN fiber. It was shown in this study that Kevlar-29 fibers could be quickly carbonized and activated to CACF with high adsorptivity and relatively low weight loss. CACF with high surface area (>500 msp2/g) and reasonable tenacity (≈1g/denier) were successfully prepared from Kevlar fibers through a three-step process: pretreatment, carbonization, and activation. X-ray diffraction, Fourier Transform Infrared Spectroscopy (FTIR), and thermal analysis were conducted to understand the evolution of physical and chemical properties during pretreatment. The influence of temperature, heating rate, and pyrolysis environment on the thermal behavior was determined by DSC and TGA/DTA and used as an indicator for optimizing the pyrolysis conditions. Surface analysis by nitrogen isotherms indicated that the resultant fibers had micropores and mesopores on the surface of CACF. This was also inferred by studies on the surface morphology through Scanning Electron Microscopy (SEM) and Scanning Tunneling Microscopy (STM). An investigation of the surface chemical structure by X-ray photoelectron spectroscopy (XPS) before and after activation and elemental analysis confirmed that adsorption of Kevlar based CACF mainly arises due to the physisorption instead of chemisorption. A multistep stabilization along with carbonization and activation was used to prepare active carbon fiber from fibrillated PAN fiber. The resultant fiber retained its fibrillar structure and provided a very high surface area, up to 1400 msp2/g, but was brittle. The characterization of the thermal behavior, mechanical properties, and surface structure of the pyrolyzed fiber at each processing step was also carried out by using various techniques, such as DSC and TGA, Instron, and SEM. These studies provide directions for preparation of CACF from novel precursors.

Non-surface activity and micellization behavior of cationic amphiphilic block copolymer synthesized by reversible addition-fragmentation chain transfer process.

PubMed

Ghosh, Arjun; Yusa, Shin-ichi; Matsuoka, Hideki; Saruwatari, Yoshiyuki

2011-08-02

Cationic amphiphilic diblock copolymers of poly(n-butylacrylate)-b-poly(3-(methacryloylamino)propyl)trimethylammonium chloride) (PBA-b-PMAPTAC) with various hydrophobic and hydrophilic chain lengths were synthesized by a reversible addition-fragmentation chain transfer (RAFT) process. Their molecular characteristics such as surface activity/nonactivity were investigated by surface tension measurements and foam formation observation. Their micelle formation behavior and micelle structure were investigated by fluorescence probe technique, static and dynamic light scattering (SLS and DLS), etc., as a function of hydrophilic and hydrophobic chain lengths. The block copolymers were found to be non-surface active because the surface tension of the aqueous solutions did not change with increasing polymer concentration. Critical micelle concentration (cmc) of the polymers could be determined by fluorescence and SLS measurements, which means that these polymers form micelles in bulk solution, although they were non-surface active. Above the cmc, the large blue shift of the emission maximum of N-phenyl-1-naphthylamine (NPN) probe and the low micropolarity value of the pyrene probe in polymer solution indicate the core of the micelle is nonpolar in nature. Also, the high value of the relative intensity of the NPN probe and the fluorescence anisotropy of the 1,6-diphenyl-1,3,5-hexatriene (DPH) probe indicated that the core of the micelle is highly viscous in nature. DLS was used to measure the average hydrodynamic radii and size distribution of the copolymer micelles. The copolymer with the longest PBA block had the poorest water solubility and consequently formed micelles with larger size while having a lower cmc. The "non-surface activity" was confirmed for cationic amphiphilic diblock copolymers in addition to anionic ones studied previously, indicating the universality of non-surface activity nature.

Effects of Activated Carbon Surface Property on Structure and Activity of Ru/AC Catalysts

NASA Astrophysics Data System (ADS)

Xu, S. K.; Li, L. M.; Guo, N. N.

2018-05-01

The activated carbon (AC) was modified by supercritical (SC) methanol, HNO3 oxidation, or HNO3 oxidation plus SC methanol, respectively. Then, the original and the modified AC were used as supports for Ru/AC catalysts prepared via the impregnation method. The results showed that the SC methanol modification decreased the content of surface acidic groups of AC. While HNO3 oxidation displayed the opposite behavior. Furthermore, the dispersion of ruthenium and the activity of catalysts were highly dependent on the content of surface acidic groups, and the SC methanol modified sample exhibited the highest activity for hydrogenation of glucose.

A Simultaneously Antimicrobial, Protein-Repellent, and Cell-Compatible Polyzwitterion Network.

PubMed

Kurowska, Monika; Eickenscheidt, Alice; Guevara-Solarte, Diana-Lorena; Widyaya, Vania Tanda; Marx, Franziska; Al-Ahmad, Ali; Lienkamp, Karen

2017-04-10

A simultaneously antimicrobial, protein-repellent, and cell-compatible surface-attached polymer network is reported, which reduces the growth of bacterial biofilms on surfaces through its multifunctionality. The coating was made from a poly(oxonorbornene)-based zwitterion (PZI), which was surface-attached and cross-linked in one step by simultaneous UV-activated CH insertion and thiol-ene reaction. The process was applicable to both laboratory surfaces like silicon, glass, and gold and real-life surfaces like polyurethane foam wound dressings. The chemical structure and physical properties of the PZI surface and the two reference surfaces SMAMP ("synthetic mimic of an antimicrobial peptide"), an antimicrobial but protein-adhesive polymer coating, and PSB (poly(sulfobetaine)), a protein-repellent but not antimicrobial polyzwitterion coating were characterized by Fourier transform infrared spectroscopy, ellipsometry, contact angle measurements, photoelectron spectroscopy, swellability measurements (using surface plasmon resonance spectroscopy, SPR), zeta potential measurements, and atomic force microscopy. The time-dependent antimicrobial activity assay (time-kill assay) confirmed the high antimicrobial activity of the PZI; SPR was used to demonstrate that it was also highly protein-repellent. Biofilm formation studies showed that the material effectively reduced the growth of Escherichia coli and Staphylococcus aureus biofilms. Additionally, it was shown that the PZI was highly compatible with immortalized human mucosal gingiva keratinocytes and human red blood cells using the Alamar Blue assay, the live-dead stain, and the hemolysis assay. PZI thus may be an attractive coating for biomedical applications, particularly for the fight against bacterial biofilms on medical devices and in other applications.

Active sites and states in the heterogeneous catalysis of carbon-hydrogen bonds.

PubMed

Somorjai, Gabor A; Marsh, Anderson L

2005-04-15

C-H bond activation for several alkenes (ethylene, propylene, isobutene, cyclohexene and 1-hexene) and alkanes (methane, ethane, n-hexane, 2-methylpentane and 3-methylpentane) has been studied on the (111) crystal face of platinum as a function of temperature at low (10(-6) Torr) and high (>/=1 Torr) pressures in the absence and presence of hydrogen pressures (>/=10 Torr). Sum frequency generation (SFG) vibrational spectroscopy has been used to characterize the adsorbate structures and high pressure scanning tunnelling microscopy (HP-STM) has been used to monitor their surface mobility under reaction conditions during hydrogenation, dehydrogenation and CO poisoning. C-H bond dissociation occurs at low temperatures, approximately 250 K, for all of these molecules, although only at high pressures for the weakly bound alkanes because of their low desorption temperatures. Bond dissociation is known to be surface structure sensitive and we find that it is also accompanied by the restructuring of the metal surface. The presence of hydrogen slows down dehydrogenation and for some of the molecules it influences the molecular rearrangement, thus altering reaction selectivity. Surface mobility of adsorbates is essential to produce catalytic activity. When surface diffusion is inhibited by CO adsorption, ordered surface structures form and the reaction is poisoned. Ethylene hydrogenation is surface structure insensitive, while cyclohexene hydrogenation and dehydrogenation are structure sensitive. n-Hexane and other C6 alkanes form either upright or flat-lying molecules on the platinum surface which react to produce branched isomers or benzene, respectively.

Effects of copper-precursors on the catalytic activity of Cu/graphene catalysts for the selective catalytic oxidation of ammonia

NASA Astrophysics Data System (ADS)

Li, Jingying; Tang, Xiaolong; Yi, Honghong; Yu, Qingjun; Gao, Fengyu; Zhang, Runcao; Li, Chenlu; Chu, Chao

2017-08-01

Different copper-precursors were used to prepare Cu/graphene catalysts by an impregnation method. XRD, Raman spectra, TEM, BET, XPS, H2-TPR, NH3-TPD, DRIFTS and catalytic activity test were used to characterize and study the effect of precursors on the catalytic activity of Cu/graphene catalysts for NH3-SCO reaction. The large specific surface area of Cu/graphene catalysts and high dispersion of the metal particles on the graphene caused the well catalytic activity of NH3-SCO reaction. Compared to Cu/GE(AC), Cu/GE(N) showed better catalytic performance, and the complete NH3 removal efficiency was obtained at 250 °C with N2 selectivity of 85%. The copper-precursors had influence on the distribution of surface Cu species and further affected the catalytic activity of Cu/GE catalysts. The more amount of surface Cu species and highly dispersed CuO particles on the graphene surface formed by using copper nitrate as precursor could significantly improve the reducibility of catalysts and enhance NH3 adsorption, thereby improving the catalytic activity of Cu/graphene catalyst.

Molecular Insight into the Slipperiness of Ice.

PubMed

Weber, Bart; Nagata, Yuki; Ketzetzi, Stefania; Tang, Fujie; Smit, Wilbert J; Bakker, Huib J; Backus, Ellen H G; Bonn, Mischa; Bonn, Daniel

2018-05-16

Measurements of the friction coefficient of steel-on-ice over a large temperature range reveal very high friction at low temperatures (-100 °C) and a steep decrease in the friction coefficient with increasing temperature. Very low friction is only found over the limited temperature range typical for ice skating. The strong decrease in the friction coefficient with increasing temperature exhibits Arrhenius behavior with an activation energy of E a ≈ 11.5 kJ mol -1 . Remarkably, molecular dynamics simulations of the ice-air interface reveal a very similar activation energy for the mobility of surface molecules. Weakly hydrogen-bonded surface molecules diffuse over the surface in a rolling motion, their number and mobility increasing with increasing temperature. This correlation between macroscopic friction and microscopic molecular mobility indicates that slippery ice arises from the high mobility of its surface molecules, making the ice surface smooth and the shearing of the weakly bonded surface molecules easy.

High Chemical Activity of a Perovskite Surface: Reaction of CO with Sr3Ru2O7

NASA Astrophysics Data System (ADS)

Stöger, Bernhard; Hieckel, Marcel; Mittendorfer, Florian; Wang, Zhiming; Fobes, David; Peng, Jin; Mao, Zhiqiang; Schmid, Michael; Redinger, Josef; Diebold, Ulrike

2014-09-01

Adsorption of CO at the Sr3Ru2O7(001) surface was studied with low-temperature scanning tunneling microscopy (STM) and density functional theory. In situ cleaved single crystals terminate in an almost perfect SrO surface. At 78 K, CO first populates impurities and then adsorbs above the apical surface O with a binding energy Eads=-0.7 eV. Above 100 K, this physisorbed CO replaces the surface O, forming a bent CO2 with the C end bound to the Ru underneath. The resulting metal carboxylate (Ru-COO) can be desorbed by STM manipulation. A low activation (0.2 eV) and high binding (-2.2 eV) energy confirm a strong reaction between CO and regular surface sites of Sr3Ru2O7; likely, this reaction causes the "UHV aging effect" reported for this and other perovskite oxides.

Hollow microspheres with a tungsten carbide kernel for PEMFC application.

PubMed

d'Arbigny, Julien Bernard; Taillades, Gilles; Marrony, Mathieu; Jones, Deborah J; Rozière, Jacques

2011-07-28

Tungsten carbide microspheres comprising an outer shell and a compact kernel prepared by a simple hydrothermal method exhibit very high surface area promoting a high dispersion of platinum nanoparticles, and an exceptionally high electrochemically active surface area (EAS) stability compared to the usual Pt/C electrocatalysts used for PEMFC application.

Organic cloud condensation nuclei: the effect of phase, surface tension, trace soluble species, and oxidative processing on particle activation.

NASA Astrophysics Data System (ADS)

Broekhuizen, K. E.; Thornberry, T.; Abbatt, J. P.

2003-12-01

The ability of organic aerosols to act as cloud condensation nuclei (CCN) will be discussed. A variety of laboratory experiments will be presented which address several key questions concerning organic particle activation. Does the particle phase impact activation? How does surface tension play a role and can a trace amount of a surface active species impact activation? Does a trace amount of a highly soluble species impact the activation of organic particles of moderate to low solubility? Can the activation properties of organic aerosols be enhanced through oxidative processing? To systematically address these issues, the CCN activity of various diacids such as oxalic, malonic, succinic, adipic and azelaic acid have been studied, as well as the addition of trace amounts of nonanoic acid and ammonium sulfate to examine the roles of surface active and soluble species, respectively. The first examination of the role of oxidative processing on CCN activity has involved investigating the effect of ozone oxidation on the activity of oleic acid particles.

Pt Single Atoms Embedded in the Surface of Ni Nanocrystals as Highly Active Catalysts for Selective Hydrogenation of Nitro Compounds.

PubMed

Peng, Yuhan; Geng, Zhigang; Zhao, Songtao; Wang, Liangbing; Li, Hongliang; Wang, Xu; Zheng, Xusheng; Zhu, Junfa; Li, Zhenyu; Si, Rui; Zeng, Jie

2018-06-13

Single-atom catalysts exhibit high selectivity in hydrogenation due to their isolated active sites, which ensure uniform adsorption configurations of substrate molecules. Compared with the achievement in catalytic selectivity, there is still a long way to go in exploiting the catalytic activity of single-atom catalysts. Herein, we developed highly active and selective catalysts in selective hydrogenation by embedding Pt single atoms in the surface of Ni nanocrystals (denoted as Pt 1 /Ni nanocrystals). During the hydrogenation of 3-nitrostyrene, the TOF numbers based on surface Pt atoms of Pt 1 /Ni nanocrystals reached ∼1800 h -1 under 3 atm of H 2 at 40 °C, much higher than that of Pt single atoms supported on active carbon, TiO 2 , SiO 2 , and ZSM-5. Mechanistic studies reveal that the remarkable activity of Pt 1 /Ni nanocrystals derived from sufficient hydrogen supply because of spontaneous dissociation of H 2 on both Pt and Ni atoms as well as facile diffusion of H atoms on Pt 1 /Ni nanocrystals. Moreover, the ensemble composed of the Pt single atom and nearby Ni atoms in Pt 1 /Ni nanocrystals leads to the adsorption configuration of 3-nitrostyrene favorable for the activation of nitro groups, accounting for the high selectivity for 3-vinylaniline.

Highly sensitive photoelectrochemical biosensor for kinase activity detection and inhibition based on the surface defect recognition and multiple signal amplification of metal-organic frameworks.

PubMed

Wang, Zonghua; Yan, Zhiyong; Wang, Feng; Cai, Jibao; Guo, Lei; Su, Jiakun; Liu, Yang

2017-11-15

A turn-on photoelectrochemical (PEC) biosensor based on the surface defect recognition and multiple signal amplification of metal-organic frameworks (MOFs) was proposed for highly sensitive protein kinase activity analysis and inhibitor evaluation. In this strategy, based on the phosphorylation reaction in the presence of protein kinase A (PKA), the Zr-based metal-organic frameworks (UiO-66) accommodated with [Ru(bpy) 3 ] 2+ photoactive dyes in the pores were linked to the phosphorylated kemptide modified TiO 2 /ITO electrode through the chelation between the Zr 4+ defects on the surface of UiO-66 and the phosphate groups in kemptide. Under visible light irradiation, the excited electrons from [Ru(bpy) 3 ] 2+ adsorbed in the pores of UiO-66 injected into the TiO 2 conduction band to generate photocurrent, which could be utilized for protein kinase activities detection. The large surface area and high porosities of UiO-66 facilitated a large number of [Ru(bpy) 3 ] 2+ that increased the photocurrent significantly, and afforded a highly sensitive PEC analysis of kinase activity. The detection limit of the as-proposed PEC biosensor was 0.0049UmL -1 (S/N!=!3). The biosensor was also applied for quantitative kinase inhibitor evaluation and PKA activities detection in MCF-7 cell lysates. The developed visible-light PEC biosensor provides a simple detection procedure and a cost-effective manner for PKA activity assays, and shows great potential in clinical diagnosis and drug discoveries. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermal behavior and catalytic activity in naphthalene destruction of Ce-, Zr- and Mn-containing oxide layers on titanium

NASA Astrophysics Data System (ADS)

Vasilyeva, Marina S.; Rudnev, Vladimir S.; Wiedenmann, Florian; Wybornov, Svetlana; Yarovaya, Tatyana P.; Jiang, Xin

2011-11-01

The present paper is devoted to studies of the composition and surface structure, including those after annealing at high temperatures, and catalytic activity in the reaction of naphthalene destruction of Ce-, Zr- and Mn-containing oxide layers on titanium obtained by means of the plasma electrolytic oxidation (PEO) method. The composition and structure of the obtained systems were investigated using the methods of X-ray phase and energy dispersive analysis and scanning electron microscopy (SEM). It was demonstrated that Ce- and Zr- containing structures had relatively high thermal stability: their element and phase compositions and surface structure underwent virtually no changes after annealing in the temperature range 600-800 °C. Annealing of Ce- and Zr-containing coatings in the temperature range 850-900 °C resulted in substantial changes of their surface composition and structure: a relatively homogeneous and porous surface becomes coated by large pole-like crystals. The catalytic studies showed rather high activity of Ce- and Zr-containing coatings in the reaction of naphthalene destruction at temperatures up to 850 °C. Mn-containing structures of the type MnOx + SiO2 + TiO2/Ti have a well-developed surface coated by “nano-whiskers”. The phase composition and surface structure of manganese-containing layers changes dramatically in the course of thermal treatment. After annealing above 600 °C nano-whiskers vanish with formation of molten structures on the surface. The Mn-containing oxide systems demonstrated lower conversion degrees than the Ce- and Zr-containing coatings, which can be attributed to substantial surface modification and formation of molten manganese silicates at high temperatures.

Activities of the Vastus Lateralis and Vastus Medialis Oblique Muscles during Squats on Different Surfaces.

PubMed

Hyong, In Hyouk; Kang, Jong Ho

2013-08-01

[Purpose] The purpose of the present study was to examine the effects of squat exercises performed on different surfaces on the activity of the quadriceps femoris muscle in order to provide information on support surfaces for effective squat exercises. [Subjects and Method] Fourteen healthy subjects performed squat exercises for five seconds each on three different support surfaces: hard plates, foam, and rubber air discs. Their performance was measured using electromyography. As the subjects performed the squat exercises on each surface, data on the activity of the vastus medialis oblique and the vastus lateralis, and the vastus medials oblique/vastus lateralis ratio, were collected. [Results] The activity of the vastus medialis oblique and the vastus medialis oblique/vastus lateralis ratio were found to be statistically significantly higher on rubber air discs than when the squats were performed on hard plates or foam. [Conclusion] To activate the vastus medialis obilique, and to enhance the vastus medialis oblique/vastus lateralis ratio, unstable surfaces that are highly unstable should be selected.

Effect of surface condition on the formation of solid lubricating films at high temperatures

NASA Technical Reports Server (NTRS)

Hanyaloglu, Bengi; Graham, E. E.

1992-01-01

Solid films were produced on active metal or ceramic surfaces using lubricants (such as tricresyl phosphate) delivered as a vapor at high temperatures, and the lubricity of these deposits under different dynamic wear conditions was investigated. A method is described for chemically activating ceramic surfaces resulting in a surface that could promote the formation of lubricating polymeric derivative of TCP. Experiments were carried out to evaluate the wear characteristics of unlubricated cast iron and of Sialon ceramic at 25 and 280 C, and lubricated with a vapor of TCP at 280 C. It is shown that continuous vapor phase lubrication of chemically treated Sialon reduced its coefficient of friction from 0.7 to less than 0.1.

Ultrahigh Surface Area Three-Dimensional Porous Graphitic Carbon from Conjugated Polymeric Molecular Framework

PubMed Central

2015-01-01

Porous graphitic carbon is essential for many applications such as energy storage devices, catalysts, and sorbents. However, current graphitic carbons are limited by low conductivity, low surface area, and ineffective pore structure. Here we report a scalable synthesis of porous graphitic carbons using a conjugated polymeric molecular framework as precursor. The multivalent cross-linker and rigid conjugated framework help to maintain micro- and mesoporous structures, while promoting graphitization during carbonization and chemical activation. The above unique design results in a class of highly graphitic carbons at temperature as low as 800 °C with record-high surface area (4073 m2 g–1), large pore volume (2.26 cm–3), and hierarchical pore architecture. Such carbons simultaneously exhibit electrical conductivity >3 times more than activated carbons, very high electrochemical activity at high mass loading, and high stability, as demonstrated by supercapacitors and lithium–sulfur batteries with excellent performance. Moreover, the synthesis can be readily tuned to make a broad range of graphitic carbons with desired structures and compositions for many applications. PMID:27162953

Ultrahigh Surface Area Three-Dimensional Porous Graphitic Carbon from Conjugated Polymeric Molecular Framework

DOE PAGES

To, John W. F.; Chen, Zheng; Yao, Hongbin; ...

2015-05-18

Porous graphitic carbon is essential for many applications such as energy storage devices, catalysts, and sorbents. However, current graphitic carbons are limited by low conductivity, low surface area, and ineffective pore structure. Here we report a scalable synthesis of porous graphitic carbons using a conjugated polymeric molecular framework as precursor. The multivalent cross-linker and rigid conjugated framework help to maintain micro- and mesoporous structures, while promoting graphitization during carbonization and chemical activation. The above unique design results in a class of highly graphitic carbons at temperature as low as 800 °C with record-high surface area (4073 m 2 g –1),more » large pore volume (2.26 cm –3), and hierarchical pore architecture. Such carbons simultaneously exhibit electrical conductivity >3 times more than activated carbons, very high electrochemical activity at high mass loading, and high stability, as demonstrated by supercapacitors and lithium–sulfur batteries with excellent performance. Moreover, the synthesis can be readily tuned to make a broad range of graphitic carbons with desired structures and compositions for many applications.« less

Controlled Defects of Zinc Oxide Nanorods for Efficient Visible Light Photocatalytic Degradation of Phenol

PubMed Central

Al-Sabahi, Jamal; Bora, Tanujjal; Al-Abri, Mohammed; Dutta, Joydeep

2016-01-01

Environmental pollution from human and industrial activities has received much attention as it adversely affects human health and bio-diversity. In this work we report efficient visible light photocatalytic degradation of phenol using supported zinc oxide (ZnO) nanorods and explore the role of surface defects in ZnO on the visible light photocatalytic activity. ZnO nanorods were synthesized on glass substrates using a microwave-assisted hydrothermal process, while the surface defect states were controlled by annealing the nanorods at various temperatures and were characterized by photoluminescence and X-ray photoelectron spectroscopy. High performance liquid chromatography (HPLC) was used for the evaluation of phenol photocatalytic degradation. ZnO nanorods with high surface defects exhibited maximum visible light photocatalytic activity, showing 50% degradation of 10 ppm phenol aqueous solution within 2.5 h, with a degradation rate almost four times higher than that of nanorods with lower surface defects. The mineralization process of phenol during degradation was also investigated, and it showed the evolution of different photocatalytic byproducts, such as benzoquinone, catechol, resorcinol and carboxylic acids, at different stages. The results from this study suggest that the presence of surface defects in ZnO nanorods is crucial for its efficient visible light photocatalytic activity, which is otherwise only active in the ultraviolet region. PMID:28773363

Controlled Defects of Zinc Oxide Nanorods for Efficient Visible Light Photocatalytic Degradation of Phenol.

PubMed

Al-Sabahi, Jamal; Bora, Tanujjal; Al-Abri, Mohammed; Dutta, Joydeep

2016-03-28

Environmental pollution from human and industrial activities has received much attention as it adversely affects human health and bio-diversity. In this work we report efficient visible light photocatalytic degradation of phenol using supported zinc oxide (ZnO) nanorods and explore the role of surface defects in ZnO on the visible light photocatalytic activity. ZnO nanorods were synthesized on glass substrates using a microwave-assisted hydrothermal process, while the surface defect states were controlled by annealing the nanorods at various temperatures and were characterized by photoluminescence and X-ray photoelectron spectroscopy. High performance liquid chromatography (HPLC) was used for the evaluation of phenol photocatalytic degradation. ZnO nanorods with high surface defects exhibited maximum visible light photocatalytic activity, showing 50% degradation of 10 ppm phenol aqueous solution within 2.5 h, with a degradation rate almost four times higher than that of nanorods with lower surface defects. The mineralization process of phenol during degradation was also investigated, and it showed the evolution of different photocatalytic byproducts, such as benzoquinone, catechol, resorcinol and carboxylic acids, at different stages. The results from this study suggest that the presence of surface defects in ZnO nanorods is crucial for its efficient visible light photocatalytic activity, which is otherwise only active in the ultraviolet region.

Protein quantification on dendrimer-activated surfaces by using time-of-flight secondary ion mass spectrometry and principal component regression

NASA Astrophysics Data System (ADS)

Kim, Young-Pil; Hong, Mi-Young; Shon, Hyun Kyong; Chegal, Won; Cho, Hyun Mo; Moon, Dae Won; Kim, Hak-Sung; Lee, Tae Geol

2008-12-01

Interaction between streptavidin and biotin on poly(amidoamine) (PAMAM) dendrimer-activated surfaces and on self-assembled monolayers (SAMs) was quantitatively studied by using time-of-flight secondary ion mass spectrometry (ToF-SIMS). The surface protein density was systematically varied as a function of protein concentration and independently quantified using the ellipsometry technique. Principal component analysis (PCA) and principal component regression (PCR) were used to identify a correlation between the intensities of the secondary ion peaks and the surface protein densities. From the ToF-SIMS and ellipsometry results, a good linear correlation of protein density was found. Our study shows that surface protein densities are higher on dendrimer-activated surfaces than on SAMs surfaces due to the spherical property of the dendrimer, and that these surface protein densities can be easily quantified with high sensitivity in a label-free manner by ToF-SIMS.

UV light induced surface modification of HDPE films with bioactive compounds

NASA Astrophysics Data System (ADS)

Daniloska, Vesna; Blazevska-Gilev, Jadranka; Dimova, Vesna; Fajgar, Radek; Tomovska, Radmila

2010-01-01

The development of different techniques for surface modification of polymers becomes popular in a last decade. These techniques preserve useful bulk polymer properties unchanged, while the activation of the polymer surface offers more possibilities for polymer applications. In this work, a new, one-step method for bio-activation of HDPE (high density polyethylene) surface by UV irradiation is presented. HDPE films coupled with selected active compound and a photoinitiator was treated by UV lamp, emitting light at 254 nm. For surface functionalization of HDPE films, the following compounds were employed: 2-aminopyridine (AP), N 1-(2-pyridylaminomethyl)-1,2,4-triazole (TA) and benzocaine (BC). The influence of irradiation time on the extent of surface changes was investigated. The modified polymer surfaces were investigated by Fourier transformed infrared (FTIR) and Raman spectroscopy, scanning electron microscopy (SEM) and contact angle measurements, demonstrating successful functionalization of HDPE surface.

Asphalt-derived high surface area activated porous carbons for carbon dioxide capture.

PubMed

Jalilov, Almaz S; Ruan, Gedeng; Hwang, Chih-Chau; Schipper, Desmond E; Tour, Josiah J; Li, Yilun; Fei, Huilong; Samuel, Errol L G; Tour, James M

2015-01-21

Research activity toward the development of new sorbents for carbon dioxide (CO2) capture have been increasing quickly. Despite the variety of existing materials with high surface areas and high CO2 uptake performances, the cost of the materials remains a dominant factor in slowing their industrial applications. Here we report preparation and CO2 uptake performance of microporous carbon materials synthesized from asphalt, a very inexpensive carbon source. Carbonization of asphalt with potassium hydroxide (KOH) at high temperatures (>600 °C) yields porous carbon materials (A-PC) with high surface areas of up to 2780 m(2) g(-1) and high CO2 uptake performance of 21 mmol g(-1) or 93 wt % at 30 bar and 25 °C. Furthermore, nitrogen doping and reduction with hydrogen yields active N-doped materials (A-NPC and A-rNPC) containing up to 9.3% nitrogen, making them nucleophilic porous carbons with further increase in the Brunauer-Emmett-Teller (BET) surface areas up to 2860 m(2) g(-1) for A-NPC and CO2 uptake to 26 mmol g(-1) or 114 wt % at 30 bar and 25 °C for A-rNPC. This is the highest reported CO2 uptake among the family of the activated porous carbonaceous materials. Thus, the porous carbon materials from asphalt have excellent properties for reversibly capturing CO2 at the well-head during the extraction of natural gas, a naturally occurring high pressure source of CO2. Through a pressure swing sorption process, when the asphalt-derived material is returned to 1 bar, the CO2 is released, thereby rendering a reversible capture medium that is highly efficient yet very inexpensive.

Hydrothermal Carbonization of Microalgae (Chlorococcum sp.) for Porous Carbons With High Cr(VI) Adsorption Performance.

PubMed

Sun, Yuanyuan; Liu, Chang; Zan, Yifan; Miao, Gai; Wang, Hao; Kong, Lingzhao

2018-04-12

Porous carbon adsorbents were prepared from microalgae (Chlorococcum sp.) via directly hydrothermal carbonization coupled with KOH or NH 3 activation for Cr(VI) adsorption. KOH-activated porous carbons exhibit high Cr(VI) adsorption capacities than those obtained via NH 3 modification (370.37 > 95.70 mg/g). The superior Cr(VI) adsorption capacity is due to high surface areas (1784 m 2 /g) and pore volumes of porous carbon with mesoporous and macroporous structures. The Cr(VI) adsorption result was well fitted to the Langmuir model, showing that the removal of Cr(VI) was attributed to the monolayer adsorption of activity site on carbon surface.

A sinter-resistant catalytic system fabricated by maneuvering the selectivity of SiO2 deposition onto the TiO2 surface versus the Pt nanoparticle surface.

PubMed

Lu, Ping; Campbell, Charles T; Xia, Younan

2013-10-09

A triphasic catalytic system (Pt/TiO2-SiO2) with an "islands in the sea" configuration was fabricated by controlling the selectivity of SiO2 deposition onto the surface of TiO2 versus the surface of Pt nanoparticles. The Pt surface was exposed, while the nanoparticles were supported on TiO2 and isolated from each other by SiO2 to achieve both significantly improved sinter resistance up to 700 °C and outstanding activity after high-temperature calcination. This work not only demonstrates the feasibility of using a new triphasic system with uncovered catalyst to maximize the thermal stability and catalytic activity but also offers a general approach to the synthesis of high-performance catalytic systems with tunable compositions.

Mechano-Electrochemical Interaction Gives Rise to Strain Relaxation in Sn Electrodes

DOE PAGES

Barai, Pallab; Huang, Bo; Dillon, Shen J.; ...

2016-01-01

Tin (Sn) anode active particles were electrochemically lithiated during simultaneous imaging in a scanning electron microscope. Relationships among the reaction mechanism, active particle local strain rate, particle size, and microcrack formation are elucidated to demonstrate the importance of strain relaxation due to mechano-electrochemical interaction in Sn-based electrodes under electrochemical cycling. At low rates of operation, due to significant creep relaxation, large Sn active particles, of size 1 μm, exhibit no significant surface crack formation. Microcrack formation within Sn active particles occurs due to two different mechanisms: (i)large concentration gradient induced stress at the two-phase interface, and (ii) high volume expansionmore » induced stress at the surface of the active particles. From the present study, it can be concluded that majority of the microcracks evolve at or near the particle surface due to high volume expansion induced tension. Concentration gradient induced damage prevails near the center of the active particle, though significantly smaller in magnitude. Comparison with experimental results indicates that at operating conditions of C/2, even 500 nm sized Sn active particles remain free from surface crack formation, which emphasizes the importance of creep relaxation. A phase map has been developed to demonstrate the preferred mechano-electrochemical window of operation of Sn-based electrodes.« less

Density Functional Theory Simulations of Water Adsorption and Activation on the (-201) β-Ga2 O3 Surface.

PubMed

Anvari, Roozbeh; Spagnoli, Dino; Parish, Giacinta; Nener, Brett

2018-03-09

Density functional theory calculations are used to study the molecular and dissociative adsorption of water on the (-201) β-Ga 2 O 3 surface. The effect of adsorption of different water-like species on the geometry, binding energies, vibrational spectra and the electronic structure of the surface are discussed. The study shows that although the hydrogen evolution reaction requires a small amount of energy to become energetically favourable, the over potential for activating the oxygen evolution reaction is quite high. The results of our calculations provide insight as to why a high voltage is required in experiments to activate the water-splitting reaction, whereas previous studies of gallium oxide predicted very low activation energies for other energetically more favourable facets. Application of this work to studies of GaN-based chemical sensors with gallium oxide surfaces shows that it is possible to select the gate bias so that the sensors are not influenced by water-splitting reactions. It was also found that in the region where water splitting does not occur, the surface can exist in two states, that is, water or hydroxyl terminated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Potent antitumor activity of a urokinase-activated engineered anthrax toxin

NASA Astrophysics Data System (ADS)

Liu, Shihui; Aaronson, Hannah; Mitola, David J.; Leppla, Stephen H.; Bugge, Thomas H.

2003-01-01

The acquisition of cell-surface urokinase plasminogen activator activity is a hallmark of malignancy. We generated an engineered anthrax toxin that is activated by cell-surface urokinase in vivo and displays limited toxicity to normal tissue but broad and potent tumoricidal activity. Native anthrax toxin protective antigen, when administered with a chimeric anthrax toxin lethal factor, Pseudomonas exotoxin fusion protein, was extremely toxic to mice, causing rapid and fatal organ damage. Replacing the furin activation sequence in anthrax toxin protective antigen with an artificial peptide sequence efficiently activated by urokinase greatly attenuated toxicity to mice. In addition, the mutation conferred cell-surface urokinase-dependent toxin activation in vivo, as determined by using a panel of plasminogen, plasminogen activator, plasminogen activator receptor, and plasminogen activator inhibitor-deficient mice. Surprisingly, toxin activation critically depended on both urokinase plasminogen activator receptor and plasminogen in vivo, showing that both proteins are essential cofactors for the generation of cell-surface urokinase. The engineered toxin displayed potent tumor cell cytotoxicity to a spectrum of transplanted tumors of diverse origin and could eradicate established solid tumors. This tumoricidal activity depended strictly on tumor cell-surface plasminogen activation. The data show that a simple change of protease activation specificity converts anthrax toxin from a highly lethal to a potent tumoricidal agent.

Surface-enhanced raman spectroscopy substrate for arsenic sensing in groundwater

DOEpatents

Yang, Peidong; Mulvihill, Martin; Tao, Andrea R.; Sinsermsuksakul, Prasert; Arnold, John

2015-06-16

A surface-enhanced Raman spectroscopy (SERS) substrate formed from a plurality of monolayers of polyhedral silver nanocrystals, wherein at least one of the monolayers has polyvinypyrrolidone (PVP) on its surface, and thereby configured for sensing arsenic is described. Highly active SERS substrates are formed by assembling high density monolayers of differently shaped silver nanocrystals onto a solid support. SERS detection is performed directly on this substrate by placing a droplet of the analyte solution onto the nanocrystal monolayer. Adsorbed polymer, polyvinypyrrolidone (PVP), on the surface of the nanoparticles facilitates the binding of both arsenate and arsenite near the silver surface, allowing for highly accurate and sensitive detection capabilities.

Shallow seismic imaging of folds above the Puente Hills blind-thrust fault, Los Angeles, California

USGS Publications Warehouse

Pratt, T.L.; Shaw, J.H.; Dolan, J.F.; Christofferson, S.A.; Williams, R.A.; Odum, J.K.; Plesch, A.

2002-01-01

High-resolution seismic reflection profiles image discrete folds in the shallow subsurface (<600 m) above two segments of the Puente Hills blind-thrust fault system, Los Angeles basin, California. The profiles demonstrate late Quaternary activity at the fault tip, precisely locate the axial surfaces of folds within the upper 100 m, and constrain the geometry and kinematics of recent folding. The Santa Fe Springs segment of the Puente Hills fault zone shows an upward-narrowing kink band with an active anticlinal axial surface, consistent with fault-bend folding above an active thrust ramp. The Coyote Hills segment shows an active synclinal axial surface that coincides with the base of a 9-m-high scarp, consistent with tip-line folding or the presence of a backthrust. The seismic profiles pinpoint targets for future geologic work to constrain slip rates and ages of past events on this important fault system.

A highly permeable and enhanced surface area carbon-cloth electrode for vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Zhou, X. L.; Zhao, T. S.; Zeng, Y. K.; An, L.; Wei, L.

2016-10-01

In this work, a high-performance porous electrode, made of KOH-activated carbon-cloth, is developed for vanadium redox flow batteries (VRFBs). The macro-scale porous structure in the carbon cloth formed by weaving the carbon fibers in an ordered manner offers a low tortuosity (∼1.1) and a broad pore distribution from 5 μm to 100 μm, rendering the electrode a high hydraulic permeability and high effective ionic conductivity, which are beneficial for the electrolyte flow and ion transport through the porous electrode. The use of KOH activation method to create nano-scale pores on the carbon-fiber surfaces leads to a significant increase in the surface area for redox reactions from 2.39 m2 g-1 to 15.4 m2 g-1. The battery assembled with the present electrode delivers an energy efficiency of 80.1% and an electrolyte utilization of 74.6% at a current density of 400 mA cm-2, as opposed to an electrolyte utilization of 61.1% achieved by using a conventional carbon-paper electrode. Such a high performance is mainly attributed to the combination of the excellent mass/ion transport properties and the high surface area rendered by the present electrode. It is suggested that the KOH-activated carbon-cloth electrode is a promising candidate in redox flow batteries.

High-performance all-solid-state flexible supercapacitors based on two-step activated carbon cloth

NASA Astrophysics Data System (ADS)

Jiang, Shulan; Shi, Tielin; Zhan, Xiaobin; Long, Hu; Xi, Shuang; Hu, Hao; Tang, Zirong

2014-12-01

A simple and effective strategy is proposed to activate carbon cloth for the fabrication of flexible and high-performance supercapacitors. Firstly, the carbon cloth surface is exfoliated as nanotextures through wet chemical treatment, then an annealing process is applied at H2/N2 atmosphere to reduce the surface oxygen functional groups which are mainly introduced from the first step. The activated carbon cloth electrode shows excellent wettablity, large surface area and delivers remarkable electrochemical performance. A maximum areal capacitance of 485.64 mF cm-2 at the current density of 2 mA cm-2 is achieved for the activated carbon cloth electrode, which is considerably larger than the resported results for carbon cloth. Furthermore, the flexible all-solid-state supercapacitor, which is fabricated based on the activated carbon cloth electrodes, shows high areal capacitance, superior cycling stability as well as stable electrochemical performance even under constant bending or twisting conditions. An areal capacitance of 161.28 mF cm-2 is achieved at the current density of 12.5 mA cm-2, and 104% of its initial capacitance is retained after 30,000 charging/discharging cycles. This study would also provide an effective way to boost devices' electrochemical performance by accommodating other active materials on the activated carbon cloth.

A Comparison of Blood Factor XII Autoactivation in Buffer, Protein Cocktail, Serum, and Plasma Solutions

PubMed Central

Golas, Avantika; Yeh, Chyi-Huey Josh; Pitakjakpipop, Harit; Siedlecki, Christopher A.; Vogler, Erwin A.

2012-01-01

Activation of blood plasma coagulation in vitro by contact with material surfaces is demonstrably dependent on plasma-volume-to-activator-surface-area ratio. The only plausible explanation consistent with current understanding of coagulation-cascade biochemistry is that procoagulant stimulus arising from the activation complex of the intrinsic pathway is dependent on activator surface area. And yet, it is herein shown that activation of the blood zymogen factor XII (Hageman factor, FXII) dissolved in buffer, protein cocktail, heat-denatured serum, and FXI deficient plasma does not exhibit activator surface-area dependence. Instead, a highly-variable burst of procoagulant-enzyme yield is measured that exhibits no measurable kinetics, sensitivity to mixing, or solution-temperature dependence. Thus, FXII activation in both buffer and protein-containing solutions does not exhibit characteristics of a biochemical reaction but rather appears to be a “mechanochemical” reaction induced by FXII molecule interactions with hydrophilic activator particles that do not formally adsorb blood proteins from solution. Results of this study strongly suggest that activator surface-area dependence observed in contact activation of plasma coagulation does not solely arise at the FXII activation step of the intrinsic pathway. PMID:23117212

Exceptional oxygen reduction reaction activity and durability of platinum–nickel nanowires through synthesis and post-treatment optimization

DOE PAGES

Alia, Shaun M.; Ngo, Chilan; Shulda, Sarah; ...

2017-04-11

For the first time, extended nanostructured catalysts are demonstrated with both high specific activity (>6000 μA cm Pt –2 at 0.9 V) and high surface areas (>90 m 2 g Pt –1). Platinum–nickel (Pt—Ni) nanowires, synthesized by galvanic displacement, have previously produced surface areas in excess of 90 m 2 g Pt –1, a significant breakthrough in and of itself for extended surface catalysts. Unfortunately, these materials were limited in terms of their specific activity and durability upon exposure to relevant electrochemical test conditions. Through a series of optimized postsynthesis steps, significant improvements were made to the activity (3-fold increasemore » in specific activity), durability (21% mass activity loss reduced to 3%), and Ni leaching (reduced from 7 to 0.3%) of the Pt—Ni nanowires. Finally, these materials show more than a 10-fold improvement in mass activity compared to that of traditional carbon-supported Pt nanoparticle catalysts and offer significant promise as a new class of electrocatalysts in fuel cell applications.« less

Exceptional oxygen reduction reaction activity and durability of platinum–nickel nanowires through synthesis and post-treatment optimization

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

Alia, Shaun M.; Ngo, Chilan; Shulda, Sarah

For the first time, extended nanostructured catalysts are demonstrated with both high specific activity (>6000 μA cm Pt –2 at 0.9 V) and high surface areas (>90 m 2 g Pt –1). Platinum–nickel (Pt—Ni) nanowires, synthesized by galvanic displacement, have previously produced surface areas in excess of 90 m 2 g Pt –1, a significant breakthrough in and of itself for extended surface catalysts. Unfortunately, these materials were limited in terms of their specific activity and durability upon exposure to relevant electrochemical test conditions. Through a series of optimized postsynthesis steps, significant improvements were made to the activity (3-fold increasemore » in specific activity), durability (21% mass activity loss reduced to 3%), and Ni leaching (reduced from 7 to 0.3%) of the Pt—Ni nanowires. Finally, these materials show more than a 10-fold improvement in mass activity compared to that of traditional carbon-supported Pt nanoparticle catalysts and offer significant promise as a new class of electrocatalysts in fuel cell applications.« less

Protection of Nonself Surfaces from Complement Attack by Factor H-Binding Peptides: Implications for Therapeutic Medicine

PubMed Central

Wu, You-Qiang; Qu, Hongchang; Sfyroera, Georgia; Tzekou, Apostolia; Kay, Brian K.; Nilsson, Bo; Ekdahl, Kristina Nilsson; Ricklin, Daniel; Lambris, John D.

2011-01-01

Exposure of nonself surfaces such as those of biomaterials or transplanted cells and organs to host blood frequently triggers innate immune responses, thereby affecting both their functionality and tolerability. Activation of the alternative pathway of complement plays a decisive role in this unfavorable reaction. Whereas previous studies demonstrated that immobilization of physiological regulators of complement activation (RCA) can attenuate this foreign body-induced activation, simple and efficient approaches for coating artificial surfaces with intact RCA are still missing. The conjugation of small molecular entities that capture RCA with high affinity is an intriguing alternative, as this creates a surface with autoregulatory activity upon exposure to blood. We therefore screened two variable cysteine-constrained phage-displayed peptide libraries for factor H-binding peptides. We discovered three peptide classes that differed with respect to their main target binding areas. Peptides binding to the broad middle region of factor H (domains 5–18) were of particular interest, as they do not interfere with either regulatory or binding activities. One peptide in this group (5C6) was further characterized and showed high factor H-capturing activity while retaining its functional integrity. Most importantly, when 5C6 was coated to a model polystyrene surface and exposed to human lepirudin-anticoagulated plasma, the bound peptide captured factor H and substantially inhibited complement activation by the alternative pathway. Our study therefore provides a promising and novel approach to produce therapeutic materials with enhanced biocompatibility. PMID:21339361

Construction of high-energy-density supercapacitors from pine-cone-derived high-surface-area carbons.

PubMed

Karthikeyan, Kaliyappan; Amaresh, Samuthirapandiyan; Lee, Sol Nip; Sun, Xueliang; Aravindan, Vanchiappan; Lee, Young-Gi; Lee, Yun Sung

2014-05-01

Very high surface area activated carbons (AC) are synthesized from pine cone petals by a chemical activation process and subsequently evaluated as an electrode material for supercapacitor applications in a nonaqueous medium. The maximum specific surface area of ∼3950 m(2)  g(-1) is noted for the material treated with a 1:5 ratio of KOH to pine cone petals (PCC5), which is much higher than that reported for carbonaceous materials derived from various other biomass precursors. A symmetric supercapacitor is fabricated with PCC5 electrodes, and the results showed enhanced supercapacitive behavior with the highest energy density of ∼61 Wh kg(-1). Furthermore, outstanding cycling ability is evidenced for such a configuration, and ∼90 % of the initial specific capacitance after 20,000 cycles under harsh conditions was observed. This result revealed that the pine-cone-derived high-surface-area AC can be used effectively as a promising electrode material to construct high-energy-density supercapacitors. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical State of Surface Oxygen on Carbon and Its Effects on the Capacity of the Carbon Anode in a Lithium-Ion Battery Investigated

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh

2001-01-01

In a lithium-ion battery, the lithium-storage capacity of the carbon anode is greatly affected by a surface layer formed during the first half cycle of lithium insertion and release into and out of the carbon anode. The formation of this solid-electrolyte interface, in turn, is affected by the chemistry of the carbon surface. A study at the NASA Glenn Research Center examined the cause-and-effect relations. Information obtained from this research could contribute in designing a high-capacity lithium-ion battery and, therefore, small, powerful spacecraft. In one test, three types of surfaces were examined: (1) a surface with low oxygen content (1.5 at.%) and a high concentration of active sites, (2) a surface with 4.5 at.% -OH or -OC type oxygen, and (3) a surface with 6.5 at.% O=C type oxygen. The samples were made from the same precursor and had similar bulk properties. They were tested under a constant current of 10 mA/g in half cells that used lithium metal as the counter electrode and 0.5 M lithium iodide in 50/50 (vol%) ethylene carbonate and dimethyl carbonate as the electrolyte. For the first cycle of the electrochemical test, the graph describes the voltage of the carbon anode versus the lithium metal as a function of the capacity (amount of lithium insertion or release). From these data, it can be observed that the surface with low oxygen and a high concentration of active sites could result in a high irreversible capacity. Such a high irreversible capacity could be prevented if the active sites were allowed to react with oxygen in air, producing -OH or -OC type oxygen. The O=C type oxygen, on the other hand, could greatly reduce the capacity of lithium intercalation and, therefore, needs to be avoided during battery fabrication.

Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces

DOE PAGES

Chen, Chen; Kang, Yijin; Huo, Ziyang; ...

2014-02-27

Control of structure at the atomic level can precisely and effectively tune catalytic properties of materials, enabling enhancement in both activity and durability. We synthesized a highly active and durable class of electrocatalysts by exploiting the structural evolution of platinum-nickel (Pt-Ni) bimetallic nanocrystals. The starting material, crystalline PtNi 3 polyhedra, transforms in solution by interior erosion into Pt 3Ni nanoframes with surfaces that offer three-dimensional molecular accessibility. The edges of the Pt-rich PtNi 3 polyhedra are maintained in the final Pt 3Ni nanoframes. Both the interior and exterior catalytic surfaces of this open-framework structure are composed of the nanosegregated Pt-skinmore » structure, which exhibits enhanced oxygen reduction reaction (ORR) activity. The Pt 3Ni nanoframe catalysts achieved a factor of 36 enhancement in mass activity and a factor of 22 enhancement in specific activity, respectively, for this reaction (relative to state-of-the-art platinum-carbon catalysts) during prolonged exposure to reaction conditions.« less

Controlling porosity in lignin-derived nanoporous carbon for supercapacitor applications

DOE PAGES

Jeon, Ju-Won; Zhang, Libing; Lutkenhaus, Jodie L.; ...

2015-02-01

Low-cost renewable lignin has been used as a precursor to produce porous carbons. However, to date, it has not been easy to obtain high surface area porous carbon without activation processes or templating agents. Here, we demonstrate that low molecular weight lignin yields highly porous carbon (1092 m² g⁻¹) with more graphitization through direct carbonization without additional activation processes or templating agents. We found that molecular weight and oxygen consumption during carbonization are critical factors to obtain high surface area, graphitized porous carbons. This highly porous carbon from low-cost renewable lignin sources is a good candidate for supercapacitor electrode materials.

Controlling porosity in lignin-derived nanoporous carbon for supercapacitor applications

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

Jeon, Ju-Won; Zhang, Libing; Lutkenhaus, Jodie L.

Low-cost renewable lignin has been used as a precursor to produce porous carbons. However, to date, it has not been easy to obtain high surface area porous carbon without activation processes or templating agents. Here, we demonstrate that low molecular weight lignin yields highly porous carbon (1092 m² g⁻¹) with more graphitization through direct carbonization without additional activation processes or templating agents. We found that molecular weight and oxygen consumption during carbonization are critical factors to obtain high surface area, graphitized porous carbons. This highly porous carbon from low-cost renewable lignin sources is a good candidate for supercapacitor electrode materials.

The theory of cyclic voltammetry of electrochemically heterogeneous surfaces: comparison of different models for surface geometry and applications to highly ordered pyrolytic graphite.

PubMed

Ward, Kristopher R; Lawrence, Nathan S; Hartshorne, R Seth; Compton, Richard G

2012-05-28

The cyclic voltammetry at electrodes composed of multiple electroactive materials, where zones of one highly active material are distributed over a substrate of a second, less active material, is investigated by simulation. The two materials are assumed to differ in terms of their electrochemical rate constants towards any given redox couple. For a one-electron oxidation or reduction, the effect on voltammetry of the size and relative surface coverages of the zones as well as the rate constant of the slower zone are considered for systems where it is much slower than the rate constant of the faster zones. The occurrence of split peak cyclic voltammetry where two peaks are observed in the forward sweep, is studied in terms of the diffusional effects present in the system. A number of surface geometries are compared: specifically the more active zones are modelled as long, thin bands, as steps in the surface, as discs, and as rings (similar to a partially blocked electrode). Similar voltammetry for the band, step and ring models is seen but the disc geometry shows significant differences. Finally, the simulation technique is applied to the modelling of highly-ordered pyrolytic graphite (HOPG) surface and experimental conditions under which it may be possible to observe split peak voltammetry are predicted.

Regulating Surface Facets of Metallic Aerogel Electrocatalysts by Size-dependent Localized Ostwald Ripening.

PubMed

Wenchao, Duan; Zhang, Peina; Xiahou, Yujiao; Song, Yahui; Bi, Cuixia; Zhan, Jie; Du, Wei; Huang, Lihui; Möhwald, Helmuth; Xia, Haibing

2018-06-21

It is well known that the activity and stability of electrocatalysts are largely dependent on their surface facets. In this work, we have successfully regulated surface facets of three-dimensional (3D) metallic Au m-n aerogels by salt-induced assembly of citrate-stabilized gold nanoparticles (Au NPs) of two different sizes and further size-dependent localized Ostwald ripening at controlled particle-number ratios, where m and n represent the size of Au NPs, respectively. In addition, 3D Au m-n @Pd aerogels were further synthesized on the basis of Au m-n aerogels and also bear controlled surface facets due to the formation of ultrathin Pd layers on Au m-n aerogels. Taking the electrooxidation of small organic molecules (such as methanol and ethanol) by the resulting Au m-n and Au m-n @Pd aerogels as examples, it is found that surface facets of metallic aerogels with excellent performance can be regulated to realize preferential surface facets for methanol oxidation and ethanol oxidation, respectively. Moreover, they also indeed simultaneously bear high activity and excellent stability. Furthermore, their activities and stability are also highly dependent on the area ratio of active facets and inactive facets on their surfaces, respectively, and these ratios are varied via the mismatch of sizes of adjacent nanoparticles. Thus, this work not only demonstrates the realization of the regulation of the surface facets of metallic aerogels by size-dependent localized Ostwald ripening, but also will open up a new way to improve electrocatalytic performance of three-dimensional metallic aerogels by surface regulation.

High-surface-area, dual-function oxygen electrocatalysts for space power applications

NASA Technical Reports Server (NTRS)

Ham, David O.; Moniz, Gary; Taylor, E. Jennings

1987-01-01

The processes of hydration/dehydration and carbonation/decarbonation are investigated as an approach to provide higher surface area mixed metal oxides that are more active electrochemically. These materials are candidates for use as electrocatalysts and electrocatalyst supports for alkaline electrolyzers and fuel cells. For the case of the perovskite, LaCoO3 , higher surface areas were achieved with no change in structure and a more active oxygen electrocatalyst.

Grain-boundary-dependent CO2 electroreduction activity.

PubMed

Feng, Xiaofeng; Jiang, Kaili; Fan, Shoushan; Kanan, Matthew W

2015-04-15

Uncovering new structure-activity relationships for metal nanoparticle (NP) electrocatalysts is crucial for advancing many energy conversion technologies. Grain boundaries (GBs) could be used to stabilize unique active surfaces, but a quantitative correlation between GBs and catalytic activity has not been established. Here we use vapor deposition to prepare Au NPs on carbon nanotubes (Au/CNT). As deposited, the Au NPs have a relatively high density of GBs that are readily imaged by transmission electron microscopy (TEM); thermal annealing lowers the density in a controlled manner. We show that the surface-area-normalized activity for CO2 reduction is linearly correlated with GB surface density on Au/CNT, demonstrating that GB engineering is a powerful approach to improving the catalytic activity of metal NPs.

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.

Simple one step synthesis of nonionic dithiol surfactants and their self-assembling with silver nanoparticles: Characterization, surface properties, biological activity

NASA Astrophysics Data System (ADS)

Abd-Elaal, Ali A.; Tawfik, Salah M.; Shaban, Samy M.

2015-07-01

Simple esterification of 2-mercaptoacetic acid and polyethylene glycol with different molecular weights was done to form the desired nonionic dithiol surfactants. The chemical structures of synthesized thiol surfactants were confirmed using FT-IR and 1H NMR spectra. The surface activity of the synthesized surfactants was determined by measurement of the surface tension at different temperatures. The surface activity measurements showed their high tendency towards adsorption and micellization. The thermodynamic parameters of micellization (ΔGmic, ΔHmic and ΔSmic) and adsorption (ΔGads, ΔGads and ΔSads) showed their tendency toward adsorption at the interfaces and also micellization in the bulk of their solutions. The nanostructure of the synthesized nonionic dithiol surfactants with silver nanoparticles was prepared and investigated using UV and TEM techniques. Screening tests of the synthesized dithiol surfactants and their nanostructure with silver nanoparticles, against gram positive bacteria (Bacillus subtilis and Microccus luteus), gram negative bacteria (Escherichia coli and Bordatella pertussis) and fungi (Aspergillus niger and Candida albicans) showed that they are highly active biocides. The presence of silver nanoparticles enhancement the biological activities of the individual synthesized nonionic dithiol surfactants.

Polyaniline-Coated Activated Carbon Aerogel/Sulfur Composite for High-performance Lithium-Sulfur Battery

NASA Astrophysics Data System (ADS)

Tang, Zhiwei; Jiang, Jinglin; Liu, Shaohong; Chen, Luyi; Liu, Ruliang; Zheng, Bingna; Fu, Ruowen; Wu, Dingcai

2017-12-01

An activated carbon aerogel (ACA-500) with high surface area (1765 m2 g-1), pore volume (2.04 cm3 g-1), and hierarchical porous nanonetwork structure is prepared through direct activation of organic aerogel (RC-500) with a low potassium hydroxide ratio (1:1). Based on this substrate, a polyaniline (PANi)-coated activated carbon aerogel/sulfur (ACA-500-S@PANi) composite is prepared via a simple two-step procedure, including melt-infiltration of sublimed sulfur into ACA-500, followed by an in situ polymerization of aniline on the surface of ACA-500-S composite. The obtained ACA-500-S@PANi composite delivers a high reversible capacity up to 1208 mAh g-1 at 0.2C and maintains 542 mAh g-1 even at a high rate (3C). Furthermore, this composite exhibits a discharge capacity of 926 mAh g-1 at the initial cycle and 615 mAh g-1 after 700 cycles at 1C rate, revealing an extremely low capacity decay rate (0.48‰ per cycle). The excellent electrochemical performance of ACA-500-S@PANi can be attributed to the synergistic effect of hierarchical porous nanonetwork structure and PANi coating. Activated carbon aerogels with high surface area and unique three-dimensional (3D) interconnected hierarchical porous structure offer an efficient conductive network for sulfur, and a highly conductive PANi-coating layer further enhances conductivity of the electrode and prevents the dissolution of polysulfide species.

The detection of intestinal spike activity on surface electroenterograms

NASA Astrophysics Data System (ADS)

Ye-Lin, Y.; Garcia-Casado, J.; Martinez-de-Juan, J. L.; Prats-Boluda, G.; Ponce, J. L.

2010-02-01

Myoelectrical recording could provide an alternative technique for assessing intestinal motility, which is a topic of great interest in gastroenterology since many gastrointestinal disorders are associated with intestinal dysmotility. The pacemaker activity (slow wave, SW) of the electroenterogram (EEnG) has been detected in abdominal surface recordings, although the activity related to bowel contractions (spike bursts, SB) has to date only been detected in experimental models with artificially favored electrical conductivity. The aim of the present work was to assess the possibility of detecting SB activity in abdominal surface recordings under physiological conditions. For this purpose, 11 recording sessions of simultaneous internal and external myolectrical signals were conducted on conscious dogs. Signal analysis was carried out in the spectral domain. The results show that in periods of intestinal contractile activity, high-frequency components of EEnG signals can be detected on the abdominal surface in addition to SW activity. The energy between 2 and 20 Hz of the surface myoelectrical recording presented good correlation with the internal intestinal motility index (0.64 ± 0.10 for channel 1 and 0.57 ± 0.11 for channel 2). This suggests that SB activity can also be detected in canine surface EEnG recording.

Antifungal activity of gold nanoparticles prepared by solvothermal method

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

Ahmad, Tokeer, E-mail: tahmad3@jmi.ac.in; Wani, Irshad A.; Lone, Irfan H.

2013-01-15

Graphical abstract: Gold nanoparticles (7 and 15 nm) of very high surface area (329 and 269 m{sup 2}/g) have been successfully synthesized through solvothermal method by using tin chloride and sodium borohydride as reducing agents. As-prepared gold nanoparticles shows very excellent antifungal activity against Candida isolates and activity increases with decrease in the particle size. Display Omitted Highlights: ► Effect of reducing agents on the morphology of gold nanoparticles. ► Highly uniform and monodisperse gold nanoparticles (7 nm). ► Highest surface area of gold nanoparticles (329 m{sup 2/}g). ► Excellent antifungal activity of gold nanoparticles against Candida strains. -- Abstract:more » Gold nanoparticles have been successfully synthesized by solvothermal method using SnCl{sub 2} and NaBH{sub 4} as reducing agents. X-ray diffraction studies show highly crystalline and monophasic nature of the gold nanoparticles with face centred cubic structure. The transmission electron microscopic studies show the formation of nearly spherical gold nanoparticles of average size of 15 nm using SnCl{sub 2}, however, NaBH{sub 4} produced highly uniform, monodispersed and spherical gold nanoparticles of average grain size of 7 nm. A high surface area of 329 m{sup 2}/g for 7 nm and 269 m{sup 2}/g for 15 nm gold nanoparticles was observed. UV–vis studies assert the excitations over the visible region due to transverse and longitudinal surface plasmon modes. The gold nanoparticles exhibit excellent size dependant antifungal activity and greater biocidal action against Candida isolates for 7 nm sized gold nanoparticles restricting the transmembrane H{sup +} efflux of the Candida species than 15 nm sized gold nanoparticles.« less

Mechanisms for Covalent Immobilization of Horseradish Peroxidase on Ion-Beam-Treated Polyethylene

PubMed Central

Kondyurin, Alexey V.; Naseri, Pourandokht; Tilley, Jennifer M. R.; Nosworthy, Neil J.; Bilek, Marcela M. M.; McKenzie, David R.

2012-01-01

The surface of polyethylene was modified by plasma immersion ion implantation. Structure changes including carbonization and oxidation were observed. High surface energy of the modified polyethylene was attributed to the presence of free radicals on the surface. The surface energy decay with storage time after treatment was explained by a decay of the free radical concentration while the concentration of oxygen-containing groups increased with storage time. Horseradish peroxidase was covalently attached onto the modified surface by the reaction with free radicals. Appropriate blocking agents can block this reaction. All aminoacid residues can take part in the covalent attachment process, providing a universal mechanism of attachment for all proteins. The native conformation of attached protein is retained due to hydrophilic interactions in the interface region. The enzymatic activity of covalently attached protein remained high. The long-term activity of the modified layer to attach protein is explained by stabilisation of unpaired electrons in sp2 carbon structures. A high concentration of free radicals can give multiple covalent bonds to the protein molecule and destroy the native conformation and with it the catalytic activity. The universal mechanism of protein attachment to free radicals could be extended to various methods of radiation damage of polymers. PMID:24278665

Photocatalytic degradation of clofibric acid, carbamazepine and iomeprol using conglomerated TiO2 and activated carbon in aqueous suspension.

PubMed

Ziegmann, Markus; Frimmel, Fritz H

2010-01-01

The combination of powdered activated carbon (PAC) and TiO(2) has been tested for synergistic/antagonistic effects in the photocatalytic degradation of carbamazepine, clofibric acid and iomeprol. Synergistic effects are thought to be caused by rapid adsorption on the PAC surface followed by diffusion to the TiO(2) surface and photocatalytic degradation. The Freundlich constant K(F) was used for comparing the sorption properties of the three substances and it was found that K(F) for clofibric acid was 3 times lower than for carbamazepine and iomeprol, regardless of the kind of PAC used. A PAC with a distinct tendency to form conglomerates was selected so that a high percentage of the PAC surface was in direct proximity to the TiO(2) surface. The photocatalytic degradation of the pharmaceutically active compounds studied followed pseudo-first order kinetics. Synergistic effects only occurred for clofibric acid (factor 1.5) and an inverse relationship between adsorption affinity and synergistic effects was found. High affinity of the target substances to the PAC surface seemed to be counterproductive for the photocatalytic degradation.

Activation of hip prostheses in high energy radiotherapy and resultant dose to nearby tissue.

PubMed

Keehan, Stephanie; Smith, Ryan L; Millar, Jeremy; Esser, Max; Taylor, Michael L; Lonski, Peta; Kron, Tomas; Franich, Rick D

2017-03-01

High energy radiotherapy can produce contaminant neutrons through the photonuclear effect. Patients receiving external beam radiation therapy to the pelvis may have high-density hip prostheses. Metallic materials such as those in hip prostheses, often have high cross-sections for neutron interaction. In this study, Thackray (UK) prosthetic hips have been irradiated by 18 MV radiotherapy beams to evaluate the additional dose to patients from the activation products. Hips were irradiated in- and out-of field at various distances from the beam isocenter to assess activation caused in-field by photo-activation, and neutron activation which occurs both in and out-of-field. NaI(Tl) scintillator detectors were used to measure the subsequent gamma-ray emissions and their half-lives. High sensitivity Mg, Cu, P doped LiF thermoluminescence dosimeter chips (TLD-100H) were used to measure the subsequent dose at the surface of a prosthesis over the 12 h following an in-field irradiation of 10,000 MU to a hip prosthesis located at the beam isocenter in a water phantom. 53 Fe, 56 Mn, and 52 V were identified within the hip following irradiation by radiotherapy beams. The dose measured at the surface of a prosthesis following irradiation in a water phantom was 0.20 mGy over 12 h. The dose at the surface of prostheses irradiated to 200 MU was below the limit of detection (0.05 mGy) of the TLD100H. Prosthetic hips are activated by incident photons and neutrons in high energy radiotherapy, however, the dose resulting from activation is very small. © 2017 The Authors. Journal of Applied Clinical Medical Physics published by Wiley Periodicals, Inc. on behalf of American Association of Physicists in Medicine.

Solid frustrated-Lewis-pair catalysts constructed by regulations on surface defects of porous nanorods of CeO2

PubMed Central

Zhang, Sai; Huang, Zheng-Qing; Ma, Yuanyuan; Gao, Wei; Li, Jing; Cao, Fangxian; Li, Lin; Chang, Chun-Ran; Qu, Yongquan

2017-01-01

Identification on catalytic sites of heterogeneous catalysts at atomic level is important to understand catalytic mechanism. Surface engineering on defects of metal oxides can construct new active sites and regulate catalytic activity and selectivity. Here we outline the strategy by controlling surface defects of nanoceria to create the solid frustrated Lewis pair (FLP) metal oxide for efficient hydrogenation of alkenes and alkynes. Porous nanorods of ceria (PN-CeO2) with a high concentration of surface defects construct new Lewis acidic sites by two adjacent surface Ce3+. The neighbouring surface lattice oxygen as Lewis base and constructed Lewis acid create solid FLP site due to the rigid lattice of ceria, which can easily dissociate H–H bond with low activation energy of 0.17 eV. PMID:28516952

Three-dimensional carbon fibers and method and apparatus for their production

DOEpatents

Muradov, Nazim Z [Melbourne, FL

2012-02-21

This invention relates to novel three-dimensional (3D) carbon fibers which are original (or primary) carbon fibers (OCF) with secondary carbon filaments (SCF) grown thereon, and, if desired, tertiary carbon filaments (TCF) are grown from the surface of SCF forming a filamentous carbon network with high surface area. The methods and apparatus are provided for growing SCF on the OCF by thermal decomposition of carbonaceous gases (CG) over the hot surface of the OCF without use of metal-based catalysts. The thickness and length of SCF can be controlled by varying operational conditions of the process, e.g., the nature of CG, temperature, residence time, etc. The optional activation step enables one to produce 3D activated carbon fibers with high surface area. The method and apparatus are provided for growing TCF on the SCF by thermal decomposition of carbonaceous gases over the hot surface of the SCF using metal catalyst particles.

Process for forming a porous silicon member in a crystalline silicon member

DOEpatents

Northrup, M. Allen; Yu, Conrad M.; Raley, Norman F.

1999-01-01

Fabrication and use of porous silicon structures to increase surface area of heated reaction chambers, electrophoresis devices, and thermopneumatic sensor-actuators, chemical preconcentrates, and filtering or control flow devices. In particular, such high surface area or specific pore size porous silicon structures will be useful in significantly augmenting the adsorption, vaporization, desorption, condensation and flow of liquids and gasses in applications that use such processes on a miniature scale. Examples that will benefit from a high surface area, porous silicon structure include sample preconcentrators that are designed to adsorb and subsequently desorb specific chemical species from a sample background; chemical reaction chambers with enhanced surface reaction rates; and sensor-actuator chamber devices with increased pressure for thermopneumatic actuation of integrated membranes. Examples that benefit from specific pore sized porous silicon are chemical/biological filters and thermally-activated flow devices with active or adjacent surfaces such as electrodes or heaters.

High-spatial-resolution mapping of catalytic reactions on single particles

DOE PAGES

Wu, Chung-Yeh; Wolf, William J.; Levartovsky, Yehonatan; ...

2017-01-26

We report the critical role in surface reactions and heterogeneous catalysis of metal atoms with low coordination numbers, such as found at atomic steps and surface defects, is firmly established. But despite the growing availability of tools that enable detailed in situ characterization, so far it has not been possible to document this role directly. Surface properties can be mapped with high spatial resolution, and catalytic conversion can be tracked with a clear chemical signature; however, the combination of the two, which would enable high-spatial-resolution detection of reactions on catalytic surfaces, has rarely been achieved. Single-molecule fluorescence spectroscopy has beenmore » used to image and characterize single turnover sites at catalytic surfaces, but is restricted to reactions that generate highly fluorescing product molecules. Herein the chemical conversion of N-heterocyclic carbene molecules attached to catalytic particles is mapped using synchrotron-radiation-based infrared nanospectroscopy with a spatial resolution of 25 nanometres, which enabled particle regions that differ in reactivity to be distinguished. Lastly, these observations demonstrate that, compared to the flat regions on top of the particles, the peripheries of the particles-which contain metal atoms with low coordination numbers-are more active in catalysing oxidation and reduction of chemically active groups in surface-anchored N-heterocyclic carbene molecules.« less

Platelet Adhesion and Activation on Chiral Surfaces: The Influence of Protein Adsorption.

PubMed

Fan, Yonghong; Luo, Rifang; Han, Honghong; Weng, Yajun; Wang, Hong; Li, Jing'an; Yang, Ping; Wang, Yunbing; Huang, Nan

2017-10-03

Adsorbed proteins and their conformational change on blood-contacting biomaterials will determine their final hemocompatibility. It has frequently been reported that surface chirality of biomaterials may highly influence their protein adsorption behavior. Here, lysine and tartaric acid with different chirality were immobilized onto TiO 2 films respectively, and the influence of surface chirality on protein adsorption, platelet adhesion, and activation was also investigated. It showed that the l- and d-molecule grafted samples had almost the same grafting density, surface topography, chemical components, and hydrophilicity in this study. However, biological behaviors such as protein adsorption, platelet adhesion, and activation were quite different. The d-lysine grafted surface had a greater ability to inhibit both bovine serum albumin and fibrinogen adsorption, along with less degeneration of fibrinogen compared to the l-lysine anchored surface. However, the d-tartaric acid grafted surface adsorbed more protein but with less denatured fibrinogen compared to the l-tartaric acid grafted one. Further studies showed that the secondary structural change of the adsorbed albumin and fibrinogen on all surfaces with deduction of the α-helix content and increase of disordered structure, while the changing degree was apparently varied. As a result, the d-lysine immobilized surface absorbed less platelets and red blood cells and achieved slightly increased platelet activation. For tartaric acid anchored surfaces, a larger number of platelets adhered to the D-surface but were less activated compared to the L-surface. In conclusion, the surface chirality significantly influenced the adsorption and conformational change of blood plasma protein, which in turn influenced both platelet adhesion and activation.

Cell behavior related to implant surfaces with different microstructure and chemical composition: an in vitro analysis.

PubMed

Conserva, Enrico; Lanuti, Anna; Menini, Maria

2010-01-01

This paper reports on an in vitro comparison of osteoblast and mesenchymal stem cell (MSC) adhesion, proliferation, and differentiation related to two different surface treatments applied to the same implant design to determine whether the interaction between cells and implants is influenced by surface structure and chemical composition of the implants. Thirty-nine implants with a sandblasted (SB) surface and 39 implants with a grit-blasted and high-temperature acid-etched (GBAE) surface were used. The implant macrostructures and microstructures were analyzed by high- and low-voltage scanning electron microscopy (SEM) and by stereo-SEM. The surface chemical composition was investigated by energy dispersive analysis and x-ray photoemission spectroscopy. SaOS-2 osteoblasts and human MSCs were used for the evaluation of cell proliferation and alkaline phosphatase enzymatic activity in contact with the two surfaces. The GBAE surface showed fewer contaminants and a very high percentage of titanium (19.7%) compared to the SB surface (14.2%). The two surfaces showed similar mean roughness (Ra), but the depth (Rz) and density (RSm) of the porosity were significantly increased in the GBAE surface. The GBAE surface presented more osteoblast and MSC proliferation than the SB surface. No statistically significant differences in alkaline phosphatase activity were found between surfaces for either cellular line. The GBAE surface showed less surface contaminants and a higher percentage of titanium (19.7%) than the SB surface. The macro/micropore structured design and chemical composition of the GBAE surface allowed greater cell adhesion and proliferation and an earlier cell spreading but did not play an obvious role in in vitro cellular differentiation.

Mechanism of H adatoms improving the O2 reduction reaction on the Zn-modified anatase TiO2 (101) surface studied by first principles calculation.

PubMed

Liu, Liangliang; Li, Chongyang; Jiang, Man; Li, Xiaodong; Huang, Xiaowei; Wang, Zhu; Jia, Yu

2018-06-05

First principles calculations were performed to cast insight into the mechanism of the improvement of O2 reduction reaction (ORR) activity by Zn and H interstitials on the anatase TiO2 (101) surface. For the Zn-modified anatase TiO2 (101) surface, both surface and subsurface Zn interstitials could contribute to O2 adsorption and dissociation, but the dissociation barriers of O2 molecules are still too high, which limits the ORR activity. After a H adatom is introduced onto the Zn-modified anatase TiO2 (101) surface, the highest energy barriers are greatly reduced compared with those of the Zn-modified surface. Meanwhile, it is observed that the dissociation barriers decrease almost linearly with the increase of the charge difference of adsorption O2 between initial and transition state configurations. Specifically, subsurface Zn and surface H interstitials facilitate O2 dissociation and subsequent oxidation reactions, and further frequency analysis shows that these dissociation processes are frequent even at the room temperature of 300 K. In a word, this work provides a theoretical support to design a high ORR activity catalyst of the TiO2 nanocrystal comparable to precious Pt catalysts.

Active surface model improvement by energy function optimization for 3D segmentation.

PubMed

Azimifar, Zohreh; Mohaddesi, Mahsa

2015-04-01

This paper proposes an optimized and efficient active surface model by improving the energy functions, searching method, neighborhood definition and resampling criterion. Extracting an accurate surface of the desired object from a number of 3D images using active surface and deformable models plays an important role in computer vision especially medical image processing. Different powerful segmentation algorithms have been suggested to address the limitations associated with the model initialization, poor convergence to surface concavities and slow convergence rate. This paper proposes a method to improve one of the strongest and recent segmentation algorithms, namely the Decoupled Active Surface (DAS) method. We consider a gradient of wavelet edge extracted image and local phase coherence as external energy to extract more information from images and we use curvature integral as internal energy to focus on high curvature region extraction. Similarly, we use resampling of points and a line search for point selection to improve the accuracy of the algorithm. We further employ an estimation of the desired object as an initialization for the active surface model. A number of tests and experiments have been done and the results show the improvements with regards to the extracted surface accuracy and computational time of the presented algorithm compared with the best and recent active surface models. Copyright © 2015 Elsevier Ltd. All rights reserved.

Activated Carbon Fibers with Hierarchical Nanostructure Derived from Waste Cotton Gloves as High-Performance Electrodes for Supercapacitors.

PubMed

Wei, Chao; Yu, Jianlin; Yang, Xiaoqing; Zhang, Guoqing

2017-12-01

One of the most challenging issues that restrict the biomass/waste-based nanocarbons in supercapacitor application is the poor structural inheritability during the activating process. Herein, we prepare a class of activated carbon fibers by carefully selecting waste cotton glove (CG) as the precursor, which mainly consists of cellulose fibers that can be transformed to carbon along with good inheritability of their fiber morphology upon activation. As prepared, the CG-based activated carbon fiber (CGACF) demonstrates a surface area of 1435 m 2  g -1 contributed by micropores of 1.3 nm and small mesopores of 2.7 nm, while the fiber morphology can be well inherited from the CG with 3D interconnected frameworks created on the fiber surface. This hierarchically porous structure and well-retained fiber-like skeleton can simultaneously minimize the diffusion/transfer resistance of the electrolyte and electron, respectively, and maximize the surface area utilization for charge accumulation. Consequently, CGACF presents a higher specific capacitance of 218 F g -1 and an excellent high-rate performance as compared to commercial activated carbon.

Cell surface control of the multiubiquitination and deubiquitination of high-affinity immunoglobulin E receptors.

PubMed Central

Paolini, R; Kinet, J P

1993-01-01

Multiubiquitination of proteins is a critical step leading to selective degradation for many polypeptides. Therefore, activation-induced multiubiquitination of cell surface receptors, such as the platelet-derived growth factor (PDGF) receptor and the T cell antigen (TCR) receptor, may correspond to a degradation pathway for ligand-receptor complexes. Here we show that the antigen-induced engagement of high-affinity immunoglobulin E receptors (Fc epsilon RI) results in the immediate multiubiquitination of Fc epsilon RI beta and gamma chains. This ubiquitination is independent of receptor phosphorylation and is restricted to activated receptors. Surprisingly, receptor multiubiquitination is immediately reversible when receptors are disengaged. Therefore, multiubiquitination and deubiquitination of Fc epsilon RI receptors is controlled at the cell surface by receptor engagement and disengagement. The rapidity, specificity and, most importantly, the reversibility of the activation-induced receptor multiubiquitination suggest that this process may turn on/off a cell surface receptor signaling function thus far unsuspected. Images PMID:8382611

Active Oxidation of a UHTC-Based CMC

NASA Technical Reports Server (NTRS)

Glass, David E.; Splinter, Scott C.

2012-01-01

The active oxidation of ceramic matrix composites (CMC) is a severe problem that must be avoided for multi-use hypersonic vehicles. Much work has been performed studying the active oxidation of silicon-based CMCs such as C/SiC and SiC-coated carbon/carbon (C/C). Ultra high temperature ceramics (UTHC) have been proposed as a possible material solution for high-temperature applications on hypersonic vehicles. However, little work has been performed studying the active oxidation of UHTCs. The intent of this paper is to present test data indicating an active oxidation process for a UHTC-based CMC similar to the active oxidation observed with Si-based CMCs. A UHTC-based CMC was tested in the HyMETS arc-jet facility (or plasma wind tunnel, PWT) at NASA Langley Research Center, Hampton, VA. The coupon was tested at a nominal surface temperature of 3000 F (1650 C), with a stagnation pressure of 0.026 atm. A sudden and large increase in surface temperature was noticed with negligible increase in the heat flux, indicative of the onset of active oxidation. It is shown that the surface conditions, both temperature and pressure, fall within the region for a passive to active transition (PAT) of the oxidation.

Development of high-sensitive, reproducible colloidal surface-enhanced Raman spectroscopy active substrate using silver nanocubes for potential biosensing applications

NASA Astrophysics Data System (ADS)

Hasna, Kudilatt; Lakshmi, Kiran; Ezhuthachan Jayaraj, Madambi Kunjukuttan; Kumar, Kumaran Rajeev; Matham, Murukeshan Vadakke

2016-04-01

Surface-enhanced Raman spectroscopy (SERS) has emerged as one of the thrust research areas that could find potential applications in bio and chemical sensing. We developed colloidal SERS active substrate with excellent sensitivity and high reproducibility using silver nanocube (AgNC) synthesized via the solvothermal method. Finite-difference time-domain simulation was carried out in detail to visualize dipole generation in the nanocube during localized surface plasmon resonance and to locate the respective hot spots in AgNC responsible for the huge Raman enhancement. The prediction is verified by the SERS analysis of the synthesized nanocubes using Rhodamine 6G molecule. An excellent sensitivity with a detection limit of 10-17 M and a very high enhancement factor of 1.2×108 confirms the "hot spots" in the nanocube. SERS activity is also carried out for crystal violet and for food adulterant Sudan I molecule. Finally, label-free DNA detection is performed to demonstrate the versatility of SERS as a potential biosensor.

Palladium nanoparticles dispersed on the hollow aluminosilicate microsphere@hierarchical γ-AlOOH as an excellent catalyst for the hydrogenation of nitroarenes under ambient conditions

NASA Astrophysics Data System (ADS)

Tian, Meng; Cui, Xueliang; Dong, Chunxu; Dong, Zhengping

2016-12-01

In this study, a novel catalyst has been prepared through supporting Pd nanoparticles (NPs) on the surface of boehmite (γ-AlOOH) based hollow aluminosilicate microspheres (HAM@γ-AlOOH). The prepared Pd/HAM@γ-AlOOH catalyst has high catalytic activity for the hydrogenation of nitroarenes to their corresponding amino derivatives with high yields at ambient conditions. The high catalytic efficiency is attributed to the large pore size of the flower-like hierarchical flakes structure of HAM@γ-AlOOH, that gives Pd NPs on the support surface easy accessibility. Moreover, the Pd/HAM@γ-AlOOH catalyst can also be easily recycled at least five times without obvious decrease of catalytic activity. This work may provide a useful method for the fabrication of supported noble metal NP-based catalysts on the surface of mesoporous hierarchical structure materials with easy accessibility and superior activity.

Stabilizing platinum in phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Remick, R. J.

1982-01-01

Platinum sintering on phosphoric acid fuel cell cathodes is discussed. The cathode of the phosphoric acid fuel cell uses a high surface area platinum catalyst dispersed on a conductive carbon support to minimize both cathode polarization and fabrication costs. During operation, however, the active surface area of these electrodes decreases, which in turn leads to decreased cell performance. This loss of active surface area is a major factor in the degradation of fuel cell performance over time.

The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen.

PubMed

Baker, Thomas A; Liu, Xiaoying; Friend, Cynthia M

2011-01-07

Recently, gold has been intensely studied as a catalyst for key synthetic reactions. Gold is an attractive catalyst because, surprisingly, it is highly active and very selective for partial oxidation processes suggesting promise for energy-efficient "green" chemistry. The underlying origin of the high activity of Au is a controversial subject since metallic gold is commonly thought to be inert. Herein, we establish that one origin of the high activity for gold catalysis is the extremely reactive nature of atomic oxygen bound in 3-fold coordination sites on metallic gold. This is the predominant form of O at low concentrations on the surface, which is a strong indication that it is most relevant to catalytic conditions. Atomic oxygen bound to metallic Au in 3-fold sites has high activity for CO oxidation, oxidation of olefins, and oxidative transformations of alcohols and amines. Among the factors identified as important in Au-O interaction are the morphology of the surface, the local binding site of oxygen, and the degree of order of the oxygen overlayer. In this Perspective, we present an overview of both theory and experiments that identify the reactive forms of O and their associated charge density distributions and bond strengths. We also analyze and model the release of Au atoms induced by O binding to the surface. This rough surface also has the potential for O(2) dissociation, which is a critical step if Au is to be activated catalytically. We further show the strong parallels between product distributions and reactivity for O-covered Au at low pressure (ultrahigh vacuum) and for nanoporous Au catalysts operating at atmospheric pressure as evidence that atomic O is the active species under working catalytic conditions when metallic Au is present. We briefly discuss the possible contributions of oxidants that may contain intact O-O bonds and of the Au-metal oxide support interface in Au catalysis. Finally, the challenges and future directions for fully understanding the activity of gold are considered.

Activities of the Vastus Lateralis and Vastus Medialis Oblique Muscles during Squats on Different Surfaces

PubMed Central

Hyong, In Hyouk; Kang, Jong Ho

2013-01-01

[Purpose] The purpose of the present study was to examine the effects of squat exercises performed on different surfaces on the activity of the quadriceps femoris muscle in order to provide information on support surfaces for effective squat exercises. [Subjects and Method] Fourteen healthy subjects performed squat exercises for five seconds each on three different support surfaces: hard plates, foam, and rubber air discs. Their performance was measured using electromyography. As the subjects performed the squat exercises on each surface, data on the activity of the vastus medialis oblique and the vastus lateralis, and the vastus medials oblique/vastus lateralis ratio, were collected. [Results] The activity of the vastus medialis oblique and the vastus medialis oblique/vastus lateralis ratio were found to be statistically significantly higher on rubber air discs than when the squats were performed on hard plates or foam. [Conclusion] To activate the vastus medialis obilique, and to enhance the vastus medialis oblique/vastus lateralis ratio, unstable surfaces that are highly unstable should be selected. PMID:24259884

Effect of Concentration on the Interfacial and Bulk Structure of Ionic Liquids in Aqueous Solution.

PubMed

Cheng, H-W; Weiss, H; Stock, P; Chen, Y-J; Reinecke, C R; Dienemann, J-N; Mezger, M; Valtiner, M

2018-02-27

Bio and aqueous applications of ionic liquids (IL) such as catalysis in micelles formed in aqueous IL solutions or extraction of chemicals from biologic materials rely on surface-active and self-assembly properties of ILs. Here, we discuss qualitative relations of the interfacial and bulk structuring of a water-soluble surface-active IL ([C 8 MIm][Cl]) on chemically controlled surfaces over a wide range of water concentrations using both force probe and X-ray scattering experiments. Our data indicate that IL structuring evolves from surfactant-like surface adsorption at low IL concentrations, to micellar bulk structure adsorption above the critical micelle concentration, to planar bilayer formation in ILs with <1 wt % of water and at high charging of the surface. Interfacial structuring is controlled by mesoscopic bulk structuring at high water concentrations. Surface chemistry and surface charges decisively steer interfacial ordering of ions if the water concentration is low and/or the surface charge is high. We also demonstrate that controlling the interfacial forces by using self-assembled monolayer chemistry allows tuning of interfacial structures. Both the ratio of the head group size to the hydrophobic tail volume as well as the surface charging trigger the bulk structure and offer a tool for predicting interfacial structures. Based on the applied techniques and analyses, a qualitative prediction of molecular layering of ILs in aqueous systems is possible.

Fabrication of Highly Stable and Efficient PtCu Alloy Nanoparticles on Highly Porous Carbon for Direct Methanol Fuel Cells.

PubMed

Khan, Inayat Ali; Qian, Yuhong; Badshah, Amin; Zhao, Dan; Nadeem, Muhammad Arif

2016-08-17

Boosting the durability of Pt nanoparticles by controlling the composition and morphology is extremely important for fuel cells commercialization. We deposit the Pt-Cu alloy nanoparticles over high surface area carbon in different metallic molar ratios and optimize the conditions to achieve desired material. The novel bimetallic electro-catalyst {Pt-Cu/PC-950 (15:15%)} offers exceptional electrocatalytic activity when tested for both oxygen reduction reaction and methanol oxidation reactions. A high mass activity of 0.043 mA/μgPt (based on Pt mass) is recorded for ORR. An outstanding longevity of this electro-catalyst is noticed when compared to 20 wt % Pt loaded either on PC-950 or commercial carbon. The high surface area carbon support offers enhanced activity and prevents the nanoparticles from agglomeration, migration, and dissolution as evident by TEM analysis.

Fabrication of transition metal-containing nanostructures via polymer templates for a multitude of applications

NASA Astrophysics Data System (ADS)

Lu, Jennifer Qing

Nanostructures such as carbon nanotubes and semiconducting nanowires offer great technological promise due to their remarkable properties. The lack of a rational synthesis method prevents fabricating these nanostructures with desirable and consistent properties at predefined locations for device applications. In this thesis, employing polymer templates, a variety of highly ordered catalytically active transition metal nanostructures, ranging from single metallic nanoparticles of Fe, Co, Ni, Au and bimetallic nanoparticles of Ni/Fe and Co/Mo to Fe-rich silicon oxide nanodomains with uniform and tunable size and spacing have been successfully synthesized. These nanostructures have been demonstrated to be excellent catalyst systems for the synthesis of carbon nanotube and silicon nanowire. High quality, small diameter carbon nanotubes and nanowires with narrow size distribution have been successfully attained. Because these catalytically active nanostructures are uniformly distributed and do not agglomerate at the growth temperatures, uniform, high density and high quality carbon nanotube mats have been obtained. Since this polymer template approach is fully compatible with conventional top-down photolithography, lithographically selective growth of carbon nanotubes on a surface or suspended carbon nanotubes across trenches have been produced by using existing semiconductor processing. We have also shown the feasibility of producing carbon nanotubes and silicon nanowires at predefined locations on a wafer format and established a wafer-level carbon nanotube based device fabrication process. The ability of the polymer template approach to control catalyst systems at the nano-, micro- and macro-scales paves a pathway for commercialization of these 1D nanostructure-enabled devices. Beside producing well-defined, highly ordered discrete catalytically active metal-containing nanostructures by the polymer template approach, Au and Ag nanotextured surfaces have also been attained by using a self-assembled ferrocenylsilane-based inorganic block copolymer template. These Au and Ag nanotextured surfaces exhibit different surface plasmon behavior than the nanotextured surface. Greatly enhanced and uniform Raman scattering have been observed on Ag nanotextured surfaces. Highly sensitive Au nanotextured surfaces suggest their potential application as sensing surfaces for SPR-based biodetection. This simple fabrication technique of producing inorganic nanostructures with adjustable properties such as size, spacing and composition offers great promise for both fundamental research and technological development.

Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution

NASA Astrophysics Data System (ADS)

Liu, Yuanyue; Wu, Jingjie; Hackenberg, Ken P.; Zhang, Jing; Wang, Y. Morris; Yang, Yingchao; Keyshar, Kunttal; Gu, Jing; Ogitsu, Tadashi; Vajtai, Robert; Lou, Jun; Ajayan, Pulickel M.; Wood, Brandon C.; Yakobson, Boris I.

2017-09-01

Low-cost, layered transition-metal dichalcogenides (MX2) based on molybdenum and tungsten have attracted substantial interest as alternative catalysts for the hydrogen evolution reaction (HER). These materials have high intrinsic per-site HER activity; however, a significant challenge is the limited density of active sites, which are concentrated at the layer edges. Here we unravel electronic factors underlying catalytic activity on MX2 surfaces, and leverage the understanding to report group-5 MX2 (H-TaS2 and H-NbS2) electrocatalysts whose performance instead mainly derives from highly active basal-plane sites, as suggested by our first-principles calculations and performance comparisons with edge-active counterparts. Beyond high catalytic activity, they are found to exhibit an unusual ability to optimize their morphology for enhanced charge transfer and accessibility of active sites as the HER proceeds, offering a practical advantage for scalable processing. The catalysts reach 10 mA cm-2 current density at an overpotential of ˜50-60 mV with a loading of 10-55 μg cm-2, surpassing other reported MX2 candidates without any performance-enhancing additives.

Sensing surface mechanical deformation using active probes driven by motor proteins

PubMed Central

Inoue, Daisuke; Nitta, Takahiro; Kabir, Arif Md. Rashedul; Sada, Kazuki; Gong, Jian Ping; Konagaya, Akihiko; Kakugo, Akira

2016-01-01

Studying mechanical deformation at the surface of soft materials has been challenging due to the difficulty in separating surface deformation from the bulk elasticity of the materials. Here, we introduce a new approach for studying the surface mechanical deformation of a soft material by utilizing a large number of self-propelled microprobes driven by motor proteins on the surface of the material. Information about the surface mechanical deformation of the soft material is obtained through changes in mobility of the microprobes wandering across the surface of the soft material. The active microprobes respond to mechanical deformation of the surface and readily change their velocity and direction depending on the extent and mode of surface deformation. This highly parallel and reliable method of sensing mechanical deformation at the surface of soft materials is expected to find applications that explore surface mechanics of soft materials and consequently would greatly benefit the surface science. PMID:27694937

Adsorption of naphthenic acids on high surface area activated carbons.

PubMed

Iranmanesh, Sobhan; Harding, Thomas; Abedi, Jalal; Seyedeyn-Azad, Fakhry; Layzell, David B

2014-01-01

In oil sands mining extraction, water is an essential component; however, the processed water becomes contaminated through contact with the bitumen at high temperature, and a portion of it cannot be recycled and ends up in tailing ponds. The removal of naphthenic acids (NAs) from tailing pond water is crucial, as they are corrosive and toxic and provide a substrate for microbial activity that can give rise to methane, which is a potent greenhouse gas. In this study, the conversion of sawdust into an activated carbon (AC) that could be used to remove NAs from tailings water was studied. After producing biochar from sawdust by a slow-pyrolysis process, the biochar was physically activated using carbon dioxide (CO2) over a range of temperatures or prior to producing biochar, and the sawdust was chemically activated using phosphoric acid (H3PO4). The physically activated carbon had a lower surface area per gram than the chemically activated carbon. The physically produced ACs had a lower surface area per gram than chemically produced AC. In the adsorption tests with NAs, up to 35 mg of NAs was removed from the water per gram of AC. The chemically treated ACs showed better uptake, which can be attributed to its higher surface area and increased mesopore size when compared with the physically treated AC. Both the chemically produced and physically produced AC provided better uptake than the commercially AC.

Electron transport in ethanol & methanol absorbed defected graphene

NASA Astrophysics Data System (ADS)

Dandeliya, Sushmita; Srivastava, Anurag

2018-05-01

In the present paper, the sensitivity of ethanol and methanol molecules on surface of single vacancy defected graphene has been investigated using density functional theory (DFT). The changes in structural and electronic properties before and after adsorption of ethanol and methanol were analyzed and the obtained results show high adsorption energy and charge transfer. High adsorption happens at the active site with monovacancy defect on graphene surface. Present work confirms that the defected graphene increases the surface reactivity towards ethanol and methanol molecules. The presence of molecules near the active site affects the electronic and transport properties of defected graphene which makes it a promising choice for designing methanol and ethanol sensor.

Hierarchically structured graphene-carbon nanotube-cobalt hybrid electrocatalyst for seawater battery

NASA Astrophysics Data System (ADS)

Suh, Dong Hoon; Park, Sul Ki; Nakhanivej, Puritut; Kim, Youngsik; Hwang, Soo Min; Park, Ho Seok

2017-12-01

The design of cost-effective and highly active catalysts is a critical challenge. Inspired by the strong points of stability and conductivity of carbon nanotubes (CNTs), high catalytic activity of Co nanoparticles, and rapid ion diffusion and large accessible area of three-dimensional (3D) graphene, we demonstrate a novel strategy to construct a hierarchical hybrid structure consisting of Co/CoOx nanoparticles-incorporated CNT branches onto the 3D reduced graphene oxide (rGO) architecture. The surface-modified 3D rGO by steam activation process has a large surface area and abundant defect sites, which serve as active sites to uniformly grow Co/CoOx nanoparticles. Furthermore, the CNTs preserve their performance stably by encapsulating Co nanoparticles, while the uniformly decorated Co/CoOx nanoparticles exhibit superior electrocatalytic activity toward oxygen evolution/reduction reaction due to highly exposed active sites. Employing the hybrid particle electrocatalyst, the seawater battery operates stably at 0.01 mA cm-2 during 50 cycles, owing to the good electrocatalytic ability.

Optimizing growth and post treatment of diamond for high capacitance neural interfaces.

PubMed

Tong, Wei; Fox, Kate; Zamani, Akram; Turnley, Ann M; Ganesan, Kumaravelu; Ahnood, Arman; Cicione, Rosemary; Meffin, Hamish; Prawer, Steven; Stacey, Alastair; Garrett, David J

2016-10-01

Electrochemical and biological properties are two crucial criteria in the selection of the materials to be used as electrodes for neural interfaces. For neural stimulation, materials are required to exhibit high capacitance and to form intimate contact with neurons for eliciting effective neural responses at acceptably low voltages. Here we report on a new high capacitance material fabricated using nitrogen included ultrananocrystalline diamond (N-UNCD). After exposure to oxygen plasma for 3 h, the activated N-UNCD exhibited extremely high electrochemical capacitance greater than 1 mF/cm(2), which originates from the special hybrid sp(2)/sp(3) structure of N-UNCD. The in vitro biocompatibility of the activated N-UNCD was then assessed using rat cortical neurons and surface roughness was found to be critical for healthy neuron growth, with best results observed on surfaces with a roughness of approximately 20 nm. Therefore, by using oxygen plasma activated N-UNCD with appropriate surface roughness, and considering the chemical and mechanical stability of diamond, the fabricated neural interfaces are expected to exhibit high efficacy, long-term stability and a healthy neuron/electrode interface. Copyright © 2016 Elsevier Ltd. All rights reserved.

Vesiculation Processes During Transient and Sustained Explosive Activity at Halema'uma'u Crater, Kīlauea in 2008-2013.

NASA Astrophysics Data System (ADS)

Houghton, B. F.; Orr, T. R.; Taddeucci, J.; Carey, R.; Del Bello, E.; Scarlato, P.; Patrick, M. R.

2015-12-01

The 2008-2015 summit eruption within Halema'uma'u crater, Kilauea has been characterized by alternations of passive degassing with two styles of explosive activity, both frequently triggered by rock falls that perturb the free surface of magma in the vent. In the first, larger rock falls trigger second vesiculation of magma at depths up to 100 m below the free surface ejecting juvenile bomb and lapilli populations of very variable vesicularity. The second, the topic of this presentation, consists of intervals of minutes to tens-of-minutes duration of low fountaining activity often from multiple locations. Vents may migrate with time, first across the free surface to its margins, and then around the margins, in response to convection processes in the underlying melt. Analysis of short sequences of high-speed, high-resolution video footage shows that the sustained fountaining is maintained by not by a continuous discharge but rather by closely spaced bursting of two-to-five meter-wide bubbles. Bubbles accelerate through the free surface at velocities of 10 to 40 m/s disrupting the viscoelastic crust and forming large fall-back, lacework pyroclasts and smaller highly vesicular bombs and lapilli.

High Resolution Rapid Revisits Insar Monitoring of Surface Deformation

NASA Astrophysics Data System (ADS)

Singhroy, V.; Li, J.; Charbonneau, F.

2014-12-01

Monitoring surface deformation on strategic energy and transportation corridors requires high resolution spatial and temporal InSAR images for mitigation and safety purposes. High resolution air photos, lidar and other satellite images are very useful in areas where the landslides can be fatal. Recently, radar interferometry (InSAR) techniques using more rapid revisit images from several radar satellites are increasingly being used in active deformation monitoring. The Canadian RADARSAT Constellation (RCM) is a three-satellite mission that will provide rapid revisits of four days interferometric (InSAR) capabilities that will be very useful for complex deformation monitoring. For instance, the monitoring of surface deformation due to permafrost activity, complex rock slide motion and steam assisted oil extraction will benefit from this new rapid revisit capability. This paper provide examples of how the high resolution (1-3 m) rapid revisit InSAR capabilities will improve our monitoring of surface deformation and provide insights in understanding triggering mechanisms. We analysed over a hundred high resolution InSAR images over a two year period on three geologically different sites with various configurations of topography, geomorphology, and geology conditions. We show from our analysis that the more frequent InSAR acquisitions are providing more information in understanding the rates of movement and failure process of permafrost triggered retrogressive thaw flows; the complex motion of an asymmetrical wedge failure of an active rock slide and the identification of over pressure zones related to oil extraction using steam injection. Keywords: High resolution, InSAR, rapid revisits, triggering mechanisms, oil extraction.

Assembling strategy to synthesize palladium modified kaolin nanocomposites with different morphologies

PubMed Central

Li, Xiaoyu; Ouyang, Jing; Zhou, Yonghua; Yang, Huaming

2015-01-01

Nanocomposites of aluminosilicate minerals, kaolins (kaolinite and halloysite) with natural different morphologies assembling with palladium (Pd) nanoparticles have been successfully synthesized through strong electrostatic adsorption and chemical bonding after surface modification with 3-aminopropyl triethoxysilane (APTES). Meanwhile, the influence of different morphologies supports on catalytic hydrogenation properties was explored. The surface concentration of amino groups on the kaolins was related to the morphology and surface nature. Electronmicroscopy revealed that the monodisperse Pd nanoparticles were uniformly deposited onto the surface of kaolins, ranging in diameter from 0.5 nm to 5.5 nm. The functional groups could not only improve the dispersion of kaolins with different morphologies in solution, but also enhance the interaction between Pd precursors and kaolins, thus preventing small Pd nanoparticles from agglomerating and leading to high activity for the catalytic hydrogenation of styrene. Pd-FK@APTES was more active compared to other samples. Selecting the kaolin morphology with a different surface nature allows the selective surface modification of a larger fraction of the reactive facets on which the active sites can be enriched and tuned. This desirable surface coordination of catalytically active atoms could substantially improve catalytic activity. PMID:26333629

Assembling strategy to synthesize palladium modified kaolin nanocomposites with different morphologies

NASA Astrophysics Data System (ADS)

Li, Xiaoyu; Ouyang, Jing; Zhou, Yonghua; Yang, Huaming

2015-09-01

Nanocomposites of aluminosilicate minerals, kaolins (kaolinite and halloysite) with natural different morphologies assembling with palladium (Pd) nanoparticles have been successfully synthesized through strong electrostatic adsorption and chemical bonding after surface modification with 3-aminopropyl triethoxysilane (APTES). Meanwhile, the influence of different morphologies supports on catalytic hydrogenation properties was explored. The surface concentration of amino groups on the kaolins was related to the morphology and surface nature. Electronmicroscopy revealed that the monodisperse Pd nanoparticles were uniformly deposited onto the surface of kaolins, ranging in diameter from 0.5 nm to 5.5 nm. The functional groups could not only improve the dispersion of kaolins with different morphologies in solution, but also enhance the interaction between Pd precursors and kaolins, thus preventing small Pd nanoparticles from agglomerating and leading to high activity for the catalytic hydrogenation of styrene. Pd-FK@APTES was more active compared to other samples. Selecting the kaolin morphology with a different surface nature allows the selective surface modification of a larger fraction of the reactive facets on which the active sites can be enriched and tuned. This desirable surface coordination of catalytically active atoms could substantially improve catalytic activity.

Assembling strategy to synthesize palladium modified kaolin nanocomposites with different morphologies.

PubMed

Li, Xiaoyu; Ouyang, Jing; Zhou, Yonghua; Yang, Huaming

2015-09-03

Nanocomposites of aluminosilicate minerals, kaolins (kaolinite and halloysite) with natural different morphologies assembling with palladium (Pd) nanoparticles have been successfully synthesized through strong electrostatic adsorption and chemical bonding after surface modification with 3-aminopropyl triethoxysilane (APTES). Meanwhile, the influence of different morphologies supports on catalytic hydrogenation properties was explored. The surface concentration of amino groups on the kaolins was related to the morphology and surface nature. Electronmicroscopy revealed that the monodisperse Pd nanoparticles were uniformly deposited onto the surface of kaolins, ranging in diameter from 0.5 nm to 5.5 nm. The functional groups could not only improve the dispersion of kaolins with different morphologies in solution, but also enhance the interaction between Pd precursors and kaolins, thus preventing small Pd nanoparticles from agglomerating and leading to high activity for the catalytic hydrogenation of styrene. Pd-FK@APTES was more active compared to other samples. Selecting the kaolin morphology with a different surface nature allows the selective surface modification of a larger fraction of the reactive facets on which the active sites can be enriched and tuned. This desirable surface coordination of catalytically active atoms could substantially improve catalytic activity.

Surface versus bulk activity of lysozyme deposited on hydrogel contact lens materials in vitro.

PubMed

Omali, Negar Babaei; Subbaraman, Lakshman N; Heynen, Miriam; Ng, Alan; Coles-Brennan, Chantal; Fadli, Zohra; Jones, Lyndon

2018-04-30

To determine and compare the levels of surface versus bulk active lysozyme deposited on several commercially available hydrogel contact lens materials. Hydrogel contact lens materials [polymacon, omafilcon A, nelfilcon A, nesofilcon A, ocufilcon and etafilcon A with polyvinylpyrrolidone (PVP)] were incubated in an artificial tear solution for 16 h. Total activity was determined using a standard turbidity assay. The surface activity of the deposited lysozyme was determined using a modified turbidity assay. The amount of active lysozyme present within the bulk of the lens material was calculated by determining the difference between the total and surface active lysozyme. The etafilcon A materials showed the highest amount of total lysozyme activity (519 ± 8 μg/lens, average of Moist and Define), followed by the ocufilcon material (200 ± 5 μg/lens) and these two were significantly different from each other (p < 0.05). The amount of surface active lysozyme on etafilcon and ocufilcon lens materials was significantly higher than that found on all other lenses (p < 0.05). There was no active lysozyme quantified in the bulk of the nelfilcon material, as all of the active lysozyme was found on the surface (1.7 ± 0.3 μg/lens). In contrast, no active lysozyme was quantified on the surface of polymacon, with all of the active lysozyme found in the bulk of the lens material (0.6 ± 0.6 μg/lens). The surface and bulk activity of lysozyme deposited on contact lenses is material dependent. Lysozyme deposited on ionic, high water content lens materials such as etafilcon A show significantly higher surface and bulk activity than many other hydrogel lens materials. Copyright © 2018 British Contact Lens Association. Published by Elsevier Ltd. All rights reserved.

Facet-Dependent Deposition of Highly Strained Alloyed Shells on Intermetallic Nanoparticles for Enhanced Electrocatalysis

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

Wang, Chenyu; Sang, Xiahan; Gamler, Jocelyn T. L.

Compressive surface strains can enhance the performance of platinum-based core@shell electrocatalysts for the oxygen reduction reaction (ORR). Bimetallic core@shell nanoparticles (NPs) are widely studied nanocatalysts but often have limited lattice mismatch and surface compositions; investigations of core@shell NPs with greater compositional complexity and lattice misfit are in their infancy. Here, a new class of multimetallic NPs composed of intermetallic cores and random alloy shells is reported. Specifically, face-centered cubic (fcc) Pt- Cu random alloy shells were deposited non-epitaxially on PdCu B2 intermetallic seeds, giving rise to faceted core@shell NPs with highly strained surfaces. In fact, high resolution transmission electron microscopymore » (HRTEM) revealed orientation-dependent surface strains, where the compressive strains were minimal on Pt-Cu {111} facets but greater on {200} facets. These core@shell NPs provide higher specific and mass activities for the ORR when compared to conventional Pt-Cu NPs. Moreover, these intermetallic@random alloy NPs displayed high endurance, undergoing 10,000 cycles with only a slight decay in activity and no apparent structural changes.« less

Facet-Dependent Deposition of Highly Strained Alloyed Shells on Intermetallic Nanoparticles for Enhanced Electrocatalysis

DOE PAGES

Wang, Chenyu; Sang, Xiahan; Gamler, Jocelyn T. L.; ...

2017-08-25

Compressive surface strains can enhance the performance of platinum-based core@shell electrocatalysts for the oxygen reduction reaction (ORR). Bimetallic core@shell nanoparticles (NPs) are widely studied nanocatalysts but often have limited lattice mismatch and surface compositions; investigations of core@shell NPs with greater compositional complexity and lattice misfit are in their infancy. Here, a new class of multimetallic NPs composed of intermetallic cores and random alloy shells is reported. Specifically, face-centered cubic (fcc) Pt- Cu random alloy shells were deposited non-epitaxially on PdCu B2 intermetallic seeds, giving rise to faceted core@shell NPs with highly strained surfaces. In fact, high resolution transmission electron microscopymore » (HRTEM) revealed orientation-dependent surface strains, where the compressive strains were minimal on Pt-Cu {111} facets but greater on {200} facets. These core@shell NPs provide higher specific and mass activities for the ORR when compared to conventional Pt-Cu NPs. Moreover, these intermetallic@random alloy NPs displayed high endurance, undergoing 10,000 cycles with only a slight decay in activity and no apparent structural changes.« less

50 CFR 218.74 - Mitigation.

Code of Federal Regulations, 2014 CFR

2014-10-01

...) Surface ships or aircraft conducting high-frequency or non-hull-mounted mid-frequency active sonar...) When marine mammals are visually detected, the Navy shall ensure that high-frequency and non-hull... using low-frequency or hull-mounted mid-frequency active sonar sources associated with anti-submarine...

Biocompatibility of modified ultra-high-molecular-weight polyethylene

NASA Astrophysics Data System (ADS)

Novotná, Z.; Lacmanová, V.; Rimpelová, S.; Juřik, P.; Polívková, M.; Å vorčik, V.

2016-09-01

Ultra-high-molecular-weight polyethylene (UHMWPE, PE) is a synthetic polymer used for biomedical applications because of its high impact resistance, ductility and stability in contact with physiological fluids. Therefore this material is being used in human orthopedic implants such as total joint replacements. Surface modification of this material relates to changes of its surface hydrophilicity, energy, microstructure, roughness, and morphology, all influencing its biological response. In our recent work, PE was treated by an Ar+ plasma discharge and then grafted with biologically active polyethylene glycol in order to enhance adhesion and proliferation of mouse fibroblast (L929). The surface properties of pristine PE and its grafted counterparts were studied by goniometry (surface wettability). Furthermore, Atomic Force Microscopy was used to determine the surface morphology and roughness. The biological response of the L929 cell lines seeded on untreated and plasma treated PE matrices was quantified in terms of the cell adhesion, density, and metabolic activity. Plasma treatment leads to the ablation of the polymer surface layers. Plasma treatment and subsequent poly(ethylene glycol) grafting lead to dramatic changes in the polymer surface morphology and roughness. Biological tests, performed in vitro, show increased adhesion and proliferation of cells on modified polymers. Grafting with poly(ethylene glycol) increases cell proliferation compared to plasma treatment.

Surface preparation for high purity alumina ceramics enabling direct brazing in hydrogen atmospheres

DOEpatents

Cadden, Charles H.; Yang, Nancy Yuan Chi; Hosking, Floyd M.

2001-01-01

The present invention relates to a method for preparing the surface of a high purity alumina ceramic or sapphire specimen that enables direct brazing in a hydrogen atmosphere using an active braze alloy. The present invention also relates to a method for directly brazing a high purity alumina ceramic or sapphire specimen to a ceramic or metal member using this method of surface preparation, and to articles produced by this brazing method. The presence of silicon, in the form of a SiO.sub.2 -containing surface layer, can more than double the tensile bond strength in alumina ceramic joints brazed in a hydrogen atmosphere using an active Au-16Ni-0.75 Mo-1.75V filler metal. A thin silicon coating applied by PVD processing can, after air firing, produce a semi-continuous coverage of the alumina surface with a SiO.sub.2 film. Room temperature tensile strength was found to be proportional to the fraction of air fired surface covered by silicon-containing films. Similarly, the ratio of substrate fracture versus interface separation was also related to the amount of surface silicon present prior to brazing. This process can replace the need to perform a "moly-manganese" metallization step.

Investigation of the electrochemically active surface area and lithium diffusion in graphite anodes by a novel OsO4 staining method

NASA Astrophysics Data System (ADS)

Pfaffmann, Lukas; Birkenmaier, Claudia; Müller, Marcus; Bauer, Werner; Mitsch, Tim; Feinauer, Julian; Krämer, Yvonne; Scheiba, Frieder; Hintennach, Andreas; Schleid, Thomas; Schmidt, Volker; Ehrenberg, Helmut

2016-03-01

Negative electrodes of lithium-ion batteries generally consist of graphite-based active materials. In order to realize batteries with a high current density and therefore accelerated charging processes, the intercalation of lithium and the diffusion processes of these carbonaceous materials must be understood. In this paper, we visualized the electrochemical active surface area for three different anode materials using a novel OsO4 staining method in combination with scanning electron microscopy techniques. The diffusion behavior of these three anode materials is investigated by potentiostatic intermittent titration technique measurements. From those we determine the diffusion coefficient with and without consideration of the electrochemical active surface area.

High-performance super capacitors based on activated anthracite with controlled porosity

NASA Astrophysics Data System (ADS)

Lee, Hyun-Chul; Byamba-Ochir, Narandalai; Shim, Wang-Geun; Balathanigaimani, M. S.; Moon, Hee

2015-02-01

Mongolian anthracite is chemically activated using potassium hydroxide as an activation agent to make activated carbon materials. Prior to the chemical activation, the chemical agent is introduced by two different methods as follows, (1) simple physical mixing, (2) impregnation. The physical properties such as specific surface area, pore volume, pore size distribution, and adsorption energy distribution are measured to assess them as carbon electrode materials for electric double-layer capacitors (EDLC). The surface functional groups and morphology are also characterized by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analyses respectively. The electrochemical results for the activated carbon electrodes in 3 M sulfuric acid electrolyte solution indicate that the activated Mongolian anthracite has relatively large specific capacitances in the range of 120-238 F g-1 and very high electrochemical stability, as they keep more than 98% of initial capacitances until 1000 charge/discharge cycles.

Intrinsic activation: the relationship between biomass inorganic content and porosity formation during pyrolysis.

PubMed

Stratford, James P; Hutchings, Tony R; de Leij, Frans A A M

2014-05-01

The utility of pyrolytic carbons is closely related to their porosity and surface area, there is a clear benefit to the development of biomass pyrolysis processes which produce highly porous carbons. The results presented in this work demonstrate that by using biomass precursors with high inorganic content along with specified process conditions, carbons can be consistently produced with specific surface areas between 900 and 1600 m(2)/g. Results from 12 different source materials show that the formation of increased porosity in pyrolytic carbons is strongly associated with the presence of inorganic elements in the precursors including: magnesium, potassium and sulfur. It was found that pyrolysis of macro-algae can produce especially high specific surface area carbons (mean: 1500 m(2)/g), without externally applied activating agents. Using cheap readily available agricultural residues such as oilseed rape straw, pyrolytic carbons can be produced with specific surface areas of around 950 m(2)/g. Copyright © 2014 Elsevier Ltd. All rights reserved.

Deactivation of photocatalytically active ZnO nanoparticle and enhancement of its compatibility with organic compounds by surface-capping with organically modified silica

NASA Astrophysics Data System (ADS)

Cao, Zhi; Zhang, Zhijun

2011-02-01

Tetraethyl orthosilicate (TEOS) and dimethyldiethoxysilane (DEDMS) were used as co-precursors to prepare organically modified silica (ormosil) via sol-gel process. The resultant ormosil was adopted for surface-capping of ZnO nanoparticle, where methyl (organic functional group) and silica (inorganic component) were simultaneously introduced onto the surface of the nanoparticles for realizing dual surface-modification. The ormosil-capped ZnO nanoparticle showed strong hydrophobicity and good compatibility with organic phases, as well as effectively decreased photocatalytic activity and almost unchanged ultraviolet (UV)-shielding ability. More importantly, the comprehensive properties of ormosil-capped ZnO nanoparticle could be manipulated by adjusting the molar ratio of TEOS to DEDMS during sol-gel process. This should help to open a wider window to better utilizing the unique and highly attractive properties such as high UV-shielding ability and high-visible light transparency of ZnO nanoparticle in sunscreen cosmetics.

Removal of nitric oxide by the highly reactive anatase TiO2 (001) surface: a density functional theory study.

PubMed

Zhao, Wenwen; Tian, Feng Hui; Wang, Xiaobin; Zhao, Linghuan; Wang, Yun; Fu, Aiping; Yuan, Shuping; Chu, Tianshu; Xia, Linhua; Yu, Jimmy C; Duan, Yunbo

2014-09-15

In this paper, density functional theory (DFT) calculation was employed to study the adsorption of nitric oxide (NO) on the highly reactive anatase TiO2 (001) surface. For comparison, the adsorption of NO on the (101) surface was also considered. Different from the physical adsorption on the (101) surface, NO molecules are found to chemisorb on the TiO2 (001) surface. The twofold coordinate oxygen atoms (O2c) on the anatase (001) surface are the active sites. Where NO is oxidized into a nitrite species (NO2(-)) trapping efficiently on the surface, with one of the surface Ti5c-O2c bonds adjacent to the adsorption site broken. Our results, therefore, supply a theoretical guidance to remove NO pollutants using highly reactive anatase TiO2 (001) facets. Copyright © 2014 Elsevier Inc. All rights reserved.

Preparation and Characterization of Mesoporous Nickel derived from Liquid crystalline Template and Evaluation of its Electro catalytic activity towards Methanol Oxidation

NASA Astrophysics Data System (ADS)

Mohanapriya, S.; Renuka devi, R.; Raj, V.

2018-02-01

Mesoporous Nickel has been prepared by electrodeposition using non-ionic surfactant based liquid crystalline template under optimized processing conditions. Physico-chemical properties of mesoporous nickel is systematically characterized through XRD, SEM and AFM analyses. Comparison of electrocatalytic activity of mesoporous nickel with smooth nickel was interrogated using cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) analyses. Distinctly enhanced electrocatalytic activity with improved surface poisoning resistance related to mesoporous nickel electrode towards methanol oxidation stems from unique mesoporous morphology. This mesoporous morphology with high surface to volume ratio is highly beneficial to promote active catalytic centers to offer readily accessible Pt catalytic sites for MOR, through facilitating mass and electron transports.

Assessing the influence of flight parameters, interferometric processing, slope and canopy density on the accuracy of X-band IFSAR-derived forest canopy height models.

Treesearch

H.-E. Andersen; R.J. McGaughey; S.E. Reutebuch

2008-01-01

High resolution, active remote sensing technologies, such as interferometric synthetic aperture radar (IFSAR) and airborne laser scanning (LIDAR) have the capability to provide forest managers with direct measurements of 3-dimensional forest canopy surface structure. Although LIDAR systems can provide highly accurate measurements of canopy and terrain surfaces, high-...

Efficient Decarbonylation of Furfural to Furan Catalyzed by Zirconia-Supported Palladium Clusters with Low Atomicity.

PubMed

Ishida, Tamao; Kume, Kurumi; Kinjo, Kota; Honma, Tetsuo; Nakada, Kengo; Ohashi, Hironori; Yokoyama, Takushi; Hamasaki, Akiyuki; Murayama, Haruno; Izawa, Yusuke; Utsunomiya, Masaru; Tokunaga, Makoto

2016-12-20

Decarbonylation of furfural to furan was efficiently catalyzed by ZrO 2 -supported Pd clusters in the liquid phase under a N 2 atmosphere without additives. Although Pd/C and Pd/Al 2 O 3 have frequently been used for decarbonylation, Pd/ZrO 2 exhibited superior catalytic performance compared with these conventional catalysts. Transmission electron microscopy and X-ray absorption fine structure measurements revealed that the size of the Pd particles decreased with an increase in the specific surface area of ZrO 2 . ZrO 2 with a high surface area immobilized Pd as clusters consisting of several (three to five) Pd atoms, whereas Pd aggregated to form nanoparticles on other supports such as carbon and Al 2 O 3 despite their high surface areas. The catalytic activity of Pd/ZrO 2 was enhanced with a decrease in particle size, and the smallest Pd/ZrO 2 was the most active catalyst for decarbonylation. When CeO 2 was used as the support, a decrease in Pd particle size with an increase in surface area was also observed. Single Pd atoms were deposited on CeO 2 with a high surface area, with a strong interaction through the formation of a Pd-O-Ce bond, which led to a lower catalytic activity than that of Pd/ZrO 2 . This result suggests that zero-valent small Pd clusters consisting of more than one Pd atom are the active species for the decarbonylation reaction. Recycling tests proved that Pd/ZrO 2 maintained its catalytic activity until its sixth use. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A surfactant free preparation of ultradispersed surface-clean Pt catalyst with highly stable electrocatalytic performance

NASA Astrophysics Data System (ADS)

Tao, Lu; Zhao, Yueping; Zhao, Yufeng; Huang, Shifei; Yang, Yunxia; Tong, Qi; Gao, Faming

2018-02-01

High efficiency platinum-based catalyst demands the ultrafine size and well dispersion of Pt nanoparticles (NPs), with clean surface and strong interactions between the supports. In this work, we demonstrate a simple strategy for the preparation of ultra-dispersed surface-clean Pt catalyst with high stability, in which the Pt nanoparticles (NPs) with 1.8 ± 0.6 nm in size are anchored tightly on a 3D hierarchical porous graphitized carbon (3D-HPG) through galvanic replacement reaction. The as-obtained catalyst can undergo 2000 voltage cycles with negligible activity decay and no apparent structure and size changes for MOR during the durability test, and its mass activity for ORR only reduce 18.3% after 5000 cycles. The excellent performance is attributed to strong anchoring effect between carbon support and Pt nanoparticles.

Roughening of Pt nanoparticles induced by surface-oxide formation.

PubMed

Zhu, Tianwei; Hensen, Emiel J M; van Santen, Rutger A; Tian, Na; Sun, Shi-Gang; Kaghazchi, Payam; Jacob, Timo

2013-02-21

Using density functional theory (DFT) and thermodynamic considerations we studied the equilibrium shape of Pt nanoparticles (NPs) under electrochemical conditions. We found that at very high oxygen coverage, obtained at high electrode potentials, the experimentally-observed tetrahexahedral (THH) NPs consist of high-index (520) faces. Since high-index surfaces often show higher (electro-)chemical activity in comparison to their close-packed counterparts, the THH NPs can be promising candidates for various (electro-)catalytic applications.

Montmorillonite-supported Ag/TiO(2) nanoparticles: an efficient visible-light bacteria photodegradation material.

PubMed

Wu, Tong-Shun; Wang, Kai-Xue; Li, Guo-Dong; Sun, Shi-Yang; Sun, Jian; Chen, Jie-Sheng

2010-02-01

Montmorillonite (MMT)-supported Ag/TiO(2) composite (Ag/TiO(2)/MMT) has been prepared through a one-step, low-temperature solvothermal technique. Powder X-ray diffraction (XRD) and transmission electron microscopy (TEM) reveal that the Ag particles coated with TiO(2) nanoparticles are well-dispersed on the surface of MMT in the composite. As a support for the Ag/TiO(2) composite, the MMT prevents the loss of the catalyst during recycling test. This Ag/TiO(2)/MMT composite exhibits high photocatalytic activity and good recycling performance in the degradation of E. coli under visible light. The high visible-light photocatalytic activity of the Ag/TiO(2)/MMT composite is ascribed to the increase in surface active centers and the localized surface plasmon effect of the Ag nanoparticles. The Ag/TiO(2)/MMT materials with excellent stability, recyclability, and bactericidal activities are promising photocatalysts for application in decontamination.

Synthesizing Pt nanoparticles in the presence of methylamine: Impact of acetic acid treatment in the electrocatalytic activity of formic acid oxidation

NASA Astrophysics Data System (ADS)

Ooi, M. D. Johan; Aziz, A. Abdul

2017-05-01

Surfactant removal from the surface of platinum nanoparticles prepared by solution based method is a prerequisite process to accomplish a high catalytic activity for electrochemical reactions. Here, we report a possible approach of combining acid acetic with thermal treatment for improving catalytic performance of formic acid oxidation. This strategy involves conversion of amine to amide in acetic acid followed by surfactant removal via subsequent thermal treatment at 85 °C. This combined activation technique produced monodisperse nanoparticle with the size of 3 to 5 nm with enhanced formic acid oxidation activity, particularly in perchloric acid solution. Pt treated in 1 h of acetic acid and heat treatment of 9 h shows high electrochemical surface area value (27.6 m2/g) compares to Pt without activation (16.6 m2/g). The treated samples also exhibit high current stability of 0.3 mA/cm2 compares to the as-prepared mA/cm2). Shorter duration of acid wash and longer duration of heating process result in high electrocatalytic activity. This work demonstrates a possible technique in improving catalytic activity of platinum nanoparticles synthesized using methylamine as surfactant.

Powder-in-tube and thick-film methods of fabricating high temperature superconductors having enhanced biaxial texture

DOEpatents

Goyal, Amit; Kroeger, Donald M.

2003-11-11

A method for forming an electronically active biaxially textured article includes the steps of providing a substrate having a single crystal metal or metal alloy surface, deforming the substrate to form an elongated substrate surface having biaxial texture and depositing an epitaxial electronically active layer on the biaxially textured surface. The method can include at least one annealing step after the deforming step to produce the biaxially textured substrate surface. The invention can be used to form improved biaxially textured articles, such as superconducting wire and tape articles having improved J.sub.c values.

Analysis of Long-Term Cloud Cover, Radiative Fluxes, and Sea Surface Temperature in the Eastern Tropical Pacific

NASA Technical Reports Server (NTRS)

Simpson, J. J.; Frouin, R.

1996-01-01

Grant activities accomplished during this reporting period are summarized. The contributions of the principle investigator are reported under four categories: (1) AHVRR (Advanced Very High Resolution Radiometer) data; (2) GOES (Geostationary Operational Environ Satellite) data; (3) system software design; and (4) ATSR (Along Track Scanning Radiometer) data. The contributions of the associate investigator are reported for:(1) longwave irradiance at the surface; (2) methods to derive surface short-wave irradiance; and (3) estimating PAR (photo-synthetically active radiation) surface. Several papers have resulted. Abstracts for each paper are provided.

Removal of daytime thermal deformations in the GBT active surface via out-of-focus holography

NASA Astrophysics Data System (ADS)

Hunter, T. R.; Mello, M.; Nikolic, B.; Mason, B.; Schwab, F.; Ghigo, F.; Dicker, S.

2009-01-01

The 100-m diameter Green Bank Telescope (GBT) was built with an active surface of 2209 actuators in order to achieve and maintain an accurate paraboloidal shape. While much of the large-scale gravitational deformation of the surface can be described by a finite element model, a significant uncompensated gravitational deformation exists. In recent years, the elevation-dependence of this residual deformation has been successfully measured during benign nighttime conditions using the out-of-focus (OOF) holography technique (Nikolic et al, 2007, A&A 465, 685). Parametrized by a set of Zernike polynomials, the OOF model correction was implemented into the active surface and has been applied during all high-frequency observations since Fall 2006, yielding a consistent gain curve that is flat with elevation. However, large-scale thermal deformation of the surface has remained a problem for daytime high-frequency observations. OOF holography maps taken throughout a clear winter day indicate that surface deformations become significant whenever the Sun is above 10 degrees elevation, but that they change slowly while tracking a single source. In this paper, we describe a further improvement to the GBT active surface that allows an observer to measure and compensate for the thermal surface deformation using the OOF technique. In order to support high-frequency observers, "AutoOOF" is a new GBT Astrid procedure that acquires a quick set of in-focus and out-of-focus on-the-fly continuum maps on a quasar using the currently active receiver. Upon completion of the maps, the data analysis software is launched automatically which produces and displays the surface map along with a set of Zernike coefficients. These coefficients are then sent to the active surface manager which combines them with the existing gravitational Zernike terms and FEM in order to compute the total active surface correction. The end-to-end functionality has been tested on the sky at Q-Band and Ka-band during several mornings and afternoons. The telescope beam profiles on a bright quasar typically change from slightly asymmetric to Gaussian, the peak antenna temperature increases, and significant sidelobes (when present) are eliminated. This technique has the potential to bring the daytime GBT aperture efficiency at high frequencies closer to its nighttime level. The total time to run the procedure and apply the corrections is about 20 minutes. The time interval over which the solutions remain valid and helpful will likely vary with the weather conditions and program of observations, and can be better evaluated once a larger dataset has been acquired. We are presently researching the OOF technique using MUSTANG, the first 90 GHz instrument on the GBT. MUSTANG is 64-pixel bolometer camera, presently operating as a shared-risk science instrument. The use of multi-pixel MUSTANG maps has the potential to significantly speed the process of measuring and correcting thermal deformations to the surface during 90 GHz observations. Of course, the efficiency of 90 GHz observations with the GBT is also limited by the small-scale surface roughness due to errors in the initial setting of the actuator zero points and the individual panel corners. We are planning to measure these errors in detail with traditional holography in the near future.

Removal of daytime thermal deformations in the GBT active surface via out-of-focus holography

NASA Astrophysics Data System (ADS)

Hunter, T. R.; Mello, M.; Nikolic, B.; Mason, B. S.; Schwab, F. R.; Ghigo, F. D.; Dicker, S. R.

2009-01-01

The 100-m diameter Green Bank Telescope (GBT) was built with an active surface of 2209 actuators in order to achieve and maintain an accurate paraboloidal shape. While much of the large-scale gravitational deformation of the surface can be described by a finite element model, a significant uncompensated gravitational deformation exists. In recent years, the elevation-dependence of this residual deformation has been successfully measured during benign nighttime conditions using the out-of-focus (OOF) holography technique (Nikolic et al, 2007, A&A 465, 685). Parametrized by a set of Zernike polynomials, the OOF model correction was implemented into the active surface and has been applied during all high frequency observations since Fall 2006, yielding a consistent gain curve that is constant with elevation. However, large-scale thermal deformation of the surface has remained a problem for daytime high-frequency observations. OOF holography maps taken throughout a clear winter day indicate that surface deformations become significant whenever the Sun is above 10 degrees elevation, but that they change slowly while tracking a single source. In this paper, we describe a further improvement to the GBT active surface that allows an observer to measure and compensate for the thermal surface deformation using the OOF technique. In order to support high-frequency observers, "AutoOOF" is a new GBT Astrid procedure that acquires a quick set of in-focus and out-of-focus on-the-fly continuum maps on a quasar using the currently active receiver. Upon completion of the maps, the data analysis software is launched automatically which produces and displays the surface map along with a set of Zernike coefficients. These coefficients are then sent to the active surface manager which combines them with the existing gravitational Zernike terms and FEM in order to compute the total active surface correction. The end-to-end functionality has been tested on the sky at Q-Band and Ka-band during several mornings and afternoons. The telescope beam profiles on a bright quasar typically change from slightly asymmetric to Gaussian, the peak antenna temperature increases, and signicant sidelobes (when present) are eliminated. This technique has the potential to bring the daytime GBT aperture efficiency at high frequencies closer to its nighttime level. The total time to run the procedure and apply the corrections is about 20 minutes. The time interval over which the solutions remain valid and helpful will likely vary with the weather conditions and program of observations, and can be better evaluated once a larger dataset has been acquired. We are presently researching the OOF technique using MUSTANG, the first 90 GHz instrument on the GBT. MUSTANG is 64-pixel bolometer camera, presently operating as a shared-risk science instrument. The use of multi-pixel MUSTANG maps has the potential to signicantly speed the process of measuring and correcting thermal deformations to the surface during 90 GHz observations. Of course, th efficiency of 90 GHz observations with the GBT is also limited by the small-scale surface roughness due to errors in the initial setting of the actuator zero points and the individual panel corners. We are planning to measure these errors in detail with traditional holography in the near future.

New Element Organic Frameworks Based on Sn, Sb, and Bi, with Permanent Porosity and High Catalytic Activity

PubMed Central

Fritsch, Julia; Rose, Marcus; Wollmann, Philipp; Böhlmann, Winfried; Kaskel, Stefan

2010-01-01

We present new element organic frameworks based on Sn, Sb and Bi atoms connected via organic linkers by element-carbon bonds. The open frameworks are characterized by specific surface areas (BET) of up to 445 m2 g-1 and a good stability under ambient conditions resulting from a highly hydrophobic inner surface. They show good performance as heterogeneous catalysts in the cyanosylilation of benzaldehyde as a test reaction. Due to their catalytic activity, this class of materials might be able to replace common homogeneous element-organic and often highly toxic catalysts especially in the food industry.

Application of a mixed metal oxide catalyst to a metallic substrate

NASA Technical Reports Server (NTRS)

Sevener, Kathleen M. (Inventor); Lohner, Kevin A. (Inventor); Mays, Jeffrey A. (Inventor); Wisner, Daniel L. (Inventor)

2009-01-01

A method for applying a mixed metal oxide catalyst to a metallic substrate for the creation of a robust, high temperature catalyst system for use in decomposing propellants, particularly hydrogen peroxide propellants, for use in propulsion systems. The method begins by forming a prepared substrate material consisting of a metallic inner substrate and a bound layer of a noble metal intermediate. Alternatively, a bound ceramic coating, or frit, may be introduced between the metallic inner substrate and noble metal intermediate when the metallic substrate is oxidation resistant. A high-activity catalyst slurry is applied to the surface of the prepared substrate and dried to remove the organic solvent. The catalyst layer is then heat treated to bind the catalyst layer to the surface. The bound catalyst layer is then activated using an activation treatment and calcinations to form the high-activity catalyst system.

Cesium and Strontium Retentions Governed by Aluminosilicate Gel in Alkali-Activated Cements

PubMed Central

Jang, Jeong Gook; Park, Sol Moi; Lee, Haeng Ki

2017-01-01

The present study investigates the retention mechanisms of cesium and strontium for alkali-activated cements. Retention mechanisms such as adsorption and precipitation were examined in light of chemical interactions. Batch adsorption experiments and multi-technical characterizations by using X-ray diffraction, zeta potential measurements, and the N2 gas adsorption/desorption methods were conducted for this purpose. Strontium was found to crystalize in alkali-activated cements, while no cesium-bearing crystalline phases were detected. The adsorption kinetics of alkali-activated cements having relatively high adsorption capacities were compatible with pseudo-second-order kinetic model, thereby suggesting that it is governed by complex multistep adsorption. The results provide new insight, demonstrating that characteristics of aluminosilicate gel with a highly negatively charged surface and high micropore surface area facilitated more effective immobilization of cesium and strontium in comparison with calcium silicate hydrates. PMID:28772803

Hydroisomerization of n-Hexane Using Acidified Metal-Organic Framework and Platinum Nanoparticles.

PubMed

Sabyrov, Kairat; Jiang, Juncong; Yaghi, Omar M; Somorjai, Gabor A

2017-09-13

Exceptionally high surface area and ordered nanopores of a metal-organic framework (MOF) are exploited to encapsulate and homogeneously disperse a considerable amount of phosphotungstic acid (PTA). When combined with platinum nanoparticles positioned on the external surface of the MOF, the construct shows a high catalytic activity for hydroisomerization of n-hexane, a reaction requiring hydrogenation/dehydrogenation and moderate to strong Brønsted acid sites. Characterization of the catalytic activity and acidic sites as a function of PTA loading demonstrates that both the concentration and strength of acidic sites are highest for the catalyst with the largest amount of PTA. The MOF construct containing 60% PTA by weight produces isoalkanes with 100% selectivity and 9-fold increased mass activity as compared to a more traditional aluminosilicate catalyst, further demonstrating the capacity of the MOF to contain a high concentration of active sites necessary for the isomerization reaction.

[Bone cement adhesion on ceramic surfaces - surface activation of retention surfaces of knee prostheses by atmospheric plasma versus thermal surface treatment].

PubMed

Marx, B; Marx, R; Reisgen, U; Wirtz, D

2015-04-01

CoCrMo alloys are contraindicated for allergy sufferers. For these patients, uncemented and cemented prostheses made of titanium alloy are indicated. Knee prostheses machined from that alloy, however, may have poor tribological behaviour, especially in relation to UHMWPE inlays. Therefore, for knee replacement cemented high-strength oxide ceramic prostheses are suitable for allergy sufferers and in cases of particle-induced aseptic loosening. For adhesion of bone cement, the ceramic surface, however, only exposes inefficient mechanical retention spots as compared with a textured metal surface. Undercuts generated by corundum blasting which in the short-term are highly efficient on a CoCrMo surface are not possible on a ceramic surface due to the brittleness of ceramics. Textures due to blasting may initiate cracks which will weaken the strength of a ceramic prosthesis. Due to the lack of textures mechanical retention is poor or even not existent. Micromotions are promoted and early aseptic loosening is predictable. Instead silicoating of the ceramic surface will allow specific adhesion and result in better hydrolytic stability of bonding thereby preventing early aseptic loosening. Silicoating, however, presupposes a clean and chemically active surface which can be achieved by atmospheric plasma or thermal surface treatment. In order to evaluate the effectiveness of silicoating the bond strengths of atmospheric plasma versus thermal surface treated and silicate layered ZPTA surfaces were compared with "as-fired" surfaces by utilising TiAlV probes (diameter 6 mm) for traction-adhesive strength tests. After preparing samples for traction-adhesive strength tests (sequence: ceramic substrate, silicate and silane, protective lacquer [PolyMA], bone cement, TiAlV probe) they were aged for up to 150 days at 37 °C in Ringer's solution. The bond strengths observed for all ageing intervals were well above 20 MPa and much higher and more hydrolytically stable for silicate layered compared with "as-fired" ZPTA samples. Silicoating may be effective for achieving high initial bond strength of bone cement on surfaces of oxide ceramics and also suitable to stabilise bond strength under hydrolytic conditions as present in the human body in the long-term. Activation by atmospheric plasma or thermal surface treatment seems to be effective for activation prior to silicoating. Due the proposed silicate layer migration, micromotions and debonding should be widely reduced or even eliminated. Georg Thieme Verlag KG Stuttgart · New York.

First principles investigation of heterogeneous catalysis on metal oxide surfaces

NASA Astrophysics Data System (ADS)

Ghoussoub, Mireille

Metal oxides possess unique electronic and structural properties that render them highly favourable for applications in heterogeneous catalysis. In this study, computational atomistic modelling based on Density Functional Theory was used to investigate the reduction of carbon dioxide over hydroxylated indium oxide nanoparticles, as well at the activation of methane over oxygen-covered bimetallic surfaces. The first study employed metadynamics-biased ab initio molecular dynamics to obtain the free energy surface of the various reaction steps at finite temperature. In the second study, the nudged elastic band method was used to probe the C-H activation mechanisms for different surface configurations. In both cases, activation energies, reaction energies, transition state structures, and charge analysis results are used to explain the underlying mechanistic pathways.

Nutrient sampling slam: high resolution surface-water sampling in streams reveals patterns in groundwater chemistry and flow paths

EPA Science Inventory

The groundwater–surface water interface (GSWI), consisting of shallow groundwater adjacent to stream channels, is a hot spot for nitrogen removal processes, a storage zone for other solutes, and a target for restoration activities. Characterizing groundwater-surface water intera...

A doped activated carbon prepared from polyaniline for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Li, Limin; Liu, Enhui; Li, Jian; Yang, Yanjing; Shen, Haijie; Huang, Zhengzheng; Xiang, Xiaoxia; Li, Wen

A novel doped activated carbon has been prepared from H 2SO 4-doped polyaniline which is prepared by the oxypolymerization of aniline. The morphology, surface chemical composition and surface area of the carbon have been investigated by scanning electron microscope, X-ray photoelectron spectroscopy and Brunaner-Emmett-Teller measurement, respectively. Electrochemical properties of the doped activated carbon have been studied by cyclic voltammograms, galvanostatic charge/discharge, and electrochemical impedance spectroscopy measurements in 6 mol l -1 KOH. The specific capacitance of the carbon is as high as 235 F g -1, the specific capacitance hardly decreases at a high current density 11 A g -1 after 10,000 cycles, which indicates that the carbon possesses excellent cycle durability and may be a promising candidate for supercapacitors.

Nanoporous activated carbon derived from Lapsi (Choerospondias axillaris) seed stone for the removal of arsenic from water.

PubMed

Rajbhandari, Rinita; Shrestha, Lok Kumar; Pradhananga, Raja Ram

2012-09-01

Activated carbons were prepared from Lapsi (Choerospondias axillaris) seed stone by zinc chloride (ZnCl2) activation at three different Lapsi seed powder (LSP):ZnCl2 ratios: 1:0.5 (AC-0.5), 1:1 (AC-1), and 1:2 (AC-2). The properties of these activated carbons (ACs), including effective surface areas, pore volumes, and pore size distributions were characterized from N2 adsorption-desorption isotherms. The ACs obtained were essentially nanoporous (including both micro- and mesoporous) with effective surface area ranging from 1167 to 1328 m2/g. Fourier-transform infrared (FTIR) spectroscopy showed the presence of functional groups on the surface of ACs. Scanning electron microscopy (SEM) images showed a high pore development in the ACs. X-ray diffraction (XRD) patterns showed that, in addition to the amorphous structure, ACs contains crystalline ZnO formed during the carbonization. Presence of amorphous carbon is further confirmed by Raman scattering, where we observed only D and G bands. Iron impregnated nanoporous AC has been found to be very effective for arsenic removal from ground water; amount of arsenic is decreased from ca. 200 ppb to 10 ppb. These experimental results indicate the potential use of Lapsi seed as a precursor material for the preparation of high surface area nanoporous activated carbons.

Optical Assessment of Caries Lesion Structure and Activity

NASA Astrophysics Data System (ADS)

Lee, Robert Chulsung

New, more sophisticated diagnostic tools are needed for the detection and characterization of caries lesions in the early stages of development. It is not sufficient to simply detect caries lesions, methods are needed to assess the activity of the lesion and determine if chemical or surgical intervention is needed. Previous studies have demonstrated that polarization sensitive optical coherence tomography (PS-OCT) can be used to nondestructively image the subsurface lesion structure and measure the thickness of the highly mineralized surface zone. Other studies have demonstrated that the rate of dehydration can be correlated with the lesion activity and that the rate can be measured using optical methods. The main objective of this work was to test the hypothesis that optical methods can be used to assess lesion activity on tooth coronal and root surfaces. Simulated caries models were used to develop and validate an algorithm for detecting and measuring the highly mineralized surface layer using PS-OCT. This work confirmed that the algorithm was capable of estimating the thickness of the highly mineralized surface layer with high accuracy. Near-infrared (NIR) reflectance and thermal imaging methods were used to assess activity of caries lesions by measuring the state of lesion hydration. NIR reflectance imaging performed the best for artificial enamel and natural coronal caries lesion samples, particularly at wavelengths coincident with the water absorption band at 1460-nm. However, thermal imaging performed the best for artificial dentin and natural root caries lesion samples. These novel optical methods outperformed the conventional methods (ICDAS II) in accurately assessing lesion activity of natural coronal and root caries lesions. Infrared-based imaging methods have shown potential for in-vivo applications to objectively assess caries lesion activity in a single examination. It is likely that if future clinical trials are a success, this novel imaging technology will be employed for the detection and monitoring of early carious lesions without the use of ionizing radiation, thereby enabling conservative non-surgical intervention and the preservation of healthy tissue structure.

Detailed Anatomical and Electrophysiological Models of Human Atria and Torso for the Simulation of Atrial Activation

PubMed Central

Ferrer, Ana; Sebastián, Rafael; Sánchez-Quintana, Damián; Rodríguez, José F.; Godoy, Eduardo J.; Martínez, Laura; Saiz, Javier

2015-01-01

Atrial arrhythmias, and specifically atrial fibrillation (AF), induce rapid and irregular activation patterns that appear on the torso surface as abnormal P-waves in electrocardiograms and body surface potential maps (BSPM). In recent years both P-waves and the BSPM have been used to identify the mechanisms underlying AF, such as localizing ectopic foci or high-frequency rotors. However, the relationship between the activation of the different areas of the atria and the characteristics of the BSPM and P-wave signals are still far from being completely understood. In this work we developed a multi-scale framework, which combines a highly-detailed 3D atrial model and a torso model to study the relationship between atrial activation and surface signals in sinus rhythm. Using this multi scale model, it was revealed that the best places for recording P-waves are the frontal upper right and the frontal and rear left quadrants of the torso. Our results also suggest that only nine regions (of the twenty-one structures in which the atrial surface was divided) make a significant contribution to the BSPM and determine the main P-wave characteristics. PMID:26523732

Evaluation of the Catalytic Activity and Cytotoxicity of Palladium Nanocubes. The Role of Oxygen

PubMed Central

Dahal, Eshan; Curtiss, Jessica; Subedi, Deepak; Chen, Gen; Houston, Jessica P.; Smirnov, Sergei

2015-01-01

Recently it has been reported that palladium nanocubes (PdNC) are capable of generating singlet oxygen without photo-excitation simply via chemisorption of molecular oxygen on its surface. Such a trait would make PdNC a highly versatile catalyst suitable in organic synthesis and a Reactive Oxygen Species (ROS) inducing cancer treatment reagent. Here we thoroughly investigated the catalytic activity of PdNC with respect to their ability to produce singlet oxygen and to oxidize 3,5,3′,5′-tetramethyl-benzidine (TMB), as well as, analyzed the cytotoxic properties of PdNC on HeLa cells. Our findings showed no evidence of singlet oxygen production by PdNC. The nanocubes’ activity is not necessarily linked to activation of oxygen. The oxidation of substrate on PdNC can be a first step followed by PdNC regeneration with oxygen or other oxidant. The catalytic activity of PdNC towards oxidation of TMB is very high and shows direct two-electrons oxidation when the surface of PdNC is clean and the ratio of TMB/PdNC is not very high. Sequential one electron oxidation is observed when the pristine quality of PdNC surface is compromised by serum or uncontrolled impurities and/or the ratio of TMB/PdNC is high. Clean PdNC in serum-free media efficiently induce apoptosis of HeLa cells. It is the primary route of cell death and is associated with hyperpolarization of mitochondria, contrary to a common mitochondrial depolarization initiated by ROS. Again, the effects are very sensitive to how well the pristine surface of PdNC is preserved, suggesting that PdNC can be used as an apoptosis inducing agent but only with appropriate drug delivery system. PMID:25886644

Enhancing Electrochemical Water-Splitting Kinetics by Polarization-Driven Formation of Near-Surface Iron(0): An In Situ XPS Study on Perovskite-Type Electrodes**

PubMed Central

Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Rameshan, Raffael; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Fleig, Jürgen; Klötzer, Bernhard

2015-01-01

In the search for optimized cathode materials for high-temperature electrolysis, mixed conducting oxides are highly promising candidates. This study deals with fundamentally novel insights into the relation between surface chemistry and electrocatalytic activity of lanthanum ferrite based electrolysis cathodes. For this means, near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and impedance spectroscopy experiments were performed simultaneously on electrochemically polarized La0.6Sr0.4FeO3−δ (LSF) thin film electrodes. Under cathodic polarization the formation of Fe0 on the LSF surface could be observed, which was accompanied by a strong improvement of the electrochemical water splitting activity of the electrodes. This correlation suggests a fundamentally different water splitting mechanism in presence of the metallic iron species and may open novel paths in the search for electrodes with increased water splitting activity. PMID:25557533

Understanding the effect of surface/bulk defects on the photocatalytic activity of TiO2: anatase versus rutile.

PubMed

Yan, Junqing; Wu, Guangjun; Guan, Naijia; Li, Landong; Li, Zhuoxin; Cao, Xingzhong

2013-07-14

The sole effect of surface/bulk defects of TiO2 samples on their photocatalytic activity was investigated. Nano-sized anatase and rutile TiO2 were prepared by hydrothermal method and their surface/bulk defects were adjusted simply by calcination at different temperatures, i.e. 400-700 °C. High temperature calcinations induced the growth of crystalline sizes and a decrease in the surface areas, while the crystalline phase and the exposed facets were kept unchanged during calcination, as indicated by the characterization results from XRD, Raman, nitrogen adsorption-desorption, TEM and UV-Vis spectra. The existence of surface/bulk defects in calcined TiO2 samples was confirmed by photoluminescence and XPS spectra, and the surface/bulk defect ratio was quantitatively analyzed according to positron annihilation results. The photocatalytic activity of calcined TiO2 samples was evaluated in the photocatalytic reforming of methanol and the photocatalytic oxidation of α-phenethyl alcohol. Based on the characterization and catalytic results, a direct correlation between the surface specific photocatalytic activity and the surface/bulk defect density ratio could be drawn for both anatase TiO2 and rutile TiO2. The surface defects of TiO2, i.e. oxygen vacancy clusters, could promote the separation of electron-hole pairs under irradiation, and therefore, enhance the activity during photocatalytic reaction.

Molecular ligand modulation of palladium nanocatalysts for highly efficient and robust heterogeneous oxidation of cyclohexenone to phenol

DOE PAGES

Xue, Teng; Lin, Zhaoyang; Chiu, Chin-Yi; ...

2017-01-06

Metallic nanoparticles are emerging as an exciting class of heterogeneous catalysts with the potential advantages of exceptional activity, stability, recyclability, and easier separation than homogeneous catalysts. The traditional colloid nanoparticle syntheses usually involve strong surface binding ligands that could passivate the surface active sites and result in poor catalytic activity. The subsequent removal of surface ligands could reactivate the surface but often leads to metal ion leaching and/or severe Ostwald ripening with diminished catalytic activity or poor stability. Molecular ligand engineering represents a powerful strategy for the design of homogeneous molecular catalysts but is insufficiently explored for nanoparticle catalysts tomore » date. We report a systematic investigation on molecular ligand modulation of palladium (Pd) nanoparticle catalysts. Our studies show that β-functional groups of butyric acid ligand on Pd nanoparticles can significantly modulate the catalytic reaction process to modify the catalytic activity and stability for important aerobic reactions. With a β-hydroxybutyric acid ligand, the Pd nanoparticle catalysts exhibit exceptional catalytic activity and stability with an unsaturated turnover number (TON) >3000 for dehydrogenative oxidation of cyclohexenone to phenol, greatly exceeding that of homogeneous Pd(II) catalysts (TON, ~30). This study presents a systematic investigation of molecular ligand modulation of nanoparticle catalysts and could open up a new pathway toward the design and construction of highly efficient and robust heterogeneous catalysts through molecular ligand engineering.« less

Report of the panel on the land surface: Process of change, section 5

NASA Technical Reports Server (NTRS)

Adams, John B.; Barron, Eric E.; Bloom, Arthur A.; Breed, Carol; Dohrenwend, J.; Evans, Diane L.; Farr, Thomas T.; Gillespie, Allan R.; Isaks, B. L.; Williams, Richard S.

1991-01-01

The panel defined three main areas of study that are central to the Solid Earth Science (SES) program: climate interactions with the Earth's surface, tectonism as it affects the Earth's surface and climate, and human activities that modify the Earth's surface. Four foci of research are envisioned: process studies with an emphasis on modern processes in transitional areas; integrated studies with an emphasis on long term continental climate change; climate-tectonic interactions; and studies of human activities that modify the Earth's surface, with an emphasis on soil degradation. The panel concluded that there is a clear requirement for global coverage by high resolution stereoscopic images and a pressing need for global topographic data in support of studies of the land surface.

Effect of support size on the catalytic activity of metal-oxide-doped silica particles in the glycolysis of polyethylene terephthalate.

PubMed

Wi, Rinbok; Imran, Muhammad; Lee, Kyoung G; Yoon, Sun Hong; Cho, Bong Gyoo; Kim, Do Hyun

2011-07-01

Zinc oxide (ZnO) and cerium oxide (CeO2) nanoparticles were deposited on the surface of preformed silica spheres with diameters ranging from 60 to 750 nm. Ultrasonic irradiation was employed to promote the deposition of the metal oxide nanoparticles on the surface of silica. Silica-supported zinc oxide or cerium oxide was used as a catalyst in the glycolysis of polyethylene terephthalate, one of the key processes in the depolymerization of polyethylene terephthalate. The effect of the support size on the catalytic activity was studied in terms of monomer yield, and the monomer concentration was analyzed via high-performance liquid chromatography (HPLC). The morphologies and surface properties of the catalysts were characterized using a scanning electron microscope, a transmission electron microscope, and a BET surface area analyzer, while the monomer was characterized via HPLC and nuclear-magnetic-resonance spectroscopy. Both the zinc oxide and cerium oxide deposited on a smaller support showed better distribution and less aggregation. The high specific surface area of the smaller support catalysts provided a large number of active sites. The highest monomer yield was obtained with a catalyst of 60-nm silica support.

Improving genetic immobilization of a cellulase on yeast cell surface for bioethanol production using cellulose.

PubMed

Yang, Jinying; Dang, Hongyue; Lu, Jian Ren

2013-04-01

In this study, Saccharomyces cerevisiae was genetically engineered to harbor the capability of utilizing celluloses for bioethanol production by displaying active cellulolytic enzymes on the cell surface. An endo-1,4-β-glucanase gene egX was cloned from Bacillus pumilus C-9 and its expression products, the EGX cellulases, were displayed on the cell surface of S. cerevisiae by fusing egX with aga2 that encodes the binding subunit of the S. cerevisiae cell wall protein α-agglutinin. To achieve high gene copies and stability, multicopy integration was obtained by integrating the fusion aga2-egX gene into the rDNA region of the S. cerevisiae chromosome. To achieve high expression and surface display efficiency, the aga2-egX gene was expressed under the control of a strong promoter. The presence of the enzymatically active cellulase fusion proteins on the S. cerevisiae cell surface was verified by carboxymethyl cellulase activity assay and immunofluorescence microscopy. This work presented a promising strategy to genetically engineer yeasts to perform efficient fermentation of cellulosic materials for bioethanol production. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High surface area LaMnO3 nanoparticles enhancing electrochemical catalytic activity for rechargeable lithium-air batteries

NASA Astrophysics Data System (ADS)

Li, Chuanhua; Yu, Zhiyong; Liu, Hanxing; Chen, Kang

2018-02-01

To improve sluggish kinetics of ORR and OER (oxygen reduction and evolution reaction) on the air electrode, the high surface area LaMnO3 nanoparticle catalysts were synthesized by sol-gel method. The specific surface area of as-synthesized pure phase LaMnO3 nanoparticles is 21.21 m2 g-1. The onset potential of high surface area LaMnO3 in alkaline solution is -0.0202 V which is comparable to commercial Pt/C. When the assembled high surface area LaMnO3-based lithium-air batteries were measured at 100 mA g-1, the initial discharge specific capacity could reach 6851.9 mA h g-1(carbon). In addition, lithium-oxygen batteries including high surface area LaMnO3 catalysts could be cycled for 52 cycles at 200 mA g-1 under a limited discharge-charge depth of 500 mA h gcarbon-1.

Facile synthesis of bird's nest-like TiO2 microstructure with exposed (001) facets for photocatalytic degradation of methylene blue

NASA Astrophysics Data System (ADS)

Zhang, Guozhong; Zhang, Shuqu; Wang, Longlu; Liu, Ran; Zeng, Yunxiong; Xia, Xinnian; Liu, Yutang; Luo, Shenglian

2017-01-01

The scrupulous design of hierarchical structure and highly active crystal facets exposure is essential for the creation of photocatalytic system. However, it is still a big challenge for scrupulous design of TiO2 architectures. In this paper, bird's nest-like anatase TiO2 microstructure with exposed highly active (001) surface has been successfully synthesized by a facile one-step solvothermal method. Methylene blue (MB) is chosen as a model pollutant to evaluate photocatalytic activity of as-obtained TiO2 samples. The results show that the photocatalytic activity of the bird's nest-like sample is more excellent than P25 in the degradation of MB due to high specific surface area and highly active (001) crystal facets exposure when tested under simulated solar light. Besides, it can be readily separated from the photocatalytic system by sedimentation after photocatalytic reaction, which is a significant advantage against conventional powder photocatalyst. The bird's nest-like microspheres with novel structure may have potential application in photocatalysis and other fields.

Structure and functional properties of TiNiZr surface layers obtained by high-velocity oxygen fuel spraying

NASA Astrophysics Data System (ADS)

Rusinov, P. O.; Blednova, Zh M.; Borovets, O. I.

2017-05-01

The authors studied a complex method of surface modification of steels for materials with shape memory effect (SME) Ti-Ni-Zr with a high-velocity oxygen-fuel spraying (HVOF) of mechanically activated (MA) powder in a protective medium. We assessed the functional properties and X-ray diffraction studies, which showed that the formation of surface layers according to the developed technology ensures the manifestation of the shape memory effect.

Surface modification of a gold-coated microcantilever and application in biomarker detection

NASA Astrophysics Data System (ADS)

Binh Pham, Van; Nhat Khoa Phan, Thanh; Nguyen, Thanh Trung; Pham, Xuan Thanh Tung; Thanh Tuyen Le, Thi; Chien Dang, Mau

2015-12-01

Biosensors have been rapidly developed recently. Biological receptors, such as antibodies, must be immobilized on these sensors’ surfaces to make the sensor capable of capturing a target analyte. In this research we studied how to modify a gold-coated surface of a microcantilever, a sensor with high potential in biological and medical applications. Thiol chemistry was adapted to create a cysteamine layer on a gold surface, and subsequently glutaraldehyde was used as a cross-linking agent to react with amine groups in receptors. In order to evaluate the efficiency of immobilizing protein on an Au surface and also whether the protein retains its biological activity, horseradish peroxidase enzyme (HRP) with its activity to catalyze a reaction between 2,2‧-azino-bis [3-ethylbenzothiazoline-6-sulphonic acid] (ABTS) and {{{H}}}2{{{{O}}}2}- was used as a testing protein. The result showed that HRP was immobilized successfully on cysteamine and glutaraldehyde layers and retained its activity. The cantilever’s tip deflection was also measured, and results showed that each layer created surface stress and made the cantilever bend—in particular, the cysteamine layer induced bending as high as 6 μm. An antibody of alpha-fetoprotein (AFP) was immobilized on the cantilever surface, and the measurement deflection showed that the sensor responded to solution containing AFP with concentration from 100 to 500 ng ml-1.

Hijacking Complement Regulatory Proteins for Bacterial Immune Evasion.

PubMed

Hovingh, Elise S; van den Broek, Bryan; Jongerius, Ilse

2016-01-01

The human complement system plays an important role in the defense against invading pathogens, inflammation and homeostasis. Invading microbes, such as bacteria, directly activate the complement system resulting in the formation of chemoattractants and in effective labeling of the bacteria for phagocytosis. In addition, formation of the membrane attack complex is responsible for direct killing of Gram-negative bacteria. In turn, bacteria have evolved several ways to evade complement activation on their surface in order to be able to colonize and invade the human host. One important mechanism of bacterial escape is attraction of complement regulatory proteins to the microbial surface. These molecules are present in the human body for tight regulation of the complement system to prevent damage to host self-surfaces. Therefore, recruitment of complement regulatory proteins to the bacterial surface results in decreased complement activation on the microbial surface which favors bacterial survival. This review will discuss recent advances in understanding the binding of complement regulatory proteins to the bacterial surface at the molecular level. This includes, new insights that have become available concerning specific conserved motives on complement regulatory proteins that are favorable for microbial binding. Finally, complement evasion molecules are of high importance for vaccine development due to their dominant role in bacterial survival, high immunogenicity and homology as well as their presence on the bacterial surface. Here, the use of complement evasion molecules for vaccine development will be discussed.

Hijacking Complement Regulatory Proteins for Bacterial Immune Evasion

PubMed Central

Hovingh, Elise S.; van den Broek, Bryan; Jongerius, Ilse

2016-01-01

The human complement system plays an important role in the defense against invading pathogens, inflammation and homeostasis. Invading microbes, such as bacteria, directly activate the complement system resulting in the formation of chemoattractants and in effective labeling of the bacteria for phagocytosis. In addition, formation of the membrane attack complex is responsible for direct killing of Gram-negative bacteria. In turn, bacteria have evolved several ways to evade complement activation on their surface in order to be able to colonize and invade the human host. One important mechanism of bacterial escape is attraction of complement regulatory proteins to the microbial surface. These molecules are present in the human body for tight regulation of the complement system to prevent damage to host self-surfaces. Therefore, recruitment of complement regulatory proteins to the bacterial surface results in decreased complement activation on the microbial surface which favors bacterial survival. This review will discuss recent advances in understanding the binding of complement regulatory proteins to the bacterial surface at the molecular level. This includes, new insights that have become available concerning specific conserved motives on complement regulatory proteins that are favorable for microbial binding. Finally, complement evasion molecules are of high importance for vaccine development due to their dominant role in bacterial survival, high immunogenicity and homology as well as their presence on the bacterial surface. Here, the use of complement evasion molecules for vaccine development will be discussed. PMID:28066340

Converting biomass waste into microporous carbon with simultaneously high surface area and carbon purity as advanced electrochemical energy storage materials

NASA Astrophysics Data System (ADS)

Sun, Fei; Wang, Lijie; Peng, Yiting; Gao, Jihui; Pi, Xinxin; Qu, Zhibin; Zhao, Guangbo; Qin, Yukun

2018-04-01

Developing carbon materials featuring both high accessible surface area and high structure stability are desirable to boost the performance of constructed electrochemical electrodes and devices. Herein, we report a new type of microporous carbon (MPC) derived from biomass waste based on a simple high-temperature chemical activation procedure. The optimized MPC-900 possesses microporous structure, high surface area, partially graphitic structure, and particularly low impurity content, which are critical features for enhancing carbon-based electrochemical process. The constructed MPC-900 symmetric supercapacitor exhibits high performances in commercial organic electrolyte such as widened voltage window up to 3 V and thereby high energy/power densities (50.95 Wh kg-1 at 0.44 kW kg-1; 25.3 Wh kg-1 at 21.5 kW kg-1). Furthermore, a simple melt infiltration method has been employed to enclose SnO2 nanocrystals onto the carbon matrix of MPC-900 as a high-performance lithium storage material. The obtained SnO2-MPC composite with ultrafine SnO2 nanocrystals delivers high capacities (1115 mAh g-1 at 0.2 A g-1; 402 mAh g-1 at 10 A g-1) and high-rate cycling lifespan of over 2000 cycles. This work not only develops a microporous carbon with high carbon purity and high surface area, but also provides a general platform for combining electrochemically active materials.

Photocatalytic CO2 reduction over SrTiO3: Correlation between surface structure and activity

NASA Astrophysics Data System (ADS)

Luo, Chao; Zhao, Jie; Li, Yingxuan; Zhao, Wen; Zeng, Yubin; Wang, Chuanyi

2018-07-01

Perovskite oxide SrTiO3 is a promising semiconductor photocatalyst for CO2 reduction, which has two possible chemical surfaces-TiO2-terminated and SrO-terminated surfaces. Up to now, the effect of chemical surface and its modification on CO2 adsorption, activation and sequential photocatalytic reduction is not established. In the work, SrTiO3, surface-Ti-rich SrTiO3 and Sr(OH)2-decorated SrTiO3 were prepared and their structural, surface, and optical properties and photocatalytic activity were explored. It is found that the absorption edge of surface-Ti-rich SrTiO3 shifted toward visible-light region as compared with that of the other two photocatalysts, which is attributed to the decreased Ti 3d ground-state level at the surface. Bicarbonate- (HCO3-) and bidentate carbonate-like (b-CO3=) species are the main species for CO2 adsorption on the surface-Ti-rich SrTiO3, whereas, besides HCO3- and b-CO3=, plenty of monodentate carbonate-like species (m-CO3=) that has relatively low reactivity is present on the SrTiO3 and Sr(OH)2-decorated photocatalysts. As a result, the surface-Ti-rich SrTiO3 exhibits the highest activity for CO2 reduction. Furthermore, although Sr(OH)2-decoration and SrO-terminated surfaces facilitate CO2 fixing, the produced surface species are attached to the weakly active Sr ions, giving rise to the lower reactivity. The present work might supply a guide for designing highly active perovskite-type semiconductors for photocatalysis.

RhoA-Mediated Functions in C3H10T1/2 Osteoprogenitors Are Substrate Topography Dependent.

PubMed

Ogino, Yoichiro; Liang, Ruiwei; Mendonça, Daniela B S; Mendonça, Gustavo; Nagasawa, Masako; Koyano, Kiyoshi; Cooper, Lyndon F

2016-03-01

Surface topography broadly influences cellular responses. Adherent cell activities are regulated, in part, by RhoA, a member of the Rho-family of GTPases. In this study, we evaluated the influence of surface topography on RhoA activity and associated cellular functions. The murine mesenchymal stem cell line C3H10T1/2 cells (osteoprogenitor cells) were cultured on titanium substrates with smooth topography (S), microtopography (M), and nanotopography (N) to evaluate the effect of surface topography on RhoA-mediated functions (cell spreading, adhesion, migration, and osteogenic differentiation). The influence of RhoA activity in the context of surface topography was also elucidated using RhoA pharmacologic inhibitor. Following adhesion, M and N adherent cells developed multiple projections, while S adherent cells had flattened and widespread morphology. RhoA inhibitor induced remarkable longer and thinner cytoplasmic projections on all surfaces. Cell adhesion and osteogenic differentiation was topography dependent with S < M and N surfaces. RhoA inhibition increased adhesion on S and M surfaces, but not N surfaces. Cell migration in a wound healing assay was greater on S versus M versus N surfaces and RhoA inhibitor increased S adherent cell migration, but not N adherent cell migration. RhoA inhibitor enhanced osteogenic differentiation in S adherent cells, but not M or N adherent cells. RhoA activity was surface topography roughness dependent (S < M, N). RhoA activity and -mediated functions are influenced by surface topography. Smooth surface adherent cells appear highly sensitive to RhoA function, while nano-scale topography adherent cell may utilize alternative cellular signaling pathway(s) to influence adherent cellular functions regardless of RhoA activity. © 2015 Wiley Periodicals, Inc.

Rutile (β-)MnO2 surfaces and vacancy formation for high electrochemical and catalytic performance.

PubMed

Tompsett, David A; Parker, Stephen C; Islam, M Saiful

2014-01-29

MnO2 is a technologically important material for energy storage and catalysis. Recent investigations have demonstrated the success of nanostructuring for improving the performance of rutile MnO2 in Li-ion batteries and supercapacitors and as a catalyst. Motivated by this we have investigated the stability and electronic structure of rutile (β-)MnO2 surfaces using density functional theory. A Wulff construction from relaxed surface energies indicates a rod-like equilibrium morphology that is elongated along the c-axis, and is consistent with the large number of nanowire-type structures that are obtainable experimentally. The (110) surface dominates the crystallite surface area. Moreover, higher index surfaces than considered in previous work, for instance the (211) and (311) surfaces, are also expressed to cap the rod-like morphology. Broken coordinations at the surface result in enhanced magnetic moments at Mn sites that may play a role in catalytic activity. The calculated formation energies of oxygen vacancy defects and Mn reduction at key surfaces indicate facile formation at surfaces expressed in the equilibrium morphology. The formation energies are considerably lower than for comparable structures such as rutile TiO2 and are likely to be important to the high catalytic activity of rutile MnO2.

Design for the fabrication of high efficiency solar cells

DOEpatents

Simmons, Joseph H.

1998-01-01

A method and apparatus for a photo-active region for generation of free carriers when a first surface is exposed to optical radiation. The photo-active region includes a conducting transparent matrix and clusters of semiconductor materials embedded within the conducting transparent matrix. The clusters are arranged in the matrix material so as to define at least a first distribution of cluster sizes ranging from those with the highest bandgap energy near a light incident surface of the photo-active region to those with the smallest bandgap energy near an opposite second surface of the photo-active region. Also disclosed is a method and apparatus for a solar cell. The solar cell includes a photo-active region containing a plurality of semiconductor clusters of varying sizes as described.

Phenol adsorption by activated carbon produced from spent coffee grounds.

PubMed

Castro, Cínthia S; Abreu, Anelise L; Silva, Carmen L T; Guerreiro, Mário C

2011-01-01

The present work highlights the preparation of activated carbons (ACs) using spent coffee grounds, an agricultural residue, as carbon precursor and two different activating agents: water vapor (ACW) and K(2)CO(3) (ACK). These ACs presented the microporous nature and high surface area (620-950 m(2) g(-1)). The carbons, as well as a commercial activated carbon (CAC) used as reference, were evaluated as phenol adsorbent showing high adsorption capacity (≈150 mg g(-1)). The investigation of the pH solution in the phenol adsorption was also performed. The different activating agents led to AC with distinct morphological properties, surface area and chemical composition, although similar phenol adsorption capacity was verified for both prepared carbons. The production of activated carbons from spent coffee grounds resulted in promising adsorbents for phenol removal while giving a noble destination to the residue.

Construction of High Activity Titanium Dioxide Crystal Surface Heterostructures and Characterization of Its Basic Properties

NASA Astrophysics Data System (ADS)

Wang, Chunxiao; Li, DanQi; Shen, Tingting; Lu, Cheng; Sun, Jing; Wang, Xikui

2018-01-01

Heterogeneous photocatalytic materials, which combine the advantages of photocatalytic materials and heterojunction, have been developed rapidly in the field of environmental pollution control. In this paper, TiO2 surface heterojunction catalysts with different catalytic activity were prepared by controlling the amount of HF, and their XRD characterization was also carried out. In addition, the optimum amount of HF was determined by photocatalytic degradation of simulated dye wastewater by methylene blue solution. And the optimal amount of catalyst and the optimal pH reaction conditions for degradation experiments were used to screen the highly reactive titania surface heterojunction system and its optimum application conditions. It provides the possibility of application in the degradation of industrial wastewater and environmental treatment.

Bridging the Gap: From Model Surfaces to Nanoparticle Analogs for Selective Oxidation and Steam Reforming of Methanol and Selective Hydrogenation Catalysis

NASA Astrophysics Data System (ADS)

Boucher, Matthew B.

Most industrial catalysts are very complex, comprising of non-uniform materials with varying structures, impurities, and interaction between the active metal and supporting substrate. A large portion of the ongoing research in heterogeneous catalysis focuses on understanding structure-function relationships in catalytic materials. In parallel, there is a large area of surface science research focused on studying model catalytic systems for which structural parameters can be tuned and measured with high precision. It is commonly argued, however, that these systems are oversimplified, and that observations made in model systems do not translate to robust catalysts operating in practical environments; this discontinuity is often referred to as a "gap." The focus of this thesis is to explore the mutual benefits of surface science and catalysis, or "bridge the gap," by studying two catalytic systems in both ultra-high vacuum (UHV) and near ambient-environments. The first reaction is the catalytic steam reforming of methanol (SRM) to hydrogen and carbon dioxide. The SRM reaction is a promising route for on-demand hydrogen production. For this catalytic system, the central hypothesis in this thesis is that a balance between redox capability and weak binding of reaction intermediates is necessary for high SRM activity and selectivity to carbon dioxide. As such, a new catalyst for the SRM reaction is developed which incorporates very small amounts of gold (<1 atomic %) supported on zinc oxide nanoparticles with controlled crystal structures. The performance of these catalysts was studied in a fixed-bed micro-reactor system at ambient pressures, and their structure was characterized by high-resolution microscopic and spectroscopic techniques. Pre-existing oxygen defects in zinc oxide {0001} surfaces, and those created by a perturbation of the defect equilibrium by addition of gold, provide an anchoring site for highly dispersed gold species. By utilizing shape control of zinc oxide supports, it is found that highly dispersed gold, capable of low-temperature redox behavior is most prominent on zinc oxide {0001} surfaces and leads to high SRM activity and selectivity to carbon dioxide. Like other Group IB metal catalysts the SRM over gold-zinc oxide proceeds through the formation and weak binding of formaldehyde, and subsequent coupling with methoxy to produce methyl formate. Mechanistic clarification of this point was achieved by studying the interaction methanol-water mixtures with model catalyst surfaces. Model catalysts were studied in a UHV chamber where the base pressure was maintained at 10-10 mbar. High resolutions surface science techniques show that hydrogen-bonded networks of water are capable of deprotonating methanol to methoxy on low index surfaces in the absence of atomic oxygen. These UHV studies show that adsorbates, other than oxygen, are capable of activating methanol on Group IB metal surfaces. The second reaction involves the selective hydrogenation of alkynes to alkenes. Selective hydrogenations of carbon-carbon multiple bonds are important for a wide range of industrial processes. The governing hypothesis for this reaction system is that cooperation between a minority metal with a low barrier for hydrogen dissociation, and a less-reactive host metal capable of hydrogen uptake via spillover will lead to high alkene selectivity. A strategy for the preparation of such a catalyst is developed using model catalyst studied in a UHV chamber. The model catalyst features isolated palladium atoms in a copper(111) surface, termed single atom alloy (SAA). Individual, isolated palladium atoms act as sites for hydrogen uptake, dissociation, and spillover onto an otherwise inert copper(111) host. Weak binding offered by copper provides a surface where selective hydrogenation reactions can take place. Palladium-copper SAA model catalysts are highly selective to the partial hydrogenation of acetylene, whereas surfaces containing larger palladium ensembles facilitate complete hydrogenation and decomposition. Nanoparticle analogs of palladium-copper SAAs were prepared to investigate the feasibility of this strategy for practical application. Very small amounts of palladium (<0.2 atomic %) on the surface of copper nanoparticles are highly active and selective catalysts for the partial hydrogenation of phenylacetylene to styrene. The performance of these catalysts was studied in a liquid-phase, stirred-tank batch reactor under a hydrogen head pressure of approximately 7 bar. Palladium alloyed into the surface of otherwise inactive copper nanoparticles shows a marked improvement in selectivity when compared to monometallic palladium catalysts with the same metal loading. This effect is attributed hydrogen spillover onto the copper surface. In summary, the development of new, highly active and selective catalysts for the methanol steam reforming reaction and for the partial hydrogenation of alkynes to alkenes was accomplished by the use of state-of-the-art techniques in both surface science and heterogeneous catalysis. The implications of this work can be extended to a wide variety of catalytic systems.

Photolithographic surface micromachining of polydimethylsiloxane (PDMS).

PubMed

Chen, Weiqiang; Lam, Raymond H W; Fu, Jianping

2012-01-21

A major technical hurdle in microfluidics is the difficulty in achieving high fidelity lithographic patterning on polydimethylsiloxane (PDMS). Here, we report a simple yet highly precise and repeatable PDMS surface micromachining method using direct photolithography followed by reactive ion etching (RIE). Our method to achieve surface patterning of PDMS applied an O(2) plasma treatment to PDMS to activate its surface to overcome the challenge of poor photoresist adhesion on PDMS for photolithography. Our photolithographic PDMS surface micromachining technique is compatible with conventional soft lithography techniques and other silicon-based surface and bulk micromachining methods. To illustrate the general application of our method, we demonstrated fabrication of large microfiltration membranes and free-standing beam structures in PDMS.

Photolithographic surface micromachining of polydimethylsiloxane (PDMS)

PubMed Central

Chen, Weiqiang; Lam, Raymond H. W.

2014-01-01

A major technical hurdle in microfluidics is the difficulty in achieving high fidelity lithographic patterning on polydimethylsiloxane (PDMS). Here, we report a simple yet highly precise and repeatable PDMS surface micromachining method using direct photolithography followed by reactive ion etching (RIE). Our method to achieve surface patterning of PDMS applied an O2 plasma treatment to PDMS to activate its surface to overcome the challenge of poor photoresist adhesion on PDMS for photolithography. Our photolithographic PDMS surface micromachining technique is compatible with conventional soft lithography techniques and other silicon-based surface and bulk micromachining methods. To illustrate the general application of our method, we demonstrated fabrications of large microfiltration membranes and free-standing beam structures in PDMS. PMID:22089984

Externally pressurized porous cylinder for multiple surface aerosol generation and method of generation

DOEpatents

Apel, Charles T.; Layman, Lawrence R.; Gallimore, David L.

1988-01-01

A nebulizer for generating aerosol having small droplet sizes and high efficiency at low sample introduction rates. The nebulizer has a cylindrical gas permeable active surface. A sleeve is disposed around the cylinder and gas is provided from the sleeve to the interior of the cylinder formed by the active surface. In operation, a liquid is provided to the inside of the gas permeable surface. The gas contacts the wetted surface and forms small bubbles which burst to form an aerosol. Those bubbles which are large are carried by momentum to another part of the cylinder where they are renebulized. This process continues until the entire sample is nebulized into aerosol sized droplets.

Secondary treatment of films of colloidal quantum dots for optoelectronics and devices produced thereby

DOEpatents

Semonin, Octavi Escala; Luther, Joseph M; Beard, Matthew C; Chen, Hsiang-Yu

2014-04-01

A method of forming an optoelectronic device. The method includes providing a deposition surface and contacting the deposition surface with a ligand exchange chemical and contacting the deposition surface with a quantum dot (QD) colloid. This initial process is repeated over one or more cycles to form an initial QD film on the deposition surface. The method further includes subsequently contacting the QD film with a secondary treatment chemical and optionally contacting the surface with additional QDs to form an enhanced QD layer exhibiting multiple exciton generation (MEG) upon absorption of high energy photons by the QD active layer. Devices having an enhanced QD active layer as described above are also disclosed.

Evolution of catalytic activity of Au-Ag bimetallic nanoparticles on mesoporous support for CO oxidation.

PubMed

Wang, Ai-Qin; Chang, Chun-Ming; Mou, Chung-Yuan

2005-10-13

We report a novel Au-Ag alloy catalyst supported on mesoporous aluminosilicate Au-Ag@MCM prepared by a one-pot synthesis procedure, which is very active for low-temperature CO oxidation. The activity was highly dependent on the hydrogen pretreatment conditions. Reduction at 550-650 degrees C led to high activity at room temperature, whereas as-synthesized or calcined samples did not show any activity at the same temperature. Using various characterization techniques, such as XRD, UV-vis, XPS, and EXAFS, we elucidated the structure and surface composition change during calcination and the reduction process. The XRD patterns show that particle size increased only during the calcination process on those Ag-containing samples. XPS and EXAFS data demonstrate that calcination led to complete phase segregation of the Au-Ag alloy and the catalyst surface is greatly enriched with AgBr after the calcination process. However, subsequent reduction treatment removed Br- completely and the Au-Ag alloy was formed again. The surface composition of the reduced Au-Ag@MCM (nominal Au/Ag = 3/1) was more enriched with Ag, with the surface Au/Ag ratio being 0.75. ESR spectra show that superoxides are formed on the surface of the catalyst and its intensity change correlates well with the trend of catalytic activity. A DFT calculation shows that CO and O2 coadsorption on neighboring sites on the Au-Ag alloy was stronger than that on either Au or Ag. The strong synergism in the coadsorption of CO and O2 on the Au-Ag nanoparticle can thus explain the observed synergetic effect in catalysis.

Utilization of turkey manure as granular activated carbon: physical, chemical and adsorptive properties.

PubMed

Lima, Isabel; Marshall, Wayne E

2005-01-01

The high availability of large quantities of turkey manure generated from turkey production makes it an attractive feedstock for carbon production. Pelletized samples of turkey litter and cake were converted to granular activated carbons (GACs) by steam activation. Water flow rate and activation time were changed to produce a range of activation conditions. The GACs were characterized for select physical (yield, surface area, bulk density, attrition), chemical (pH, surface charge) and adsorptive properties (copper ion uptake). Carbon physical and adsorptive properties were dependent on activation time and quantity of steam used as activant. Yields varied from 23% to 37%, surface area varied from 248 to 472 m(2)/g and copper ion adsorption varied from 0.72 to 1.86 mmol Cu(2+)/g carbon. Copper ion adsorption greatly exceeded the values for two commercial GACs. GACs from turkey litter and cake show considerable potential to remove metal ions from water.

Catalysts for hydrogen evolution from the [NiFe] hydrogenase to the Ni2P(001) surface: the importance of ensemble effect.

PubMed

Liu, Ping; Rodriguez, José A

2005-10-26

Density functional theory (DFT) was employed to investigate the behavior of a series of catalysts used in the hydrogen evolution reaction (HER, 2H(+) + 2e(-) --> H(2)). The kinetics of the HER was studied on the [NiFe] hydrogenase, the [Ni(PS3*)(CO)](1)(-) and [Ni(PNP)(2)](2+) complexes, and surfaces such as Ni(111), Pt(111), or Ni(2)P(001). Our results show that the [NiFe] hydrogenase exhibits the highest activity toward the HER, followed by [Ni(PNP)(2)](2+) > Ni(2)P > [Ni(PS3*)(CO)](1)(-) > Pt > Ni in a decreasing sequence. The slow kinetics of the HER on the surfaces is due to the fact that the metal hollow sites bond hydrogen too strongly to allow the facile removal of H(2). In fact, the strong H-Ni interaction on Ni(2)P(001) can lead to poisoning of the highly active sites of the surface, which enhances the rate of the HER and makes it comparable to that of the [NiFe] hydrogenase. In contrast, the promotional effect of H-poisoning on the HER on Pt and Ni surfaces is relatively small. Our calculations suggest that among all of the systems investigated, Ni(2)P should be the best practical catalyst for the HER, combining the high thermostability of the surfaces and high catalytic activity of the [NiFe] hydrogenase. The good behavior of Ni(2)P(001) toward the HER is found to be associated with an ensemble effect, where the number of active Ni sites is decreased due to presence of P, which leads to moderate bonding of the intermediates and products with the surface. In addition, the P sites are not simple spectators and directly participate in the HER.

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

Porous carbon with a large surface area and an ultrahigh carbon purity via templating carbonization coupling with KOH activation as excellent supercapacitor electrode materials

NASA Astrophysics Data System (ADS)

Sun, Fei; Gao, Jihui; Liu, Xin; Pi, Xinxin; Yang, Yuqi; Wu, Shaohua

2016-11-01

Large surface area and good structural stability, for porous carbons, are two crucial requirements to enable the constructed supercapacitors with high capacitance and long cycling lifespan. Herein, we successfully prepare porous carbon with a large surface area (3175 m2 g-1) and an ultrahigh carbon purity (carbon atom ratio of 98.25%) via templating carbonization coupling with KOH activation. As-synthesized MTC-KOH exhibits excellent performances as supercapacitor electrode materials in terms of high specific capacitance and ultrahigh cycling stability. In a three electrode system, MTC-KOH delivers a high capacitance of 275 F g-1 at 0.5 A g-1 and still 120 F g-1 at a high rate of 30 A g-1. There is almost no capacitance decay even after 10,000 cycles, demonstrating outstanding cycling stability. In comparison, pre-activated MTC with a hierarchical pore structure shows a better rate capability than microporous MTC-KOH. Moreover, the constructed symmetric supercapacitor using MTC-KOH can achieve high energy densities of 8.68 Wh kg-1 and 4.03 Wh kg-1 with the corresponding power densities of 108 W kg-1 and 6.49 kW kg-1, respectively. Our work provides a simple design strategy to prepare highly porous carbons with high carbon purity for supercapacitors application.

Adsorption-Induced Changes in Ribonuclease A Structure and Enzymatic Activity on Solid Surfaces

PubMed Central

2015-01-01

Ribonuclease A (RNase A) is a small globular enzyme that lyses RNA. The remarkable solution stability of its structure and enzymatic activity has led to its investigation to develop a new class of drugs for cancer chemotherapeutics. However, the successful clinical application of RNase A has been reported to be limited by insufficient stability and loss of enzymatic activity when it was coupled with a biomaterial carrier for drug delivery. The objective of this study was to characterize the structural stability and enzymatic activity of RNase A when it was adsorbed on different surface chemistries (represented by fused silica glass, high-density polyethylene, and poly(methyl-methacrylate)). Changes in protein structure were measured by circular dichroism, amino acid labeling with mass spectrometry, and in vitro assays of its enzymatic activity. Our results indicated that the process of adsorption caused RNase A to undergo a substantial degree of unfolding with significant differences in its adsorbed structure on each material surface. Adsorption caused RNase A to lose about 60% of its native-state enzymatic activity independent of the material on which it was adsorbed. These results indicate that the native-state structure of RNase A is greatly altered when it is adsorbed on a wide range of surface chemistries, especially at the catalytic site. Therefore, drug delivery systems must focus on retaining the native structure of RNase A in order to maintain a high level of enzymatic activity for applications such as antitumor chemotherapy. PMID:25420087

Superior supercapacitors based on nitrogen and sulfur co-doped hierarchical porous carbon: Excellent rate capability and cycle stability

NASA Astrophysics Data System (ADS)

Zhang, Deyi; Han, Mei; Wang, Bing; Li, Yubing; Lei, Longyan; Wang, Kunjie; Wang, Yi; Zhang, Liang; Feng, Huixia

2017-08-01

Vastly improving the charge storage capability of supercapacitors without sacrificing their high power density and cycle performance would bring bright application prospect. Herein, we report a nitrogen and sulfur co-doped hierarchical porous carbon (NSHPC) with very superior capacitance performance fabricated by KOH activation of nitrogen and sulfur co-doped ordered mesoporous carbon (NSOMC). A high electrochemical double-layer (EDL) capacitance of 351 F g-1 was observed for the reported NSHPC electrodes, and the capacitance remains at 288 F g-1 even under a large current density of 20 A g-1. Besides the high specific capacitance and outstanding rate capability, symmetrical supercapacitor cell based on the NSHPC electrodes also exhibits an excellent cycling performance with 95.61% capacitance retention after 5000 times charge/discharge cycles. The large surface area caused by KOH activation (2056 m2 g-1) and high utilized surface area owing to the ideal micro/mesopores ratio (2.88), large micropores diameter (1.38 nm) and short opened micropores structure as well as the enhanced surface wettability induced by N and S heteroatoms doping and improved conductivity induced by KOH activation was found to be responsible for the very superior capacitance performance.

Carbon-based supercapacitors produced by activation of graphene.

PubMed

Zhu, Yanwu; Murali, Shanthi; Stoller, Meryl D; Ganesh, K J; Cai, Weiwei; Ferreira, Paulo J; Pirkle, Adam; Wallace, Robert M; Cychosz, Katie A; Thommes, Matthias; Su, Dong; Stach, Eric A; Ruoff, Rodney S

2011-06-24

Supercapacitors, also called ultracapacitors or electrochemical capacitors, store electrical charge on high-surface-area conducting materials. Their widespread use is limited by their low energy storage density and relatively high effective series resistance. Using chemical activation of exfoliated graphite oxide, we synthesized a porous carbon with a Brunauer-Emmett-Teller surface area of up to 3100 square meters per gram, a high electrical conductivity, and a low oxygen and hydrogen content. This sp(2)-bonded carbon has a continuous three-dimensional network of highly curved, atom-thick walls that form primarily 0.6- to 5-nanometer-width pores. Two-electrode supercapacitor cells constructed with this carbon yielded high values of gravimetric capacitance and energy density with organic and ionic liquid electrolytes. The processes used to make this carbon are readily scalable to industrial levels.

Carbon-Based Supercapacitors Produced by Activation of Graphene

NASA Astrophysics Data System (ADS)

Zhu, Yanwu; Murali, Shanthi; Stoller, Meryl D.; Ganesh, K. J.; Cai, Weiwei; Ferreira, Paulo J.; Pirkle, Adam; Wallace, Robert M.; Cychosz, Katie A.; Thommes, Matthias; Su, Dong; Stach, Eric A.; Ruoff, Rodney S.

2011-06-01

Supercapacitors, also called ultracapacitors or electrochemical capacitors, store electrical charge on high-surface-area conducting materials. Their widespread use is limited by their low energy storage density and relatively high effective series resistance. Using chemical activation of exfoliated graphite oxide, we synthesized a porous carbon with a Brunauer-Emmett-Teller surface area of up to 3100 square meters per gram, a high electrical conductivity, and a low oxygen and hydrogen content. This sp2-bonded carbon has a continuous three-dimensional network of highly curved, atom-thick walls that form primarily 0.6- to 5-nanometer-width pores. Two-electrode supercapacitor cells constructed with this carbon yielded high values of gravimetric capacitance and energy density with organic and ionic liquid electrolytes. The processes used to make this carbon are readily scalable to industrial levels.

Automated segmentation of blood-flow regions in large thoracic arteries using 3D-cine PC-MRI measurements.

PubMed

van Pelt, Roy; Nguyen, Huy; ter Haar Romeny, Bart; Vilanova, Anna

2012-03-01

Quantitative analysis of vascular blood flow, acquired by phase-contrast MRI, requires accurate segmentation of the vessel lumen. In clinical practice, 2D-cine velocity-encoded slices are inspected, and the lumen is segmented manually. However, segmentation of time-resolved volumetric blood-flow measurements is a tedious and time-consuming task requiring automation. Automated segmentation of large thoracic arteries, based solely on the 3D-cine phase-contrast MRI (PC-MRI) blood-flow data, was done. An active surface model, which is fast and topologically stable, was used. The active surface model requires an initial surface, approximating the desired segmentation. A method to generate this surface was developed based on a voxel-wise temporal maximum of blood-flow velocities. The active surface model balances forces, based on the surface structure and image features derived from the blood-flow data. The segmentation results were validated using volunteer studies, including time-resolved 3D and 2D blood-flow data. The segmented surface was intersected with a velocity-encoded PC-MRI slice, resulting in a cross-sectional contour of the lumen. These cross-sections were compared to reference contours that were manually delineated on high-resolution 2D-cine slices. The automated approach closely approximates the manual blood-flow segmentations, with error distances on the order of the voxel size. The initial surface provides a close approximation of the desired luminal geometry. This improves the convergence time of the active surface and facilitates parametrization. An active surface approach for vessel lumen segmentation was developed, suitable for quantitative analysis of 3D-cine PC-MRI blood-flow data. As opposed to prior thresholding and level-set approaches, the active surface model is topologically stable. A method to generate an initial approximate surface was developed, and various features that influence the segmentation model were evaluated. The active surface segmentation results were shown to closely approximate manual segmentations.

Radon (222Rn) in ground water of fractured rocks: A diffusion/ion exchange model

USGS Publications Warehouse

Wood, W.W.; Kraemer, T.F.; Shapiro, A.

2004-01-01

Ground waters from fractured igneous and high-grade sialic metamorphic rocks frequently have elevated activity of dissolved radon (222Rn). A chemically based model is proposed whereby radium (226Ra) from the decay of uranium (238U) diffuses through the primary porosity of the rock to the water-transmitting fracture where it is sorbed on weathering products. Sorption of 226Ra on the fracture surface maintains an activity gradient in the rock matrix, ensuring a continuous supply of 226Ra to fracture surfaces. As a result of the relatively long half-life of 226Ra (1601 years), significant activity can accumulate on fracture surfaces. The proximity of this sorbed 226Ra to the active ground water flow system allows its decay progeny 222Rn to enter directly into the water. Laboratory analyses of primary porosity and diffusion coefficients of the rock matrix, radon emanation, and ion exchange at fracture surfaces are consistent with the requirements of a diffusion/ion- exchange model. A dipole-brine injection/withdrawal experiment conducted between bedrock boreholes in the high-grade metamorphic and granite rocks at the Hubbard Brook Experimental Forest, Grafton County, New Hampshire, United States (42??56???N, 71??43???W) shows a large activity of 226Ra exchanged from fracture surfaces by a magnesium brine. The 226Ra activity removed by the exchange process is 34 times greater than that of 238U activity. These observations are consistent with the diffusion/ion-exchange model. Elutriate isotopic ratios of 223Ra/226Ra and 238U/226Ra are also consistent with the proposed chemically based diffusion/ion-exchange model.

Electrochemical Hydrogen Evolution at Ordered Mo 7 Ni 7

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

Csernica, Peter M.; McKone, James R.; Mulzer, Catherine R.

2017-04-11

Ni–Mo alloys containing up to ~15 mol % Mo are excellent non-noble electrocatalysts for the hydrogen evolution reaction (HER) in alkaline aqueous electrolytes. To date, studies have not addressed the details of HER activity of ordered Ni–Mo intermetallic compounds, which can contain a significantly larger fraction of Mo (up to 50 mol %) than can be accessed through high-temperature alloying. Here, we present a straightforward and facile synthesis of three phase-pure electrocatalyst powders using a precipitation–reduction approach: ordered Mo7Ni7, disordered Ni0.92Mo0.08, and pure Ni. The Ni0.92Mo0.08 alloy exhibited a nearly 10-fold higher mass-specific HER activity than either pure Ni ormore » Mo7Ni7, where much of the difference could be attributed to relative surface area. Therefore, we attempted to quantify and account for differences in surface areas using electron microscopy, impedance spectroscopy, and gas adsorption measurements. These data suggest that Ni–Mo alloys and intermetallic compounds exhibit substantial pseudocapacitance at potentials near the onset of hydrogen evolution, which can cause impedance spectroscopy to overestimate the interfacial capacitance, and thus the electrochemically active surface area, of these materials. From these observations, we postulate Mo redox activity as the chemical basis for the observed pseudocapacitance of Ni–Mo composites. Furthermore, using gas adsorption measurements, rather than capacitance, to estimate active surface area, we find that ordered Mo7Ni7 is more intrinsically active than the Ni0.92Mo0.08 alloy, implying that Mo7Ni7 intermetallics with high surface area will also give higher mass-specific activities than alloys with comparable roughness.« less

Shape-Controllable Gold Nanoparticle-MoS2 Hybrids Prepared by Tuning Edge-Active Sites and Surface Structures of MoS2 via Temporally Shaped Femtosecond Pulses.

PubMed

Zuo, Pei; Jiang, Lan; Li, Xin; Li, Bo; Xu, Yongda; Shi, Xuesong; Ran, Peng; Ma, Tianbao; Li, Dawei; Qu, Liangti; Lu, Yongfeng; Grigoropoulos, Costas P

2017-03-01

Edge-active site control of MoS 2 is crucial for applications such as chemical catalysis, synthesis of functional composites, and biochemical sensing. This work presents a novel nonthermal method to simultaneously tune surface chemical (edge-active sites) and physical (surface periodic micro/nano structures) properties of MoS 2 using temporally shaped femtosecond pulses, through which shape-controlled gold nanoparticles are in situ and self-assembly grown on MoS 2 surfaces to form Au-MoS 2 hybrids. The edge-active sites with unbound sulfurs of laser-treated MoS 2 drive the reduction of gold nanoparticles, while the surface periodic structures of laser-treated MoS 2 assist the shape-controllable growth of gold nanoparticles. The proposed novel method highlights the broad application potential of MoS 2 ; for example, these Au-MoS 2 hybrids exhibit tunable and highly sensitive SERS activity with an enhancement factor up to 1.2 × 10 7 , indicating the marked potential of MoS 2 in future chemical and biological sensing applications.

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

Microbial enhanced oil recovery research. [Peptides

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

Sharma, M.M.; Georgiou, G.

1992-01-01

The surface active lipopeptide produced by Bacillus licheniformis JF-2 was isolated to near apparent homogeneity. NMR experiments revealed that this compound consists of a heptapeptide with an amino acid sequence similar to surfactin and a heterogeneous fatty acid consisting of the normal-, anteiso-, and iso- branched isomers. The surface activity of the B. licheniformis JF-2 surfactant was shown to depend on the presence of fermentation products and is strongly affected by the pH. Under conditions of optimal salinity and pH the interfacial tension against decane was 6 [times] 10[sup 3] mN/m which is one of the lowest values ever obtainedmore » with a microbial surfactant. Microbial compounds which exhibit particularly high surface activity are classified as biosurfactants. Microbial biosurfactants include a wide variety of surface and interfacially active compounds, such as glycolipids, lipopeptides polysaccharideprotein complexes, phospholipids, fatty acids and neutral lipids. Biosurfactants are easily biodegradable and thus are particularly suited for environmental applications such as bioremediation and the dispersion of oil spills. Bacillus licheniformis strain JF-2 has been shown to be able to grow and produce a very effective biosurfactant under both aerobic and anaerobic conditions and in the presence of high salt concentrations. The production of biosurfactants in anaerobic, high salt environments is potentially important for a variety of in situ applications such as microbial enhanced oil recovery. As a first step towards evaluating the commercial utility of the B. licheniformis JF-2 surfactant, we isolated t-he active. compound from the culture supernatant, characterized its chemical structure and investigated its phase behavior. We found that the surface activity of the surfactant is strongly dependent on the pH of the aqueous. phase. This may be important for the biological function of the surfactant and is of interest for several applications in surfactancy.« less

Microbial enhanced oil recovery research. Annex 5, Summary annual report, 1991--1992

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

Sharma, M.M.; Georgiou, G.

1992-12-31

The surface active lipopeptide produced by Bacillus licheniformis JF-2 was isolated to near apparent homogeneity. NMR experiments revealed that this compound consists of a heptapeptide with an amino acid sequence similar to surfactin and a heterogeneous fatty acid consisting of the normal-, anteiso-, and iso- branched isomers. The surface activity of the B. licheniformis JF-2 surfactant was shown to depend on the presence of fermentation products and is strongly affected by the pH. Under conditions of optimal salinity and pH the interfacial tension against decane was 6 {times} 10{sup 3} mN/m which is one of the lowest values ever obtainedmore » with a microbial surfactant. Microbial compounds which exhibit particularly high surface activity are classified as biosurfactants. Microbial biosurfactants include a wide variety of surface and interfacially active compounds, such as glycolipids, lipopeptides polysaccharideprotein complexes, phospholipids, fatty acids and neutral lipids. Biosurfactants are easily biodegradable and thus are particularly suited for environmental applications such as bioremediation and the dispersion of oil spills. Bacillus licheniformis strain JF-2 has been shown to be able to grow and produce a very effective biosurfactant under both aerobic and anaerobic conditions and in the presence of high salt concentrations. The production of biosurfactants in anaerobic, high salt environments is potentially important for a variety of in situ applications such as microbial enhanced oil recovery. As a first step towards evaluating the commercial utility of the B. licheniformis JF-2 surfactant, we isolated t-he active. compound from the culture supernatant, characterized its chemical structure and investigated its phase behavior. We found that the surface activity of the surfactant is strongly dependent on the pH of the aqueous. phase. This may be important for the biological function of the surfactant and is of interest for several applications in surfactancy.« less

Bioorthogonal in Situ Hydrogels Based on Polyether Polyols for New Biosensor Materials with High Sensitivity.

PubMed

Herrmann, Anna; Kaufmann, Lena; Dey, Pradip; Haag, Rainer; Schedler, Uwe

2018-04-04

Both noncovalent and covalent encapsulations of active biomolecules, for example, proteins and oligonucleotides, for a new biosensor matrix in an in situ bioorthogonal hydrogel formation via a strain-promoted azide-alkyne cycloaddition reaction were investigated. Unspecific interaction between the gel and the biomolecules as well as protein denaturation was prevented by the bioorthogonal gel components, which ensure a uniform aqueous environment in the hydrogel network. No leaching of the active biomolecules was observed. Additionally, a much higher and also adjustable loading of biomolecules in the hydrogel matrix was achieved compared to conventional biosensor surfaces, where the sensor molecules are immobilized on monolayers (2D surfaces) or brushlike structures (3D surfaces). Spotting experiments of the hydrogel confirm the possibility to use this new surface for microarray-based multiplex applications which require very high signal-to-noise ratios.

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.

Influence of Cu-Ti thin film surface properties on antimicrobial activity and viability of living cells.

PubMed

Wojcieszak, Damian; Kaczmarek, Danuta; Antosiak, Aleksandra; Mazur, Michal; Rybak, Zbigniew; Rusak, Agnieszka; Osekowska, Malgorzata; Poniedzialek, Agata; Gamian, Andrzej; Szponar, Bogumila

2015-11-01

The paper describes properties of thin-film coatings based on copper and titanium. Thin films were prepared by co-sputtering of Cu and Ti targets in argon plasma. Deposited coatings consist of 90at.% of Cu and 10at.% of Ti. Characterization of the film was made on the basis of investigations of microstructure and physicochemical properties of the surface. Methods such as scanning electron microscopy, x-ray microanalysis, x-ray diffraction, x-ray photoelectron spectroscopy, atomic force microscopy, optical profilometry and wettability measurements were used to assess the properties of deposited thin films. An impact of Cu-Ti coating on the growth of selected bacteria and viability of the living cells (line L929, NCTC clone 929) was described in relation to the structure, surface state and wettability of the film. It was found that as-deposited films were amorphous. However, in such surroundings the nanocrystalline grains of 10-15nm and 25-35nm size were present. High surface active area with a roughness of 8.9nm, had an effect on receiving relatively high water contact angle value (74.1°). Such wettability may promote cell adhesion and result in an increase of the probability of copper ion transfer from the film surface into the cell. Thin films revealed bactericidal and fungicidal effects even in short term-contact. High activity of prepared films was directly related to high amount (ca. 51 %) of copper ions at 1+ state as x-ray photoelectron spectroscopy results have shown. Copyright © 2015 Elsevier B.V. All rights reserved.

High-performance flexible surface-enhanced Raman scattering substrates fabricated by depositing Ag nanoislands on the dragonfly wing

NASA Astrophysics Data System (ADS)

Wang, Yuhong; Wang, Mingli; Shen, Lin; Sun, Xin; Shi, Guochao; Ma, Wanli; Yan, Xiaoya

2018-04-01

Natural dragonfly wing (DW), as a template, was deposited on noble metal sliver (Ag) nanoislands by magnetron sputtering to fabricate a flexible, low-cost, large-scale and environment-friendly surface-enhanced Raman scattering (SERS) substrate (Ag/DW substrate). Generally, materials with regular surface nanostructures are chosen for the templates, the selection of our new material with irregular surface nanostructures for substrates provides a new idea for the preparation of high-performance SERS-active substrates and many biomimetic materials. The optimum sputtering time of metal Ag was also investigated at which the prepared SERS-active substrates revealed remarkable SERS activities to 4-aminothiophenol (4-ATP) and crystal violet (CV). Even more surprisingly, the Ag/DW substrate with such an irregular template had reached the enhancement factor (EF) of ∼1.05 × 105 and the detection limit of 10-10 M to 4-ATP. The 3D finite-different time-domain (3D-FDTD) simulation illustrated that the "hot spots" between neighbouring Ag nanoislands at the top of pillars played a most important role in generating electromagnetic (EM) enhancement and strengthening Raman signals.

Catalysis by Atomic-Sized Centers: Methane Activation for Partial Oxidation and Combustion

DTIC Science & Technology

2015-07-21

example, H adsorbed alone on an oxide surface will bind to oxygen to form a hydroxide . However, if a Lewis base (e.g. any electron donor) is...that on a gold surface, which is not surprising considering the bonding character between the cluster and metal surfaces. The high mobility verifies

Surface-enhanced Raman scattering (SERS) detection of multiple viral antigens using magnetic capture of SERS-active nanoparticles

USDA-ARS?s Scientific Manuscript database

A highly sensitive immunoassay based on surface-enhanced Raman scattering (SERS) spectroscopy has been developed for multiplex detection of surface envelope and capsid antigens of the viral zoonotic pathogens West Nile virus (WNV) and Rift Valley fever virus (RVFV). Detection was mediated by antibo...

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

Wu, Chung-Yeh; Wolf, William J.; Levartovsky, Yehonatan

We report the critical role in surface reactions and heterogeneous catalysis of metal atoms with low coordination numbers, such as found at atomic steps and surface defects, is firmly established. But despite the growing availability of tools that enable detailed in situ characterization, so far it has not been possible to document this role directly. Surface properties can be mapped with high spatial resolution, and catalytic conversion can be tracked with a clear chemical signature; however, the combination of the two, which would enable high-spatial-resolution detection of reactions on catalytic surfaces, has rarely been achieved. Single-molecule fluorescence spectroscopy has beenmore » used to image and characterize single turnover sites at catalytic surfaces, but is restricted to reactions that generate highly fluorescing product molecules. Herein the chemical conversion of N-heterocyclic carbene molecules attached to catalytic particles is mapped using synchrotron-radiation-based infrared nanospectroscopy with a spatial resolution of 25 nanometres, which enabled particle regions that differ in reactivity to be distinguished. Lastly, these observations demonstrate that, compared to the flat regions on top of the particles, the peripheries of the particles-which contain metal atoms with low coordination numbers-are more active in catalysing oxidation and reduction of chemically active groups in surface-anchored N-heterocyclic carbene molecules.« less

Surface-Activated Coupling Reactions Confined on a Surface.

PubMed

Dong, Lei; Liu, Pei Nian; Lin, Nian

2015-10-20

Chemical reactions may take place in a pure phase of gas or liquid or at the interface of two phases (gas-solid or liquid-solid). Recently, the emerging field of "surface-confined coupling reactions" has attracted intensive attention. In this process, reactants, intermediates, and products of a coupling reaction are adsorbed on a solid-vacuum or a solid-liquid interface. The solid surface restricts all reaction steps on the interface, in other words, the reaction takes place within a lower-dimensional, for example, two-dimensional, space. Surface atoms that are fixed in the surface and adatoms that move on the surface often activate the surface-confined coupling reactions. The synergy of surface morphology and activity allow some reactions that are inefficient or prohibited in the gas or liquid phase to proceed efficiently when the reactions are confined on a surface. Over the past decade, dozens of well-known "textbook" coupling reactions have been shown to proceed as surface-confined coupling reactions. In most cases, the surface-confined coupling reactions were discovered by trial and error, and the reaction pathways are largely unknown. It is thus highly desirable to unravel the mechanisms, mechanisms of surface activation in particular, of the surface-confined coupling reactions. Because the reactions take place on surfaces, advanced surface science techniques can be applied to study the surface-confined coupling reactions. Among them, scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) are the two most extensively used experimental tools. The former resolves submolecular structures of individual reactants, intermediates, and products in real space, while the latter monitors the chemical states during the reactions in real time. Combination of the two methods provides unprecedented spatial and temporal information on the reaction pathways. The experimental findings are complemented by theoretical modeling. In particular, density-functional theory (DFT) transition-state calculations have been used to shed light on reaction mechanisms and to unravel the trends of different surface materials. In this Account, we discuss recent progress made in two widely studied surface-confined coupling reactions, aryl-aryl (Ullmann-type) coupling and alkyne-alkyne (Glaser-type) coupling, and focus on surface activation effects. Combined experimental and theoretical studies on the same reactions taking place on different metal surfaces have clearly demonstrated that different surfaces not only reduce the reaction barrier differently and render different reaction pathways but also control the morphology of the reaction products and, to some degree, select the reaction products. We end the Account with a list of questions to be addressed in the future. Satisfactorily answering these questions may lead to using the surface-confined coupling reactions to synthesize predefined products with high yield.

Catalytic behavior of metal catalysts in high-temperature RWGS reaction: In-situ FT-IR experiments and first-principles calculations

PubMed Central

Choi, Sungjun; Sang, Byoung-In; Hong, Jongsup; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Kim, Byung-Kook; Kim, Hyoungchul

2017-01-01

High-temperature chemical reactions are ubiquitous in (electro) chemical applications designed to meet the growing demands of environmental and energy protection. However, the fundamental understanding and optimization of such reactions are great challenges because they are hampered by the spontaneous, dynamic, and high-temperature conditions. Here, we investigated the roles of metal catalysts (Pd, Ni, Cu, and Ag) in the high-temperature reverse water-gas shift (RWGS) reaction using in-situ surface analyses and density functional theory (DFT) calculations. Catalysts were prepared by the deposition-precipitation method with urea hydrolysis and freeze-drying. Most metals show a maximum catalytic activity during the RWGS reaction (reaching the thermodynamic conversion limit) with formate groups as an intermediate adsorbed species, while Ag metal has limited activity with the carbonate species on its surface. According to DFT calculations, such carbonate groups result from the suppressed dissociation and adsorption of hydrogen on the Ag surface, which is in good agreement with the experimental RWGS results. PMID:28120896

Catalytic behavior of metal catalysts in high-temperature RWGS reaction: In-situ FT-IR experiments and first-principles calculations.

PubMed

Choi, Sungjun; Sang, Byoung-In; Hong, Jongsup; Yoon, Kyung Joong; Son, Ji-Won; Lee, Jong-Ho; Kim, Byung-Kook; Kim, Hyoungchul

2017-01-25

High-temperature chemical reactions are ubiquitous in (electro) chemical applications designed to meet the growing demands of environmental and energy protection. However, the fundamental understanding and optimization of such reactions are great challenges because they are hampered by the spontaneous, dynamic, and high-temperature conditions. Here, we investigated the roles of metal catalysts (Pd, Ni, Cu, and Ag) in the high-temperature reverse water-gas shift (RWGS) reaction using in-situ surface analyses and density functional theory (DFT) calculations. Catalysts were prepared by the deposition-precipitation method with urea hydrolysis and freeze-drying. Most metals show a maximum catalytic activity during the RWGS reaction (reaching the thermodynamic conversion limit) with formate groups as an intermediate adsorbed species, while Ag metal has limited activity with the carbonate species on its surface. According to DFT calculations, such carbonate groups result from the suppressed dissociation and adsorption of hydrogen on the Ag surface, which is in good agreement with the experimental RWGS results.

Cyclic lipopeptide signature as fingerprinting for the screening of halotolerant Bacillus strains towards microbial enhanced oil recovery.

PubMed

Farias, Bárbara C S; Hissa, Denise C; do Nascimento, Camila T M; Oliveira, Samuel A; Zampieri, Davila; Eberlin, Marcos N; Migueleti, Deivid L S; Martins, Luiz F; Sousa, Maíra P; Moyses, Danuza N; Melo, Vânia M M

2018-02-01

Cyclic lipopeptides (CLPs) are non-ribosomal biosurfactants produced by Bacillus species that exhibit outstanding interfacial activity. The synthesis of CLPs is under genetic and environmental influence, and representatives from different families are generally co-produced, generating isoforms that differ in chemical structure and biological activities. This study to evaluate the effect of low and high NaCl concentrations on the composition and surface activity of CLPs produced by Bacillus strains TIM27, TIM49, TIM68, and ICA13 towards microbial enhanced oil recovery (MEOR). The strains were evaluated in mineral medium containing NaCl 2.7, 66, or 100 g L -1 and growth, surface tension and emulsification activity were monitored. Based on the analysis of 16S rDNA, gyrB and rpoB sequences TIM27 and TIM49 were assigned to Bacillus subtilis, TIM68 to Bacillus vallismortis, and ICA13 to Bacillus amyloliquefaciens. All strains tolerated up to 100-g L -1 NaCl, but only TIM49 and TIM68 were able to reduce surface tension at this concentration. TIM49 also showed emulsification activity at concentrations up to 66-g L -1 NaCl. ESI-MS analysis showed that the strains produced a mixture of CLPs, which presented distinct CLP profiles at low and high NaCl concentrations. High NaCl concentration favored the synthesis of surfactins and/or fengycins that correlated with the surface activities of TIM49 and TIM68, whereas low concentration favored the synthesis of iturins. Taken together, these findings suggest that the determination of CLP signatures under the expected condition of oil reservoirs can be useful in the guidance for choosing well-suited strains to MEOR.

Surface Texture-Induced Enhancement of Optical and Photoelectrochemical Activity of Cu2ZnSnS4 Photocathodes

NASA Astrophysics Data System (ADS)

Sarswat, Prashant K.; Deka, Nipon; Jagan Mohan Rao, S.; Free, Michael L.; Kumar, Gagan

2017-08-01

The objective of this work is to understand and improve the photocatalytic activity of Cu2ZnSnS4 (CZTS) through postgrowth modification techniques to create surface textures. This objective can be achieved using a combination of solvents, etching agents, and anodization techniques. One of the most effective surface treatments for enhancing the surface properties of photovoltaic materials is formation of nanoscale flakes, although other surface modifications were also evaluated. The superior performance of textured films can be attributed to enhanced surface area of absorber material exposed to electrolyte, ZnS deficiency, and high catalytic activity due to reduced charge-transfer resistance. Fine-tuning of ion flux and electrolyte stoichiometry can be used to create a controlled growth algorithm for CZTS thin films. The resulting information can be utilized to optimize film properties. The utility of nanostructured or engineered surfaces was evaluated using photoelectrochemical measurements. Finite-difference time-domain (FDTD)-assisted simulations were conducted for selected texturing, revealing enhanced surface area of absorbing medium that ultimately resulted in greater power loss of light in the medium.

Interaction of Molecular Oxygen with a Hexagonally Reconstructed Au(001) Surface

DOE PAGES

Loheac, Andrew; Barbour, Andi; Komanicky, Vladimir; ...

2016-09-19

Kinetics of molecular oxygen/Au(001) surface interaction has been studied at high temperature and near atmospheric pressures of O 2 gas with in situ X-ray scattering measurements. In this study, we find that the hexagonal reconstruction (hex) of Au(001) surface lifts to (1 × 1) in the presence of O 2 gas, indicating that the (1 × 1) is more favored when some oxygen atoms present on the surface. The measured lifting rate constant vs temperature is found to be highest at intermediate temperature exhibiting a “volcano”-type behavior. At low temperature, the hex-to-(1 × 1) activation barrier (E act = 1.3(3)more » eV) limits the lifting. At high temperature, oxygen adsorption energy (E ads = 1.6(2) eV) limits the lifting. The (1 × 1)-to-hex activation barrier (E hex = 0.41(14) eV) is also obtained from hex recovery kinetics. The pressure–temperature (PT) surface phase diagram obtained in this study shows three regions: hex at low P and T, (1 × 1) at high P and T, and coexistence of the hex and (1 × 1) at the intermediate P and T.« less

High power density supercapacitors based on the carbon dioxide activated D-glucose derived carbon electrodes and 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid

NASA Astrophysics Data System (ADS)

Tooming, T.; Thomberg, T.; Kurig, H.; Jänes, A.; Lust, E.

2015-04-01

The electrochemical impedance spectroscopy, cyclic voltammetry, constant current charge/discharge and the constant power discharge methods have been applied to establish the electrochemical characteristics of the electrical double-layer capacitor (EDLC) consisting of the 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) ionic liquid and microporous carbon electrodes. Microporous carbon material used for preparation of electrodes (GDAC - glucose derived activated carbon), has been synthesised from D-(+)-glucose by the hydrothermal carbonization method, including subsequent pyrolysis, carbon dioxide activation and surface cleaning step with hydrogen. The Brunauer-Emmett-Teller specific surface area (SBET = 1540 m2 g-1), specific surface area calculated using the non-local density functional theory in conjunction with stable adsorption integral equation using splines (SAIEUS) model SSAIEUS = 1820 m2 g-1, micropore surface area (Smicro = 1535 m2 g-1), total pore volume (Vtot = 0.695 cm3 g-1) and the pore size distribution were obtained from the N2 sorption data. The SBET, Smicro and Vtot values have been correlated with the electrochemical characteristics strongly dependent on the carbon activation conditions applied for EDLCs. Wide region of ideal polarizability (ΔV ≤ 3.2 V), very short charging/discharging time constant (2.7 s), and high specific series capacitance (158 F g-1) have been calculated for the optimized carbon material GDAC-10h (activation of GDAC with CO2 during 10 h) in EMImBF4 demonstrating that this system can be used for completing the EDLC with high energy- and power densities.

In vivo recordings of brain activity using organic transistors

PubMed Central

Khodagholy, Dion; Doublet, Thomas; Quilichini, Pascale; Gurfinkel, Moshe; Leleux, Pierre; Ghestem, Antoine; Ismailova, Esma; Hervé, Thierry; Sanaur, Sébastien; Bernard, Christophe; Malliaras, George G.

2013-01-01

In vivo electrophysiological recordings of neuronal circuits are necessary for diagnostic purposes and for brain-machine interfaces. Organic electronic devices constitute a promising candidate because of their mechanical flexibility and biocompatibility. Here we demonstrate the engineering of an organic electrochemical transistor embedded in an ultrathin organic film designed to record electrophysiological signals on the surface of the brain. The device, tested in vivo on epileptiform discharges, displayed superior signal-to-noise ratio due to local amplification compared with surface electrodes. The organic transistor was able to record on the surface low-amplitude brain activities, which were poorly resolved with surface electrodes. This study introduces a new class of biocompatible, highly flexible devices for recording brain activity with superior signal-to-noise ratio that hold great promise for medical applications. PMID:23481383

In vivo recordings of brain activity using organic transistors.

PubMed

Khodagholy, Dion; Doublet, Thomas; Quilichini, Pascale; Gurfinkel, Moshe; Leleux, Pierre; Ghestem, Antoine; Ismailova, Esma; Hervé, Thierry; Sanaur, Sébastien; Bernard, Christophe; Malliaras, George G

2013-01-01

In vivo electrophysiological recordings of neuronal circuits are necessary for diagnostic purposes and for brain-machine interfaces. Organic electronic devices constitute a promising candidate because of their mechanical flexibility and biocompatibility. Here we demonstrate the engineering of an organic electrochemical transistor embedded in an ultrathin organic film designed to record electrophysiological signals on the surface of the brain. The device, tested in vivo on epileptiform discharges, displayed superior signal-to-noise ratio due to local amplification compared with surface electrodes. The organic transistor was able to record on the surface low-amplitude brain activities, which were poorly resolved with surface electrodes. This study introduces a new class of biocompatible, highly flexible devices for recording brain activity with superior signal-to-noise ratio that hold great promise for medical applications.

Protein consensus-based surface engineering (ProCoS): a computer-assisted method for directed protein evolution.

PubMed

Shivange, Amol V; Hoeffken, Hans Wolfgang; Haefner, Stefan; Schwaneberg, Ulrich

2016-12-01

Protein consensus-based surface engineering (ProCoS) is a simple and efficient method for directed protein evolution combining computational analysis and molecular biology tools to engineer protein surfaces. ProCoS is based on the hypothesis that conserved residues originated from a common ancestor and that these residues are crucial for the function of a protein, whereas highly variable regions (situated on the surface of a protein) can be targeted for surface engineering to maximize performance. ProCoS comprises four main steps: ( i ) identification of conserved and highly variable regions; ( ii ) protein sequence design by substituting residues in the highly variable regions, and gene synthesis; ( iii ) in vitro DNA recombination of synthetic genes; and ( iv ) screening for active variants. ProCoS is a simple method for surface mutagenesis in which multiple sequence alignment is used for selection of surface residues based on a structural model. To demonstrate the technique's utility for directed evolution, the surface of a phytase enzyme from Yersinia mollaretii (Ymphytase) was subjected to ProCoS. Screening just 1050 clones from ProCoS engineering-guided mutant libraries yielded an enzyme with 34 amino acid substitutions. The surface-engineered Ymphytase exhibited 3.8-fold higher pH stability (at pH 2.8 for 3 h) and retained 40% of the enzyme's specific activity (400 U/mg) compared with the wild-type Ymphytase. The pH stability might be attributed to a significantly increased (20 percentage points; from 9% to 29%) number of negatively charged amino acids on the surface of the engineered phytase.

Identifying the Active Surfaces of Electrochemically Tuned LiCoO 2 for Oxygen Evolution Reaction

DOE PAGES

Lu, Zhiyi; Chen, Guangxu; Li, Yanbin; ...

2017-04-18

Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (1120) and polar (0112) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces andmore » their OER activities can be understood by the increase of Co 4+ sites relative to Co 3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (~0.1 V in overpotential shift at 10 mA cm –2) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. In addition, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.« less

Incorporation of low energy activated nitrogen onto HOPG surface: Chemical states and thermal stability studies by in-situ XPS and Raman spectroscopy

NASA Astrophysics Data System (ADS)

Chandran, Maneesh; Shasha, Michal; Michaelson, Shaul; Hoffman, Alon

2016-09-01

In this paper we report the chemical states analysis of activated nitrogen incorporated highly oriented pyrolytic graphite (HOPG) surface under well-controlled conditions. Nitrogen incorporation is carried out by two different processes: an indirect RF nitrogen plasma and low energy (1 keV) N2+ implantation. Bonding configuration, concentration and thermal stability of the incorporated nitrogen species by aforesaid processes are systematically compared by in-situ X-ray photoelectron spectroscopy (XPS). Relatively large concentration of nitrogen is incorporated onto RF nitride HOPG surface (16.2 at.%), compared to N2+ implanted HOPG surface (7.7 at.%). The evolution of N 1s components (N1, N2, N3) with annealing temperature is comprehensively discussed, which indicates that the formation and reorganization of local chemical bonding states are determined by the process of nitridation and not by the prior chemical conditioning (i.e., amorphization or hydrogenation) of the HOPG surface. A combined XPS and Raman spectroscopy studies revealed that N2+ implantation process resulted in a high level of defects to the HOPG surface, which cannot be annealed-out by heat treatment up to 1000 °C. On the other hand, the RF nitrogen plasma process did not produce a high level of surface defects, while incorporating nearly the same amount of stable nitrogen species.

Synthesis of sulfonated porous carbon nanospheres solid acid by a facile chemical activation route

NASA Astrophysics Data System (ADS)

Chang, Binbin; Guo, Yanzhen; Yin, Hang; Zhang, Shouren; Yang, Baocheng

2015-01-01

Generally, porous carbon nanospheres materials are usually prepared via a template method, which is a multi-steps and high-cost strategy. Here, we reported a porous carbon nanosphere solid acid with high surface area and superior porosity, as well as uniform nanospheical morphology, which prepared by a facile chemical activation with ZnCl2 using resorcinol-formaldehyde (RF) resins spheres as precursor. The activation of RF resins spheres by ZnCl2 at 400 °C brought high surface area and large volume, and simultaneously retained numerous oxygen-containing and hydrogen-containing groups due to the relatively low processing temperature. The presence of these functional groups is favorable for the modification of -SO3H groups by a followed sulfonation treating with sulphuric acid and organic sulfonic acid. The results of N2 adsorption-desorption and electron microscopy clearly showed the preservation of porous structure and nanospherical morphology. Infrared spectra certified the variation of surface functional groups after activation and the successful modification of -SO3H groups after sulfonation. The acidities of catalysts were estimated by an indirect titration method and the modified amount of -SO3H groups were examined by energy dispersive spectra. The results suggested sulfonated porous carbon nanospheres catalysts possessed high acidities and -SO3H densities, which endowed their significantly catalytic activities for biodiesel production. Furthermore, their excellent stability and recycling property were also demonstrated by five consecutive cycles.

Ordered mesoporous porphyrinic carbons with very high electrocatalytic activity for the oxygen reduction reaction

PubMed Central

Cheon, Jae Yeong; Kim, Taeyoung; Choi, YongMan; Jeong, Hu Young; Kim, Min Gyu; Sa, Young Jin; Kim, Jaesik; Lee, Zonghoon; Yang, Tae-Hyun; Kwon, Kyungjung; Terasaki, Osamu; Park, Gu-Gon; Adzic, Radoslav R.; Joo, Sang Hoon

2013-01-01

The high cost of the platinum-based cathode catalysts for the oxygen reduction reaction (ORR) has impeded the widespread application of polymer electrolyte fuel cells. We report on a new family of non-precious metal catalysts based on ordered mesoporous porphyrinic carbons (M-OMPC; M = Fe, Co, or FeCo) with high surface areas and tunable pore structures, which were prepared by nanocasting mesoporous silica templates with metalloporphyrin precursors. The FeCo-OMPC catalyst exhibited an excellent ORR activity in an acidic medium, higher than other non-precious metal catalysts. It showed higher kinetic current at 0.9 V than Pt/C catalysts, as well as superior long-term durability and MeOH-tolerance. Density functional theory calculations in combination with extended X-ray absorption fine structure analysis revealed a weakening of the interaction between oxygen atom and FeCo-OMPC compared to Pt/C. This effect and high surface area of FeCo-OMPC appear responsible for its significantly high ORR activity. PMID:24056308

Pressure-induced phase transitions of exposed curved surface nano-TiO{sub 2} with high photocatalytic activity

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

Huang, Yanwei, E-mail: yanwei.huang@hpstar.ac.cn, E-mail: wangling@hpstar.ac.cn; College of Materials and Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018; Chen, Fengjiao

We report a unique phase transition in compressed exposed curved surface nano-TiO{sub 2} with high photocatalytic activity using in situ synchrotron X-ray diffraction and Raman Spectroscopy. High-pressure studies indicate that the anatase phase starts to transform into baddeleyite phase upon compression at 19.4 GPa, and completely transforms into the baddeleyite phase above 24.6 GPa. Upon decompression, the baddeleyite phase was maintained until the pressure was released to 6.4 GPa and then transformed into the α-PbO{sub 2} phase at 2.7 GPa. Together with the results of high-resolution transmission electron microscopy and the pressure-volume relationship, this phase transition's characteristics during the compression-decompression cycle demonstrate that themore » truncated biconic morphology possessed excellent stability. This study may provide an insight to the mechanisms of stability for high photocatalytic activity of nano-TiO{sub 2}.« less

Micro-mesoporous carbon spheres derived from carrageenan as electrode material for supercapacitors

NASA Astrophysics Data System (ADS)

Fan, Yang; Yang, Xin; Zhu, Bing; Liu, Pei-Fang; Lu, Hai-Ting

2014-12-01

The polysaccharide carrageenan is used as a natural precursor to prepare micro-mesoporous carbon spheres. The carbon spheres were synthesized by hydrothermal carbonization of carrageenan, and subsequent chemical activation by KOH at different temperatures. The obtained micro-mesoporous carbon spheres have high surface area (up to 2502 m2 g-1) and large pore volume (up to 1.43 cm3 g-1). Moreover, the micro- and mesoporosity can be finely tuned be modifying the activation temperatures in the range of 700-900 °C. The carbon spheres activated at 900 °C present high specific capacitance of 230 F g-1 at a current density of 1 A g-1 and good ion transport kinetics. The good capacitive performance can be ascribed to the high specific surface area, well-controlled micro- and mesoporosity and narrow pore size distribution.

Catalytic activity and stability of oxides: The role of near-surface atomic structures and compositions

DOE PAGES

Feng, Zhenxing; Hong, Wesley T.; Fong, Dillon D.; ...

2016-05-05

Electrocatalysts play an important role in catalyzing the kinetics for oxygen reduction and oxygen evolution reactions for many air-based energy storage and conversion devices, such as metal$-$air batteries and fuel cells. Although noble metals have been extensively used as electrocatalysts, their limited natural abundance and high costs have motivated the search for more cost-effective catalysts. Oxides are suitable candidates since they are relatively inexpensive andhave shown reasonably high activity for various electrochemical reactions. However, a lack of fundamental understanding of the reaction mechanisms has been a major hurdle toward improving electrocatalytic activity. Here, detailed studies of the oxide surface atomicmore » structure and chemistry (e.g.,cation migration) can provide much needed insights for the design of highly efficient and stable oxide electrocatalysts.« less

XPS analysis of activated carbon supported ionic liquids: Enhanced purity and reduced charging

NASA Astrophysics Data System (ADS)

Foelske-Schmitz, A.; Weingarth, D.; Kötz, R.

2011-12-01

Herein we report on XPS measurements on five different [EMIM] based ionic liquids (IL) prepared on activated carbon and aluminium supports. The anions were [TFSI], [BF4], [FAP], [B(CN)4] and [EtOSO3]. The results show that impurities such as O, Si or hydrocarbons were significantly reduced or no longer detected when preparation was performed on the high surface area carbon support. All core level spectra were fitted and for [EMIM][FAP], [EMIM][B(CN)4] and [EMIM][EtOSO3] de-convolution procedures of the C 1s lines are suggested. Comparison of the determined binding energies with published data strongly suggests that sample charging is irrelevant when preparation is performed on the activated carbon support. This observation is supposed to refer to the high capacitance of the high surface area carbon.

Design of anticoagulant surfaces based on cellulose nanocrystals.

PubMed

Ehmann, Heike M A; Mohan, Tamilselvan; Koshanskaya, Maria; Scheicher, Sylvia; Breitwieser, Doris; Ribitsch, Volker; Stana-Kleinschek, Karin; Spirk, Stefan

2014-11-07

The anticoagulant activity of surfaces decorated with cellulose nanocrystals (CNCs) prepared via sulfuric acid hydrolysis, is explored. Such surfaces bear a high amount of negatively charged sulfate groups, which mimic the naturally occurring anticoagulant heparin in terms of charge density. It is demonstrated that CNC decorated surfaces significantly enhance the coagulation times of blood plasma and whole blood as proven by QCM-D and simple clotting tests.

GARP: a surface molecule of regulatory T cells that is involved in the regulatory function and TGF-β releasing.

PubMed

Sun, Liping; Jin, Hao; Li, Hui

2016-07-05

There are many molecules that define regulatory T cells (Tregs) phenotypically and functionally. Glycoprotein A repetitions predominant (GARP) is a transmembrane protein containing leucine rich repeats. Recently, GARP is found to express highly on the surface of activated Tregs. The combination of GARP and other surface molecules isolates Tregs with higher purity. Besides, GARP is a cell surface molecule of Tregs that maintains their regulatory function and homeosatsis. GARP has also been proved to promote the activation and secretion of transforming growth factor β (TGF-β). Moreover, its potential value in cancer immunotherapy is also discussed in this work.

Contact Activation of Blood Plasma and Factor XII by Ion-exchange Resins

PubMed Central

Yeh, Chyi-Huey Josh; Dimachkie, Ziad O.; Golas, Avantika; Cheng, Alice; Parhi, Purnendu; Vogler, Erwin A.

2011-01-01

Sepharose ion-exchange particles bearing strong Lewis acid/base functional groups (sulfopropyl, carboxymethyl, quarternary ammonium, dimethyl aminoethyl, and iminodiacetic acid) exhibiting high plasma protein adsorbent capacities are shown to be more efficient activators of blood factor XII in neat-buffer solution than either hydrophilic clean-glass particles or hydrophobic octyl sepharose particles ( FXII→surfaceactivatorFXIIa; a.k.a autoactivation, where FXII is the zymogen and FXIIa is a procoagulant protease). In sharp contrast to the clean-glass standard of comparison, ion-exchange activators are shown to be inefficient activators of blood plasma coagulation. These contrasting activation properties are proposed to be due to the moderating effect of plasma-protein adsorption on plasma coagulation. Efficient adsorption of blood plasma proteins unrelated to the coagulation cascade impedes FXII contacts with ion-exchange particles immersed in plasma, reducing autoactivation, and causing sluggish plasma coagulation. By contrast, plasma proteins do not adsorb to hydrophilic clean glass and efficient autoactivation leads directly to efficient activation of plasma coagulation. It is also shown that competitive-protein adsorption can displace FXIIa adsorbed to the surface of ion-exchange resins. As a consequence of highly-efficient autoactivation and FXIIa displacement by plasma proteins, ion-exchange particles are slightly more efficient activators of plasma coagulation than hydrophobic octyl sepharose particles that do not bear strong Lewis acid/base surface functionalities but to which plasma proteins adsorb efficiently. Plasma proteins thus play a dual role in moderating contact activation of the plasma coagulation cascade. The principal role is impeding FXII contact with activating surfaces but this same effect can displace FXIIa from an activating surface into solution where the protease can potentiate subsequent steps of the plasma coagulation cascade. PMID:21982294

Magnetite impregnation effects on the sorbent properties of activated carbons and biochars.

PubMed

Han, Zhantao; Sani, Badruddeen; Mrozik, Wojciech; Obst, Martin; Beckingham, Barbara; Karapanagioti, Hrissi K; Werner, David

2015-03-01

This paper discusses the sorbent properties of magnetic activated carbons and biochars produced by wet impregnation with iron oxides. The sorbents had magnetic susceptibilities consistent with theoretical predictions for carbon-magnetite composites. The high BET surface areas of the activated carbons were preserved in the synthesis, and enhanced for one low surface area biochar by dissolving carbonates. Magnetization decreased the point of zero charge. Organic compound sorption correlated strongly with BET surface areas for the pristine and magnetized materials, while metal cation sorption did not show such a correlation. Strong sorption of the hydrophobic organic contaminant phenanthrene to the activated carbon or biochar surfaces was maintained following magnetite impregnation, while phenol sorption was diminished, probably due to enhanced carbon oxidation. Copper, zinc and lead sorption to the activated carbons and biochars was unchanged or slightly enhanced by the magnetization, and iron oxides also contributed to the composite metal sorption capacity. While a magnetic biochar with 219 ± 3.7 m(2)/g surface area nearly reached the very strong organic pollutant binding capacity of the two magnetic activated carbons, a magnetic biochar with 68 ± 2.8 m(2)/g surface area was the best metal sorbent. Magnetic biochars thus hold promise as more sustainable alternatives to coal-derived magnetic activated carbons. Copyright © 2014 Elsevier Ltd. All rights reserved.

Activity and selectivity of photocatalysts in photodegradation of phenols.

PubMed

Emeline, A V; Zhang, X; Murakami, T; Fujishima, A

2012-04-15

Photodegradation of phenol and 4-chlorophenol over six different TiO(2) samples was tested in order to establish whether an interconnection between the activity and selectivity of photocatalysts exists. The obtained experimental data were analyzed using correlation analysis. Some correlations between the activity in phenol(s) photodegradation and selectivity toward formation of primary intermediate products were established. The type of correlations depends on the type of studied photoreactions. The discussion of the observed correlations between the activity and selectivity of photocatalysts is given in terms of the difference of surface concentrations of electrons and holes and corresponding surface active sites which might be dependent on the types of dominating surface faces. On the basis of the obtained results of correlation analysis it was assumed that a higher activity of photocatalysts could be achieved provided that both reduction and oxidation reaction pathways occur with equally high efficiency. Copyright © 2011 Elsevier B.V. All rights reserved.

Isolation of biologically active nanomaterial (inclusion bodies) from bacterial cells

PubMed Central

2010-01-01

Background In recent years bacterial inclusion bodies (IBs) were recognised as highly pure deposits of active proteins inside bacterial cells. Such active nanoparticles are very interesting for further downstream protein isolation, as well as for many other applications in nanomedicine, cosmetic, chemical and pharmaceutical industry. To prepare large quantities of a high quality product, the whole bioprocess has to be optimised. This includes not only the cultivation of the bacterial culture, but also the isolation step itself, which can be of critical importance for the production process. To determine the most appropriate method for the isolation of biologically active nanoparticles, three methods for bacterial cell disruption were analyzed. Results In this study, enzymatic lysis and two mechanical methods, high-pressure homogenization and sonication, were compared. During enzymatic lysis the enzyme lysozyme was found to attach to the surface of IBs, and it could not be removed by simple washing. As this represents an additional impurity in the engineered nanoparticles, we concluded that enzymatic lysis is not the most suitable method for IBs isolation. During sonication proteins are released (lost) from the surface of IBs and thus the surface of IBs appears more porous when compared to the other two methods. We also found that the acoustic output power needed to isolate the IBs from bacterial cells actually damages proteins structures, thereby causing a reduction in biological activity. High-pressure homogenization also caused some damage to IBs, however the protein loss from the IBs was negligible. Furthermore, homogenization had no side-effects on protein biological activity. Conclusions The study shows that among the three methods tested, homogenization is the most appropriate method for the isolation of active nanoparticles from bacterial cells. PMID:20831775

Isolation of biologically active nanomaterial (inclusion bodies) from bacterial cells.

PubMed

Peternel, Spela; Komel, Radovan

2010-09-10

In recent years bacterial inclusion bodies (IBs) were recognised as highly pure deposits of active proteins inside bacterial cells. Such active nanoparticles are very interesting for further downstream protein isolation, as well as for many other applications in nanomedicine, cosmetic, chemical and pharmaceutical industry.To prepare large quantities of a high quality product, the whole bioprocess has to be optimised. This includes not only the cultivation of the bacterial culture, but also the isolation step itself, which can be of critical importance for the production process.To determine the most appropriate method for the isolation of biologically active nanoparticles, three methods for bacterial cell disruption were analyzed. In this study, enzymatic lysis and two mechanical methods, high-pressure homogenization and sonication, were compared.During enzymatic lysis the enzyme lysozyme was found to attach to the surface of IBs, and it could not be removed by simple washing. As this represents an additional impurity in the engineered nanoparticles, we concluded that enzymatic lysis is not the most suitable method for IBs isolation.During sonication proteins are released (lost) from the surface of IBs and thus the surface of IBs appears more porous when compared to the other two methods. We also found that the acoustic output power needed to isolate the IBs from bacterial cells actually damages proteins structures, thereby causing a reduction in biological activity.High-pressure homogenization also caused some damage to IBs, however the protein loss from the IBs was negligible. Furthermore, homogenization had no side-effects on protein biological activity. The study shows that among the three methods tested, homogenization is the most appropriate method for the isolation of active nanoparticles from bacterial cells.

FAME: freeform active mirror experiment

NASA Astrophysics Data System (ADS)

Aitink-Kroes, Gabby; Agócs, Tibor; Miller, Chris; Black, Martin; Farkas, Szigfrid; Lemared, Sabri; Bettonvil, Felix; Montgomery, David; Marcos, Michel; Jaskó, Attila; van Duffelen, Farian; Challita, Zalpha; Fok, Sandy; Kiaeerad, Fatemeh; Hugot, Emmanuel; Schnetler, Hermine; Venema, Lars

2016-07-01

FAME is a four-year project and part of the OPTICON/FP7 program that is aimed at providing a breakthrough component for future compact, wide field, high resolution imagers or spectrographs, based on both Freeform technology, and the flexibility and versatility of active systems. Due to the opening of a new parameter space in optical design, Freeform Optics are a revolution in imaging systems for a broad range of applications from high tech cameras to astronomy, via earth observation systems, drones and defense. Freeform mirrors are defined by a non-rotational symmetry of the surface shape, and the fact that the surface shape cannot be simply described by conicoids extensions, or off-axis conicoids. An extreme freeform surface is a significantly challenging optical surface, especially for UV/VIS/NIR diffraction limited instruments. The aim of the FAME effort is to use an extreme freeform mirror with standard optics in order to propose an integrated system solution for use in future instruments. The work done so far concentrated on identification of compact, fast, widefield optical designs working in the visible, with diffraction limited performance; optimization of the number of required actuators and their layout; the design of an active array to manipulate the face sheet, as well as the actuator design. In this paper we present the status of the demonstrator development, with focus on the different building blocks: an extreme freeform thin face sheet, the active array, a highly controllable thermal actuator array, and the metrology and control system.

The role of electrostatic interactions in protease surface diffusion and the consequence for interfacial biocatalysis.

PubMed

Feller, Bob E; Kellis, James T; Cascão-Pereira, Luis G; Robertson, Channing R; Frank, Curtis W

2010-12-21

This study examines the influence of electrostatic interactions on enzyme surface diffusion and the contribution of diffusion to interfacial biocatalysis. Surface diffusion, adsorption, and reaction were investigated on an immobilized bovine serum albumin (BSA) multilayer substrate over a range of solution ionic strength values. Interfacial charge of the enzyme and substrate surface was maintained by performing the measurements at a fixed pH; therefore, electrostatic interactions were manipulated by changing the ionic strength. The interfacial processes were investigated using a combination of techniques: fluorescence recovery after photobleaching, surface plasmon resonance, and surface plasmon fluorescence spectroscopy. We used an enzyme charge ladder with a net charge ranging from -2 to +4 with respect to the parent to systematically probe the contribution of electrostatics in interfacial enzyme biocatalysis on a charged substrate. The correlation between reaction rate and adsorption was determined for each charge variant within the ladder, each of which displayed a maximum rate at an intermediate surface concentration. Both the maximum reaction rate and adsorption value at which this maximum rate occurs increased in magnitude for the more positive variants. In addition, the specific enzyme activity increased as the level of adsorption decreased, and for the lowest adsorption values, the specific enzyme activity was enhanced compared to the trend at higher surface concentrations. At a fixed level of adsorption, the specific enzyme activity increased with positive enzyme charge; however, this effect offers diminishing returns as the enzyme becomes more highly charged. We examined the effect of electrostatic interactions on surface diffusion. As the binding affinity was reduced by increasing the solution ionic strength, thus weakening electrostatic interaction, the rate of surface diffusion increased considerably. The enhancement in specific activity achieved at the lowest adsorption values is explained by the substantial rise in surface diffusion at high ionic strength due to decreased interactions with the surface. Overall, knowledge of the electrostatic interactions can be used to control surface parameters such as surface concentration and surface diffusion, which intimately correlate with surface biocatalysis. We propose that the maximum reaction rate results from a balance between adsorption and surface diffusion. The above finding suggests enzyme engineering and process design strategies for improving interfacial biocatalysis in industrial, pharmaceutical, and food applications.

Surface phase of TiO{sub 2} modified with La{sub 2}O{sub 3} and its effect on the photocatalytic H{sub 2} evolution

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

Zhang, Yangyang; Zhang, Jing, E-mail: jingzhang_dicp@live.cn; Xu, Qian

2014-05-01

Graphical abstract: The La{sub 2}O{sub 3}/TiO{sub 2}-900 °C (or La{sub 2}O{sub 3}/Ti(OH){sub 4}-900 °C), with surface anatase phase, show the similar photocatalytic activity. The presence of the surface anatase phase is important for high photocatalytic activity of TiO{sub 2} modified with La{sub 2}O{sub 3} (La{sub 2}O{sub 3}/Ti(OH){sub 4}-900 °C or La{sub 2}O{sub 3}/Ti(OH){sub 4}-900 °C){sub .} - Highlights: • Loading La{sub 2}O{sub 3} on anatase TiO{sub 2} is an effective method for stabilizing the anatase phases both in the surface and in the bulk region. • The high crystallinity of the surface anatase phase is important for high photocatalytic activitymore » of TiO{sub 2} modified with La{sub 2}O{sub 3.} - Abstract: TiO{sub 2} nanoparticles modified with La{sub 2}O{sub 3} were prepared by an impregnation method using anatase TiO{sub 2} support (La{sub 2}O{sub 3}/TiO{sub 2}) or amorphous Ti(OH){sub 4} support (La{sub 2}O{sub 3}/Ti(OH){sub 4}). The bulk and surface crystalline phases of La{sub 2}O{sub 3}/TiO{sub 2} (or La{sub 2}O{sub 3}/Ti(OH){sub 4}) have been characterized by X-ray powder diffraction (XRD) and UV Raman spectroscopy. Besides, morphology and particle size of La{sub 2}O{sub 3}/TiO{sub 2} and La{sub 2}O{sub 3}/Ti(OH){sub 4} samples have been determined by TEM (transmission electron microscope) and Brunauer–Emmett–Teller (BET), respectively. It is found that the phase transformation and increase of the particle size of TiO{sub 2} can be more effectively inhibited in the La{sub 2}O{sub 3}/TiO{sub 2} than in the La{sub 2}O{sub 3}/Ti(OH){sub 4}. Photocatalytic experiments indicated that the La{sub 2}O{sub 3}/TiO{sub 2} (or La{sub 2}O{sub 3}/Ti(OH){sub 4}) samples with surface anatase phase have the similar overall photocatalytic activities. Moreover, it is found that the high crystallinity of surface anatase phase is benefit for the high photocatalytic activity of TiO{sub 2} modified with La{sub 2}O{sub 3}.« less

Using high-resolution HiRISE digital elevation models to study early activity in polar regions

NASA Astrophysics Data System (ADS)

Portyankina, G.; Pommerol, A.; Aye, K.; Thomas, N.; Mattson, S.; Hansen, C. J.

2013-12-01

Martian polar areas are known for their very dynamic seasonal activity. It is believed that many observed seasonal phenomena here (cold CO2 jets, seasonal ice cracks, fan deposits, blotches) are produced by spring sublimation of CO2 slab ice. The Mars Reconnaissance Orbiter (MRO) High Resolution Imaging Science Experiment (HiRISE) has exceptional capabilities to image polar areas at times when surface processes there are most active, i.e. in early local spring. HiRISE data can be also used to create digital elevation models (DEMs) of the martian surface if two images with similar lighting but different observation geometry are available. Polar areas pose some specific problems in this because of the oblique illumination conditions and seasonally changing ice cover. Nevertheless, HiRISE DEMs with spatial resolution up to 1 meter were produced for a few polar locations with active spring sublimation. These DEMs improve our ability to directly compare observations from different local times, sols, seasons and martian years. These observations may now be orthorectified by projecting them onto the well-defined topography thus eliminating the ambiguities of different observational geometries. In addition, the DEM can serve as a link between the observations and models of seasonal activity. Observations of martian polar areas in springs of multiple martian years have led to the hypothesis that meter-scale topography is triggering the activity in early spring. Solar energy input is critical for the timing of spring activity. In this context, variations of surface inclination are important especially in early spring, when orientation towards the sun is one of critical parameters determining the level of solar energy input, the amount of CO2 sublimation, and hence the level of any activity connected to it. In the present study existing DEMs of two polar locations serve as model terrains to test the previously proposed hypothesis of early initialization of CO2 activity by solar illumination. We use the NAIF SPICE system to calculate precise energy input to each surface facet accounting for their slope and aspect orientation and shadowing by neighbor terrains. We show that the energy distribution over the surface is highly heterogeneous and maximized on the sides of the channels and other small topographical features. Our study supports the hypothesis that solar energy input in polar areas in spring is directly related to the activity observed.

CD45RO enriches for activated, highly mutated human germinal center B cells

PubMed Central

Jackson, Stephen M.; Harp, Natessa; Patel, Darshna; Zhang, Jeffrey; Willson, Savannah; Kim, Yoon J.; Clanton, Christian

2007-01-01

To date, there is no consensus regarding the influence of different CD45 isoforms during peripheral B-cell development. Examining correlations between surface CD45RO expression and various physiologic processes ongoing during the germinal center (GC) reaction, we hypothesized that GC B cells, like T cells, that up-regulate surface RO should progressively acquire phenotypes commonly associated with activated, differentiating lymphocytes. GC B cells (IgD−CD38+) were subdivided into 3 surface CD45RO fractions: RO−, RO+/−, and RO+. We show here that the average number of mutations per IgVH transcript increased in direct correlation with surface RO levels. Conjunctional use of RO and CD69 further delineated low/moderately and highly mutated fractions. Activation-induced cytidine deaminase (AID) mRNA was slightly reduced among RO+ GC B cells, suggesting that higher mutation averages are unlikely due to elevated somatic mutation activity. Instead, RO+ GC B cells were negative for Annexin V, comprised mostly (93%) of CD77− centrocytes, and were enriched for CD69+ cells. Collectively, RO+ GC B cells occupy what seems to be a specialized niche comprised mostly of centrocytes that may be in transition between activation states. These findings are among the first to sort GC B cells into populations enriched for live mutated cells solely using a single extracellular marker. PMID:17644737

Engineering electrocatalytic activity in nanosized perovskite cobaltite through surface spin-state transition

PubMed Central

Zhou, Shiming; Miao, Xianbing; Zhao, Xu; Ma, Chao; Qiu, Yuhao; Hu, Zhenpeng; Zhao, Jiyin; Shi, Lei; Zeng, Jie

2016-01-01

The activity of electrocatalysts exhibits a strongly dependence on their electronic structures. Specifically, for perovskite oxides, Shao-Horn and co-workers have reported a correlation between the oxygen evolution reaction activity and the eg orbital occupation of transition-metal ions, which provides guidelines for the design of highly active catalysts. Here we demonstrate a facile method to engineer the eg filling of perovskite cobaltite LaCoO3 for improving the oxygen evolution reaction activity. By reducing the particle size to ∼80 nm, the eg filling of cobalt ions is successfully increased from unity to near the optimal configuration of 1.2 expected by Shao-Horn's principle. Consequently, the activity is significantly enhanced, comparable to those of recently reported cobalt oxides with eg∼1.2 configurations. This enhancement is ascribed to the emergence of spin-state transition from low-spin to high-spin states for cobalt ions at the surface of the nanoparticles, leading to more active sites with increased reactivity. PMID:27187067

Nitrogen-doped porous carbon nanosheets made from biomass as highly active electrocatalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Pan, Fuping; Cao, Zhongyue; Zhao, Qiuping; Liang, Hongyu; Zhang, Junyan

2014-12-01

The successful commercialization of fuel cells requires the efficient electrocatalyst to make the oxygen reduction reaction (ORR) fast because of the sluggish nature of ORR and the high cost of the platinum catalysts. In this work, we report the excellent performance of metal-free nitrogen-doped porous carbon nanosheets (NPCN) with hierarchical porous structure and a high surface area of 1436.02 m2 g-1 for catalyzing ORR. The active NPCN is synthesized via facile high-temperature carbonization of natural ginkgo leaves followed by purification and ammonia post-treatment without using additional supporting templates and activation processes. In O2-saturated 0.1 M KOH solution, the resultant NPCN exhibits a high kinetic-limiting current density of 13.57 mA cm-2 at -0.25 V (vs. Ag/AgCl) approaching that of the commercial Pt/C catalyst (14 mA cm-2) and long-term electrochemical stability. Notably, the NPCN shows a slightly negative ORR half-wave potential in comparison with Pt/C (ΔE1/2 = 19 mV). The excellent electrocatalytic properties of NPCN originate from the combined effect of optimal nitrogen doping, high surface area, and porous architecture, which induce the high-density distribution of highly active and stable catalytic sites.

The Effect of Solution Chemistry on Nucleation of Nesquehonite

NASA Astrophysics Data System (ADS)

Zhao, L.; Zhu, C.; Wang, Z.

2016-12-01

The interfaces between minerals and aqueous solutions are key to important Earth surface processes, including chemical weathering, mineral dissolution/precipitation, and pollutant absorption/release. Mineral surface properties, such as the surface structure and the surface energy, determine the outcomes of many geochemical reactions. Several factors could affect surface energy, but the effect of solution chemistry, particularly the solution stoichiometry, on the surface energy and nucleation process is poorly understood. The goal of this study is to understand the effect of solution chemistry on the nucleation of nesquehonite. Nesquehonite nucleation experiments were conducted in aqueous solutions having similar Mg2+/ CO32- activity ratios, but different saturation states and solution pH. The experimental results show that induction-time estimates from our precipitation experiments with similar Mg2+/CO32- activity ratios are consistent with classical nucleation theory (CNT), while the surface energy derived from CNT varies with Mg2+/CO32- activity ratios. Our observations can be explained by the different absorption behaviors of Mg2+ and CO32- and and/or reduced Gibbs free energies through better screening of the electric double layer. A surface energy model involving solution composition is developed that combines surface complexation with electrostatic models. The new model takes into account how surface charge may affect surface energy. It implies that the highest surface energy may occur around the point of zero charge (p.z.c), where the nucleation is fastest (or conversely, where the induction time is shortest) under low saturation states, but not under high saturation states. An accelerated attachment rate of monomers at the p.z.c. is consistent with high surface energy, since it represents higher reactivity of surface ions and less work needed to break the solvated water molecules. This study provides deeper insights into mechanisms of nesquehonite nucleation in nature, and guidelines for accelerating the precipitation rates of nesquehonite.

Externally pressurized porous cylinder for multiple surface aerosol generation and method of generation

DOEpatents

Apel, C.T.; Layman, L.R.; Gallimore, D.L.

1988-05-10

A nebulizer is described for generating aerosol having small droplet sizes and high efficiency at low sample introduction rates. The nebulizer has a cylindrical gas permeable active surface. A sleeve is disposed around the cylinder and gas is provided from the sleeve to the interior of the cylinder formed by the active surface. In operation, a liquid is provided to the inside of the gas permeable surface. The gas contacts the wetted surface and forms small bubbles which burst to form an aerosol. Those bubbles which are large are carried by momentum to another part of the cylinder where they are renebulized. This process continues until the entire sample is nebulized into aerosol sized droplets. 2 figs.

Design of elevator control surface actuated by LIPCA for small unmanned air vehicle

NASA Astrophysics Data System (ADS)

Yoon, K. J.; Setiawan, Hery; Goo, N. S.

2006-03-01

There have been persistent interests in high performance actuators suitable for the actuation of control surfaces of small aircraft and helicopter blades and for active vibration control of aerospace and submarine structures that need high specific force and displacement. What is really needed for active actuation is a large-displacement actuator with a compact source, i.e., much higher strain. A lot of effort has been made to develop compact actuators with large displacement at a high force. One of the representative actuator is LIPCA actuator that was introduced by Yoon et al. The LIPCA design offers the advantages to be applied as actuator for the small aerial vehicle comparing with any other actuators. The weight is one of the main concerns for aerospace field, and since LIPCA has lighter weight than any other piezo-actuator thus it is suitable as actuator for small aircraft control surface. In this paper, a conceptual design of LIPCA-actuated control surface is introduced. A finite element model was constructed and analyzed to predict the deflection angle of the control surface. The hinge moment that produced by the aerodynamic forces was calculated to determine the optimum position of the hinge point, which could produce the deflection as high as possible with reasonable hinge moment. To verify the prediction, a prototype of SUAV (small unmanned air vehicle) control surface was manufactured and tested both in static condition and in the wind tunnel. The prediction and test results showed a good agreement on the control surface deflection angle.

The Effect of Involuntary Motor Activity on Myoelectric Pattern Recognition: A Case Study with Chronic Stroke Patients

PubMed Central

Zhang, Xu; Li, Yun; Chen, Xiang; Li, Guanglin; Rymer, William Zev; Zhou, Ping

2013-01-01

This study investigates the effect of involuntary motor activity of paretic-spastic muscles on classification of surface electromyography (EMG) signals. Two data collection sessions were designed for 8 stroke subjects to voluntarily perform 11 functional movements using their affected forearm and hand at a relatively slow and fast speed. For each stroke subject, the degree of involuntary motor activity present in voluntary surface EMG recordings was qualitatively described from such slow and fast experimental protocols. Myoelectric pattern recognition analysis was performed using different combinations of voluntary surface EMG data recorded from slow and fast sessions. Across all tested stroke subjects, our results revealed that when involuntary surface EMG was absent or present in both training and testing datasets, high accuracies (> 96%, > 98%, respectively, averaged over all the subjects) can be achieved in classification of different movements using surface EMG signals from paretic muscles. When involuntary surface EMG was solely involved in either training or testing datasets, the classification accuracies were dramatically reduced (< 89%, < 85%, respectively). However, if both training and testing datasets contained EMG signals with presence and absence of involuntary EMG interference, high accuracies were still achieved (> 97%). The findings of this study can be used to guide appropriate design and implementation of myoelectric pattern recognition based systems or devices toward promoting robot-aided therapy for stroke rehabilitation. PMID:23860192

Preparation of robust braid-reinforced poly(vinyl chloride) ultrafiltration hollow fiber membrane with antifouling surface and application to filtration of activated sludge solution.

PubMed

Zhou, Zhuang; Rajabzadeh, Saeid; Fang, Lifeng; Miyoshi, Taro; Kakihana, Yuriko; Matsuyama, Hideto

2017-08-01

Braid-reinforced hollow fiber membranes with high mechanical properties and considerable antifouling surface were prepared by blending poly(vinyl chloride) (PVC) with poly(vinyl chloride-co-poly(ethylene glycol) methyl ether methacrylate) (poly(VC-co-PEGMA)) copolymer via non-solvent induced phase separation (NIPS). The tensile strength of the braid-reinforced PVC hollow fiber membranes were significantly larger than those of previously reported various types of PVC hollow fiber membranes. The high interfacial bonding strength indicated the good compatibility between the coating materials and the surface of polyethylene terephthalate (PET)-braid. Owing to the surface segregation phenomena, the membrane surface PEGMA coverage increased upon increasing the poly(VC-co-PEGMA)/PVC blending ratio, resulting in higher hydrophilicities and bovine serum albumin (BSA) repulsion. To compare the fouling properties, membranes with similar PWPs were prepared by adjusting the dope solution composition to eliminate the effect of hydrodynamic conditions on the membrane fouling performance. The blend membranes surface exhibited considerable fouling resistance to the molecular adsorption from both BSA solution and activated sludge solution. In both cases, the flux recovered to almost 80% of the initial flux using only water backflush. Considering their great mechanical properties and antifouling resistance to activated sludge solution, these novel membranes show good potential for application in wastewater treatment. Copyright © 2017 Elsevier B.V. All rights reserved.

A highly active and stable IrO x/SrIrO 3 catalyst for the oxygen evolution reaction

DOE PAGES

Seitz, Linsey C.; Dickens, Colin F.; Nishio, Kazunori; ...

2016-09-02

Oxygen electrochemistry plays a key role in renewable energy technologies such as fuel cells and electrolyzers, but the slow kinetics of the oxygen evolution reaction (OER) limit the performance and commercialization of such devices. Here we report an iridium oxide/strontium iridium oxide (IrO x/SrIrO 3) catalyst formed during electrochemical testing by strontium leaching from surface layers of thin films of SrIrO 3. This catalyst has demonstrated specific activity at 10 milliamps per square centimeter of oxide catalyst (OER current normalized to catalyst surface area), with only 270 to 290 millivolts of overpotential for 30 hours of continuous testing in acidicmore » electrolyte. Here, density functional theory calculations suggest the formation of highly active surface layers during strontium leaching with IrO 3 or anatase IrO 2 motifs. The IrO x/SrIrO 3 catalyst outperforms known IrO x and ruthenium oxide (RuO x) systems, the only other OER catalysts that have reasonable activity in acidic electrolyte.« less

Experimental and computational investigation of acetic acid deoxygenation over oxophilic molybdenum carbide: Surface chemistry and active site identity

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

Schaidle, Joshua A.; Blackburn, Jeffrey; Farberow, Carrie A.

Ex situ catalytic fast pyrolysis (CFP) is a promising route for producing fungible biofuels; however, this process requires bifunctional catalysts that favor C–O bond cleavage, activate hydrogen at near atmospheric pressure and high temperature (350–500 °C), and are stable under high-steam, low hydrogen-to-carbon environments. Recently, early transition-metal carbides have been reported to selectively cleave C–O bonds of alcohols, aldehydes, and oxygenated aromatics, yet there is limited understanding of the metal carbide surface chemistry under reaction conditions and the identity of the active sites for deoxygenation. In this study, we evaluated molybdenum carbide (Mo 2C) for the deoxygenation of acetic acid,more » an abundant component of biomass pyrolysis vapors, under ex situ CFP conditions, and we probed the Mo 2C surface chemistry, identity of the active sites, and deoxygenation pathways using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations.« less

A highly active and stable IrOx/SrIrO3 catalyst for the oxygen evolution reaction.

PubMed

Seitz, Linsey C; Dickens, Colin F; Nishio, Kazunori; Hikita, Yasuyuki; Montoya, Joseph; Doyle, Andrew; Kirk, Charlotte; Vojvodic, Aleksandra; Hwang, Harold Y; Norskov, Jens K; Jaramillo, Thomas F

2016-09-02

Oxygen electrochemistry plays a key role in renewable energy technologies such as fuel cells and electrolyzers, but the slow kinetics of the oxygen evolution reaction (OER) limit the performance and commercialization of such devices. Here we report an iridium oxide/strontium iridium oxide (IrO x /SrIrO 3 ) catalyst formed during electrochemical testing by strontium leaching from surface layers of thin films of SrIrO 3 This catalyst has demonstrated specific activity at 10 milliamps per square centimeter of oxide catalyst (OER current normalized to catalyst surface area), with only 270 to 290 millivolts of overpotential for 30 hours of continuous testing in acidic electrolyte. Density functional theory calculations suggest the formation of highly active surface layers during strontium leaching with IrO 3 or anatase IrO 2 motifs. The IrO x /SrIrO 3 catalyst outperforms known IrO x and ruthenium oxide (RuO x ) systems, the only other OER catalysts that have reasonable activity in acidic electrolyte. Copyright © 2016, American Association for the Advancement of Science.

Experimental and computational investigation of acetic acid deoxygenation over oxophilic molybdenum carbide: Surface chemistry and active site identity

DOE PAGES

Schaidle, Joshua A.; Blackburn, Jeffrey; Farberow, Carrie A.; ...

2016-01-21

Ex situ catalytic fast pyrolysis (CFP) is a promising route for producing fungible biofuels; however, this process requires bifunctional catalysts that favor C–O bond cleavage, activate hydrogen at near atmospheric pressure and high temperature (350–500 °C), and are stable under high-steam, low hydrogen-to-carbon environments. Recently, early transition-metal carbides have been reported to selectively cleave C–O bonds of alcohols, aldehydes, and oxygenated aromatics, yet there is limited understanding of the metal carbide surface chemistry under reaction conditions and the identity of the active sites for deoxygenation. In this study, we evaluated molybdenum carbide (Mo 2C) for the deoxygenation of acetic acid,more » an abundant component of biomass pyrolysis vapors, under ex situ CFP conditions, and we probed the Mo 2C surface chemistry, identity of the active sites, and deoxygenation pathways using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations.« less

(100) facets of γ-Al2O3: the active surfaces for alcohol dehydration reactions

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

Kwak, Ja Hun; Mei, Donghai; Peden, Charles HF

2011-05-01

Temperature programmed desorption (TPD) of ethanol, and methanol dehydration reaction were studied on γ-Al2O3 in order to identify the catalytic active sites for alcohol dehydration reactions. Two high temperature (> 473 K) desorption features were observed following ethanol adsorption. Samples calcined at T≤473 K displayed a desorption feature in the 523-533 K temperature range, while those calcined at T ≥ 673 K showed a single desorption feature at 498 K. The switch from the high to low temperature ethanol desorption correlated well with the dehydroxylation of the (100) facets of γ-Al2O3 that was predicted at 550 K DFT calculations. Theoreticalmore » DFT simulations of the mechanism of dehydration. on clean and hydroxylated γ-Al2O3(100) surfaces, find that a concerted elimination of ethylene from an ethanol molecule chemisorbed at an Al3+ pentacoordinated site is the rate limiting step for catalytic cycle on both surfaces. Furthermore, titration of the pentacoordinate Al3+ sites on the (100) facets of γ-Al2O3 by BaO completely turned off the methanol dehydration reaction activity. These results unambiguously demonstrate that only the (100) facets on γ-Al2O3 are the catalytic active surfaces for alcohol dehydration.« less

Liquid-permeable electrode

DOEpatents

Folser, George R.

1980-01-01

Electrodes for use in an electrolytic cell, which are liquid-permeable and have low electrical resistance and high internal surface area are provided of a rigid, porous, carbonaceous matrix having activated carbon uniformly embedded throughout. The activated carbon may be catalyzed with platinum for improved electron transfer between electrode and electrolyte. Activated carbon is mixed with a powdered thermosetting phenolic resin and compacted to the desired shape in a heated mold to melt the resin and form the green electrode. The compact is then heated to a pyrolyzing temperature to carbonize and volatilize the resin, forming a rigid, porous structure. The permeable structure and high internal surface area are useful in electrolytic cells where it is necessary to continuously remove the products of the electrochemical reaction.

Using Amphiphilic Nanostructures to Enable Long-Range Ensemble Coalescence and Surface Rejuvenation in Dropwise Condensation

DTIC Science & Technology

2012-01-01

in high-humidity environments. Nature-inspired superhydrophobic surfaces have been actively explored to enhance heat and mass transfer rates by...challenge with superhydrophobic surfaces, as observed in nature on the lotus leaf21 and on synthetic surfaces,22,23 is that they are often rendered...Dynamics. Rev. Mod. Phys. 1985, 57, 827–863. 2. Kim, S. H. Fabrication of Superhydrophobic Surfaces. J. Adhes. Sci. Technol. 2008, 22, 235–250. 3

Imine-Linked Polymer Based Nitrogen-Doped Porous Activated Carbon for Efficient and Selective CO2 Capture.

PubMed

Alabadi, Akram; Abbood, Hayder A; Li, Qingyin; Jing, Ni; Tan, Bien

2016-12-13

The preparation of nitrogen-doped activated carbon (NACs) has received significant attention because of their applications in CO 2 capture and sequestration (CCS) owing to abundant nitrogen atoms on their surface and controllable pore structures by carefully controlled carbonization. We report high-surface-area porous N-doped activated carbons (NAC) by using soft-template-assisted self-assembly followed by thermal decomposition and KOH activation. The activation process was carried out under different temperature conditions (600-800 °C) using polyimine as precursor. The NAC-800 was found to have a high specific surface area (1900 m 2  g -1 ), a desirable micropore size below 1 nm and, more importantly, a large micropore volume (0.98 cm 3  g -1 ). NAC-800 also exhibits a significant capacity of CO 2 capture i.e., over 6. 25 and 4.87 mmol g -1 at 273 K and 298 K respectively at 1.13 bar, which is one of among the highest values reported for porous carbons so far. Moreover, NAC also shows an excellent separation selectivity for CO 2 over N 2 .

Imine-Linked Polymer Based Nitrogen-Doped Porous Activated Carbon for Efficient and Selective CO2 Capture

PubMed Central

Alabadi, Akram; Abbood, Hayder A.; Li, Qingyin; Jing, Ni; Tan, Bien

2016-01-01

The preparation of nitrogen-doped activated carbon (NACs) has received significant attention because of their applications in CO2 capture and sequestration (CCS) owing to abundant nitrogen atoms on their surface and controllable pore structures by carefully controlled carbonization. We report high-surface-area porous N-doped activated carbons (NAC) by using soft-template-assisted self-assembly followed by thermal decomposition and KOH activation. The activation process was carried out under different temperature conditions (600–800 °C) using polyimine as precursor. The NAC-800 was found to have a high specific surface area (1900 m2 g−1), a desirable micropore size below 1 nm and, more importantly, a large micropore volume (0.98 cm3 g−1). NAC-800 also exhibits a significant capacity of CO2 capture i.e., over 6. 25 and 4.87 mmol g−1 at 273 K and 298 K respectively at 1.13 bar, which is one of among the highest values reported for porous carbons so far. Moreover, NAC also shows an excellent separation selectivity for CO2 over N2. PMID:27958305

Pore size distribution and supercritical hydrogen adsorption in activated carbon fibers

NASA Astrophysics Data System (ADS)

Purewal, J. J.; Kabbour, H.; Vajo, J. J.; Ahn, C. C.; Fultz, B.

2009-05-01

Pore size distributions (PSD) and supercritical H2 isotherms have been measured for two activated carbon fiber (ACF) samples. The surface area and the PSD both depend on the degree of activation to which the ACF has been exposed. The low-surface-area ACF has a narrow PSD centered at 0.5 nm, while the high-surface-area ACF has a broad distribution of pore widths between 0.5 and 2 nm. The H2 adsorption enthalpy in the zero-coverage limit depends on the relative abundance of the smallest pores relative to the larger pores. Measurements of the H2 isosteric adsorption enthalpy indicate the presence of energy heterogeneity in both ACF samples. Additional measurements on a microporous, coconut-derived activated carbon are presented for reference.

Palladium Coated Copper Nanowires as a Hydrogen Oxidation Electrocatalyst in Base

DOE PAGES

Alia, Shaun M.; Yan, Yushan

2015-05-09

The palladium (Pd) nanotubes we synthesized by the spontaneous galvanic displacement of copper (Cu) nanowires, are forming extended surface nanostructures highly active for the hydrogen oxidation reaction (HOR) in base. The synthesized catalysts produce specific activities in rotating disk electrode half-cells 20 times greater than Pd nanoparticles and about 80% higher than polycrystalline Pd. Although the surface area of the Pd nanotubes was low compared to conventional catalysts, partial galvanic displacement thrifted the noble metal layer and increased the Pd surface area. Moreover, the use of Pd coated Cu nanowires resulted in a HOR mass exchange current density 7 timesmore » greater than the Pd nanoparticles. The activity of the Pd coated Cu nanowires further nears Pt/C, producing 95% of the mass activity.« less

Pore size distribution and supercritical hydrogen adsorption in activated carbon fibers.

PubMed

Purewal, J J; Kabbour, H; Vajo, J J; Ahn, C C; Fultz, B

2009-05-20

Pore size distributions (PSD) and supercritical H2 isotherms have been measured for two activated carbon fiber (ACF) samples. The surface area and the PSD both depend on the degree of activation to which the ACF has been exposed. The low-surface-area ACF has a narrow PSD centered at 0.5 nm, while the high-surface-area ACF has a broad distribution of pore widths between 0.5 and 2 nm. The H2 adsorption enthalpy in the zero-coverage limit depends on the relative abundance of the smallest pores relative to the larger pores. Measurements of the H2 isosteric adsorption enthalpy indicate the presence of energy heterogeneity in both ACF samples. Additional measurements on a microporous, coconut-derived activated carbon are presented for reference.

High performance and reusable SERS substrates using Ag/ZnO heterostructure on periodic silicon nanotube substrate

NASA Astrophysics Data System (ADS)

Lai, Yi-Chen; Ho, Hsin-Chia; Shih, Bo-Wei; Tsai, Feng-Yu; Hsueh, Chun-Hway

2018-05-01

Surface-enhanced Raman scattering (SERS) substrate with a higher surface area, enhanced light harvesting, multiple hot spots and strong electromagnetic field enhancements would exhibit enhanced Raman signals. Herein, the Ag nanoparticle/ZnO nanowire heterostructure decorated periodic silicon nanotube (Ag@ZnO@SiNT) substrate was proposed and fabricated. The proposed structure employed as SERS-active substrate was examined, and the results showed both the high performance in terms of high sensitivity and good reproducibility. Furthermore, the Ag@ZnO@SiNT substrate demonstrated the self-cleaning performance through the photocatalytic degradation of probed molecules upon UV-irradiation. The results showed that the proposed nanostructure had high performance, good reproducibility and reusability, and it is a promising SERS-active substrate for molecular sensing and cleaning.

Regulated internalization of NMDA receptors drives PKD1-mediated suppression of the activity of residual cell-surface NMDA receptors.

PubMed

Fang, Xiao-Qian; Qiao, Haifa; Groveman, Bradley R; Feng, Shuang; Pflueger, Melissa; Xin, Wen-Kuan; Ali, Mohammad K; Lin, Shuang-Xiu; Xu, Jindong; Duclot, Florian; Kabbaj, Mohamed; Wang, Wei; Ding, Xin-Sheng; Santiago-Sim, Teresa; Jiang, Xing-Hong; Salter, Michael W; Yu, Xian-Min

2015-11-19

Constitutive and regulated internalization of cell surface proteins has been extensively investigated. The regulated internalization has been characterized as a principal mechanism for removing cell-surface receptors from the plasma membrane, and signaling to downstream targets of receptors. However, so far it is still not known whether the functional properties of remaining (non-internalized) receptor/channels may be regulated by internalization of the same class of receptor/channels. The N-methyl-D-aspartate receptor (NMDAR) is a principal subtype of glutamate-gated ion channel and plays key roles in neuronal plasticity and memory functions. NMDARs are well-known to undergo two types of regulated internalization - homologous and heterologous, which can be induced by high NMDA/glycine and DHPG, respectively. In the present work, we investigated effects of regulated NMDAR internalization on the activity of residual cell-surface NMDARs and neuronal functions. In electrophysiological experiments we discovered that the regulated internalization of NMDARs not only reduced the number of cell surface NMDARs but also caused an inhibition of the activity of remaining (non-internalized) surface NMDARs. In biochemical experiments we identified that this functional inhibition of remaining surface NMDARs was mediated by increased serine phosphorylation of surface NMDARs, resulting from the activation of protein kinase D1 (PKD1). Knockdown of PKD1 did not affect NMDAR internalization but prevented the phosphorylation and inhibition of remaining surface NMDARs and NMDAR-mediated synaptic functions. These data demonstrate a novel concept that regulated internalization of cell surface NMDARs not only reduces the number of NMDARs on the cell surface but also causes an inhibition of the activity of remaining surface NMDARs through intracellular signaling pathway(s). Furthermore, modulating the activity of remaining surface receptors may be an effective approach for treating receptor internalization-induced changes in neuronal functions of the CNS.

Synthesis and catalytic activity of polysaccharide templated nanocrystalline sulfated zirconia

NASA Astrophysics Data System (ADS)

Sherly, K. B.; Rakesh, K.

2014-01-01

Nanoscaled materials are of great interest due to their unique enhanced optical, electrical and magnetic properties. Sulfate-promoted zirconia has been shown to exhibit super acidic behavior and high activity for acid catalyzed reactions. Nanocrystalline zirconia was prepared in the presence of polysaccharide template by interaction between ZrOCl2ṡ8H2O and chitosan template. The interaction was carried out in aqueous phase, followed by the removal of templates by calcination at optimum temperature and sulfation. The structural and textural features were characterized by powder XRD, TG, SEM and TEM. XRD patterns showed the peaks of the diffractogram were in agreement with the theoretical data of zirconia with the catalytically active tetragonal phase and average crystalline size of the particles was found to be 9 nm, which was confirmed by TEM. TPD using ammonia as probe, FTIR and BET surface area analysis were used for analyzing surface features like acidity and porosity. The BET surface area analysis showed the sample had moderately high surface area. FTIR was used to find the type species attached to the surface of zirconia. UV-DRS found the band gap of the zirconia was found to be 2.8 eV. The benzylation of o-xylene was carried out batchwise in atmospheric pressure and 433K temperature using sulfated zirconia as catalyst.

Expression and nutritional regulation of the (pro)renin receptor in rat visceral adipose tissue.

PubMed

Achard, V; Tassistro, V; Boullu-Ciocca, S; Grino, M

2011-12-01

Early life nutritional environment plays an important role in the development of visceral adipose tissue and interacts with nutritional regulations in adulthood, leading to metabolic dysregulations. We hypothesized that the renin-angiotensin system may play a role in the programming-induced development of visceral adipose tissue. We studied, using a model of programming of overweight and glucose intolerance, obtained by post-natal overfeeding with consecutive highfat diet, the status of plasma renin activity and mesenteric adipose renin-angiotensin system, including the recently identified (pro)renin receptor, in adult rats. Post-natal overfeeding or high-fat feeding lead to overweight with increased visceral fat mass and adipocytes surface. When both paradigms were associated, adipocytes surface showed a disproportionate increase. A strong immunoreactivity for (pro)renin receptor was found in stromal cells. Plasma renin activity increased in programmed animals whereas (pro)renin receptor expressing cells density was stimulated by high-fat diet. There was a positive, linear relationship between plasma renin activity and (pro)renin receptor expressing cells density and adipocytes surface. Our experiments demonstrate that association of post-natal overfeeding and high-fat diet increased plasma renin activity and adipose (pro)renin receptor expression. Such phenomenon could explain, at least in part, the associated disproportionate adipocyte hypertrophy and its accompanying increased glucose intolerance.

The high surface energy of NiO {110} facets incorporated into TiO2 hollow microspheres by etching Ti plate for enhanced photocatalytic and photoelectrochemical activity

NASA Astrophysics Data System (ADS)

Li, Jian; Cui, Hongzhi; Song, Xiaojie; Wei, Na; Tian, Jian

2017-02-01

We present a rational design for the controllable synthesis of NiO/TiO2 hollow microspheres (NTHMs) with Ti plate via a one-pot template-free synthesis strategy. Specifically, to enhance the formation of hollow microspheres, part of the titanium source is provided by the Ti plate. The hollow spherical NiO/TiO2 particles possess unique microstructural characteristics, namely, a higher specific surface area (∼65.82 m2 g-1), a larger mesoporous structure (∼7.79 nm), and hierarchical nanoarchitectures connected with mesopores within the shell (monodispersed size of ∼1 μm and shell thickness of ∼80 nm). In addition, as a cocatalyst for improved catalytic activity, the incorporated NiO nanoparticles with exposed high surface energy {110} facets displayed an outstanding performance. It has been proven that this facile nanostructure possesses remarkably high photoelectrochemical and photocatalytic activities. The main mechanism for enhancement of photocatalytic activity is attributed to the construction of p-n junctions with an inner electric field between TiO2 and NiO, which can dramatically enhance the separation efficiency of the photogenerated electron-hole pairs. This strategy could be applied to fabricate mixed metal oxide hollow microspheres toward the photoelectrochemical catalysis.

Construction of the yeast whole-cell Rhizopus oryzae lipase biocatalyst with high activity.

PubMed

Chen, Mei-ling; Guo, Qin; Wang, Rui-zhi; Xu, Juan; Zhou, Chen-wei; Ruan, Hui; He, Guo-qing

2011-07-01

Surface display is effectively utilized to construct a whole-cell biocatalyst. Codon optimization has been proven to be effective in maximizing production of heterologous proteins in yeast. Here, the cDNA sequence of Rhizopus oryzae lipase (ROL) was optimized and synthesized according to the codon bias of Saccharomyces cerevisiae, and based on the Saccharomyces cerevisiae cell surface display system with α-agglutinin as an anchor, recombinant yeast displaying fully codon-optimized ROL with high activity was successfully constructed. Compared with the wild-type ROL-displaying yeast, the activity of the codon-optimized ROL yeast whole-cell biocatalyst (25 U/g dried cells) was 12.8-fold higher in a hydrolysis reaction using p-nitrophenyl palmitate (pNPP) as the substrate. To our knowledge, this was the first attempt to combine the techniques of yeast surface display and codon optimization for whole-cell biocatalyst construction. Consequently, the yeast whole-cell ROL biocatalyst was constructed with high activity. The optimum pH and temperature for the yeast whole-cell ROL biocatalyst were pH 7.0 and 40 °C. Furthermore, this whole-cell biocatalyst was applied to the hydrolysis of tributyrin and the resulted conversion of butyric acid reached 96.91% after 144 h.

Integrating high electrical conductivity and photocatalytic activity in cotton fabric by cationizing for enriched coating of negatively charged graphene oxide.

PubMed

Sahito, Iftikhar Ali; Sun, Kyung Chul; Arbab, Alvira Ayoub; Qadir, Muhammad Bilal; Jeong, Sung Hoon

2015-10-05

Electroconductive textiles have attended tremendous focus recently and researchers are making efforts to increase conductivity of e-textiles, in order to increase the use of such flexible and low cost textile materials. In this study, surface conductivity and photo catalytic activity of standard cotton fabric (SCF) was enhanced by modifying its surface charge, from negative to positive, using Bovine Serum Albumin (BSA) as a cationic agent, to convert it into cationised cotton fabric (CCF). Then, both types of fabrics were dip coated with a simple dip and dry technique for the adsorption of negatively charged graphene oxide (GO) sheets onto its surface. This resulted in 67.74% higher loading amount of GO on the CCF making self-assembly. Finally, this coating was chemically converted by vapor reduction using hydrazine hydrate to reduced graphene oxide (rGO) for restoration of a high electrical conductivity at the fabric surface. Our results revealed that with such high loading of GO, the surface resistance of CCF was only 40Ω/sq as compared to 510Ω/sq of the SCF and a 66% higher photo catalytic activity was also achieved through cationization for improved GO coating. Graphene coated SCF and CCF were characterized using FE-SEM, FTIR, Raman, UV-vis, WAXD, EDX and XPS spectroscopy to ascertain successful reduction of GO to rGO. The effect of BSA treatment on adsorption of cotton fabric was studied using drop shape analyzer to measure contact angle and for thermal and mechanical resistance, the fabric was tested for TGA and tensile strength, respectively. rGO coated fabric also showed slightly improved thermal stability yet a minor loss of strength was observed. The high flexibility, photocatalytic activity and excellent conductivity of this fabric suggests that it can be used as an electrode material for various applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

A Novel Surface Structure Consisting of Contact-active Antibacterial Upper-layer and Antifouling Sub-layer Derived from Gemini Quaternary Ammonium Salt Polyurethanes.

PubMed

He, Wei; Zhang, Yi; Li, Jiehua; Gao, Yunlong; Luo, Feng; Tan, Hong; Wang, Kunjie; Fu, Qiang

2016-08-26

Contact-active antibacterial surfaces play a vital role in preventing bacterial contamination of artificial surfaces. In the past, numerous researches have been focused on antibacterial surfaces comprising of antifouling upper-layer and antibacterial sub-layer. In this work, we demonstrate a reversed surface structure which integrate antibacterial upper-layer and antifouling sub-layer. These surfaces are prepared by simply casting gemini quaternary ammonium salt waterborne polyurethanes (GWPU) and their blends. Due to the high interfacial energy of gemini quaternary ammonium salt (GQAS), chain segments containing GQAS can accumulate at polymer/air interface to form an antibacterial upper-layer spontaneously during the film formation. Meanwhile, the soft segments composed of polyethylene glycol (PEG) formed the antifouling sub-layer. Our findings indicate that the combination of antibacterial upper-layer and antifouling sub-layer endow these surfaces strong, long-lasting antifouling and contact-active antibacterial properties, with a more than 99.99% killing efficiency against both gram-positive and gram-negative bacteria attached to them.

A Novel Surface Structure Consisting of Contact-active Antibacterial Upper-layer and Antifouling Sub-layer Derived from Gemini Quaternary Ammonium Salt Polyurethanes

PubMed Central

He, Wei; Zhang, Yi; Li, Jiehua; Gao, Yunlong; Luo, Feng; Tan, Hong; Wang, Kunjie; Fu, Qiang

2016-01-01

Contact-active antibacterial surfaces play a vital role in preventing bacterial contamination of artificial surfaces. In the past, numerous researches have been focused on antibacterial surfaces comprising of antifouling upper-layer and antibacterial sub-layer. In this work, we demonstrate a reversed surface structure which integrate antibacterial upper-layer and antifouling sub-layer. These surfaces are prepared by simply casting gemini quaternary ammonium salt waterborne polyurethanes (GWPU) and their blends. Due to the high interfacial energy of gemini quaternary ammonium salt (GQAS), chain segments containing GQAS can accumulate at polymer/air interface to form an antibacterial upper-layer spontaneously during the film formation. Meanwhile, the soft segments composed of polyethylene glycol (PEG) formed the antifouling sub-layer. Our findings indicate that the combination of antibacterial upper-layer and antifouling sub-layer endow these surfaces strong, long-lasting antifouling and contact-active antibacterial properties, with a more than 99.99% killing efficiency against both gram-positive and gram-negative bacteria attached to them. PMID:27561546

Tobacco Stem-Based Activated Carbons for High Performance Supercapacitors

NASA Astrophysics Data System (ADS)

Xia, Xiaohong; Liu, Hongbo; Shi, Lei; He, Yuede

2012-09-01

Tobacco stem-based activated carbons (TS-ACs) were prepared by simple KOH activation and their application as electrodes in the electrical double layer capacitor (EDLC) performed successfully. The BET surface area, pore volume, and pore size distribution of the TS-ACs were evaluated based on N2 adsorption isotherms at 77 K. The surface area of the obtained activated carbons varies over a wide range (1472.8-3326.7 m2/g) and the mesoporosity was enhanced significantly as the ratio of KOH to tobacco stem (TS) increased. The electrochemical behaviors of series TS-ACs were characterized by means of galvanostatic charging/discharging, cyclic voltammetry, and impedance spectroscopy. The correlation between electrochemical properties and pore structure was investigated. A high specific capacitance value as 190 F/g at 1 mA/cm2 was obtained in 1 M LiPF6-EC/DMC/DEC electrolyte solution. Furthermore, good performance is also achieved even at high current densities. A development of new use for TS into a valuable energy storage material is explored.

Effects of CO{sub 2} activation on electrochemical performance of microporous carbons derived from poly(vinylidene fluoride)

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

Lee, Seul-Yi; Park, Soo-Jin, E-mail: sjpark@inha.ac.kr

In this work, we have prepared microporous carbons (MPCs) derived from poly(vinylidene fluoride) (PVDF), and the physical activation of MPCs using CO{sub 2} gas is subsequently carried out with various activation temperatures to investigate the electrochemical performance. PVDF is successfully converted into MPCs with a high specific surface area and well-developed micropores. After CO{sub 2} activation, the specific surface areas of MPCs (CA-MPCs) are enhanced by 12% compared with non-activated MPCs. With increasing activation temperature, the micropore size distributions of A-MPCs also become narrower and shift to larger pore size. It is also confirmed that the CO{sub 2} activation hadmore » developed the micropores and introduced the oxygen-containing groups to MPCs′ surfaces. From the results, the specific capacitances of the electrodes in electric double layer capacitors (EDLCs) based on CA-MPCs are distinctly improved through CO{sub 2} activation. The highest specific capacitance of the A-MPCs activated at 700 °C is about 125 F/g, an enhancement of 74% in comparison with NA-MPCs, at a discharge current of 2 A/g in a 6 M KOH electrolyte solution. We also found that micropore size of 0.67 nm has a specific impact on the capacitance behaviors, besides the specific surface area of the electrode samples. - Graphical abstract: The A-MPC samples with high specific surface area (ranging from 1030 to 1082 m{sup 2}/g), corresponding to micropore sizes of 0.67 and 0.72 nm, and with the amount of oxygen-containing groups ranging from 3.2% to 4.4% have been evaluated as electrodes for EDLC applications. . Display Omitted - Highlights: • Microporous carbons (MPCs) were synthesized without activation process. • Next, we carried out the CO{sub 2} activation of MPCs with activation temperatures. • It had developed the micropores and introduced the O-functional groups to MPCs. • The highest specific capacitance: 125 F/g, an increase of 74% compared to MPCs.« less

Identification of a Catalytically Highly Active Surface Phase for CO Oxidation over PtRh Nanoparticles under Operando Reaction Conditions

NASA Astrophysics Data System (ADS)

Hejral, U.; Franz, D.; Volkov, S.; Francoual, S.; Strempfer, J.; Stierle, A.

2018-03-01

Pt-Rh alloy nanoparticles on oxide supports are widely employed in heterogeneous catalysis with applications ranging from automotive exhaust control to energy conversion. To improve catalyst performance, an atomic-scale correlation of the nanoparticle surface structure with its catalytic activity under industrially relevant operando conditions is essential. Here, we present x-ray diffraction data sensitive to the nanoparticle surface structure combined with in situ mass spectrometry during near ambient pressure CO oxidation. We identify the formation of ultrathin surface oxides by detecting x-ray diffraction signals from particular nanoparticle facets and correlate their evolution with the sample's enhanced catalytic activity. Our approach opens the door for an in-depth characterization of well-defined, oxide-supported nanoparticle based catalysts under operando conditions with unprecedented atomic-scale resolution.

Surface functionalization of 3D glass-ceramic porous scaffolds for enhanced mineralization in vitro

NASA Astrophysics Data System (ADS)

Ferraris, Sara; Vitale-Brovarone, Chiara; Bretcanu, Oana; Cassinelli, Clara; Vernè, Enrica

2013-04-01

Bone reconstruction after tissue loosening due to traumatic, pathological or surgical causes is in increasing demand. 3D scaffolds are a widely studied solution for supporting new bone growth. Bioactive glass-ceramic porous materials can offer a three-dimensional structure that is able to chemically bond to bone. The ability to surface modify these devices by grafting biologically active molecules represents a challenge, with the aim of stimulating physiological bone regeneration with both inorganic and organic signals. In this research work glass ceramic scaffolds with very high mechanical properties and moderate bioactivity have been functionalized with the enzyme alkaline phosphatase (ALP). The material surface was activated in order to expose hydroxyl groups. The activated surface was further grafted with ALP both via silanization and also via direct grafting to the surface active hydroxyl groups. Enzymatic activity of grafted samples were measured by means of UV-vis spectroscopy before and after ultrasonic washing in TRIS-HCl buffer solution. In vitro inorganic bioactivity was investigated by soaking the scaffolds after the different steps of functionalization in a simulated body fluid (SBF). SEM observations allowed the monitoring of the scaffold morphology and surface chemical composition after soaking in SBF. The presence of ALP enhanced the in vitro inorganic bioactivity of the tested material.

Motor unit recruitment and bursts of activity in the surface electromyogram during a sustained contraction.

PubMed

Riley, Zachary A; Terry, Mary E; Mendez-Villanueva, Alberto; Litsey, Jane C; Enoka, Roger M

2008-06-01

Bursts of activity in the surface electromyogram (EMG) during a sustained contraction have been interpreted as corresponding to the transient recruitment of motor units, but this association has never been confirmed. The current study compared the timing of trains of action potentials discharged by single motor units during a sustained contraction with the bursts of activity detected in the surface EMG signal. The 20 motor units from 6 subjects [recruitment threshold, 35.3 +/- 11.3% maximal voluntary contraction (MVC) force] that were detected with fine wire electrodes discharged 2-9 trains of action potentials (7.2 +/- 5.6 s in duration) when recruited during a contraction that was sustained at a force below its recruitment threshold (target force, 25.4 +/- 10.6% MVC force). High-pass filtering the bipolar surface EMG signal improved its correlation with the single motor unit signal. An algorithm applied to the surface EMG was able to detect 75% of the trains of motor unit action potentials. The results indicate that bursts of activity in the surface EMG during a constant-force contraction correspond to the transient recruitment of higher-threshold motor units in healthy individuals, and these results could assist in the diagnosis and design of treatment in individuals who demonstrate deficits in motor unit activation.

Size-dependent electrocatalytic activity of gold nanoparticles on HOPG and highly boron-doped diamond surfaces.

PubMed

Brülle, Tine; Ju, Wenbo; Niedermayr, Philipp; Denisenko, Andrej; Paschos, Odysseas; Schneider, Oliver; Stimming, Ulrich

2011-12-06

Gold nanoparticles were prepared by electrochemical deposition on highly oriented pyrolytic graphite (HOPG) and boron-doped, epitaxial 100-oriented diamond layers. Using a potentiostatic double pulse technique, the average particle size was varied in the range from 5 nm to 30 nm in the case of HOPG as a support and between < 1 nm and 15 nm on diamond surfaces, while keeping the particle density constant. The distribution of particle sizes was very narrow, with standard deviations of around 20% on HOPG and around 30% on diamond. The electrocatalytic activity towards hydrogen evolution and oxygen reduction of these carbon supported gold nanoparticles in dependence of the particle sizes was investigated using cyclic voltammetry. For oxygen reduction the current density normalized to the gold surface (specific current density) increased for decreasing particle size. In contrast, the specific current density of hydrogen evolution showed no dependence on particle size. For both reactions, no effect of the different carbon supports on electrocatalytic activity was observed.

Role of Oxygen as Surface-Active Element in Linear GTA Welding Process

NASA Astrophysics Data System (ADS)

Yadaiah, Nirsanametla; Bag, Swarup

2013-11-01

Although the surface-active elements such as oxygen and sulfur have an adverse effect on momentum transport in liquid metals during fusion welding, such elements can be used beneficially up to a certain limit to increase the weld penetration in the gas tungsten arc (GTA) welding process. The fluid flow pattern and consequently the weld penetration and width change due to a change in coefficient of surface tension from a negative value to a positive value. The present work is focused on the analysis of possible effects of surface-active elements to change the weld pool dimensions in linear GTA welding. A 3D finite element-based heat transfer and fluid flow model is developed to study the effect of surface-active elements on stainless steel plates. A velocity in the order of 180 mm/s due to surface tension force is estimated at an optimum concentration of surface-active elements. Further, the differential evolution-based global optimization algorithm is integrated with the numerical model to estimate uncertain model parameters such as arc efficiency, effective arc radius, and effective values of material properties at high temperatures. The effective values of thermal conductivity and viscosity are estimated to be enhanced nine and seven times, respectively, over corresponding room temperature values. An error analysis is also performed to find out the overall reliability of the computed results, and a maximum reliability of 0.94 is achieved.

Photosynthetic Activity and Adaptation Capacities of Lichens and Cyanobacteria to Martian Surface Conditions

NASA Astrophysics Data System (ADS)

De Vera, Jean-Pierre; Schulze-Makuch, D.; Khan, A.; Lorek, A.; Koncz, A.; Stivaletta, N.; Möhlmann, D.; Spohn, T.

2012-05-01

We observed an increase in photosynthetic activity in the lichen Pleopsidium chlorophanum but a strong negative effect on the photosynthetic activity of endolithic cyanobacteria when subjected for 34 days to environmental stresses likely to be encountered in semi-protected habitats on the Martian surface. Stresses were simulated in a Mars Simulation Chamber (MSC) and included high UV fluxes, low temperatures, low water activity, high atmospheric CO2 concentrations, and an atmospheric pressure of about 6 mbar. P. chlorophanum is an extremophile: it lives in very cold, dry, high-altitude habitats which are Earth's best approximation of the Martian surface. Our lichen samples came from North Victoria Land in Antarctica whereas the investigated samples of cyanobacteria came from tropic regions in the Sahara. Three samples of each group of organisms were exposed uninterruptedly to simulated conditions (as above) of the naked, unprotected Martian surface for 34 days, receiving the full Martian solar spectrum (200 - 2500 nm) for a cumulative UV dose of 6343.6 kJm-2. For a second sample set - containing also three lichen thalli and three endolithic cyanobacteria communities - the cumulative (34-day) UV dose was reduced to 268.8 kJm-2, to reasonably simulate the amount the microorganisms might receive in (semi-) protected surface sites (e.g., fissures, cracks and micro-caves within rocks or permafrost soil). In the 'unprotected' experiment it was unclear if the lichen was still actively photosynthesizing but still clear that the cyanobacteria were affected. However, under 'protected site' conditions, the cyanobacteria had no clear photosynthetic response under and after simulated Martian conditions but the lichen not only survived and remained photosynthetically active, it even adapted physiologically by increasing its photosynthetic activity over 34 days. Comparison with other Mars simulation experiments on exposure platforms in space and in the laboratory with other investigated species show results of remarkable survival rates and maintained photosynthesizing activity which strongly supports the interconnected notions (1) that terrestrial life most likely can adapt physiologically to live on Mars (hence justifying stringent measures to prevent human activities from contaminating/infecting Mars with terrestrial organisms); (2) that in searching for extant life on Mars we should focus on "protected" habitats; and (3) that early-originating (Noachian Period) indigenous Martian life might still survive in such habitats despite Mars' cooling and drying during the last 4 billion years.

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

Lu, Zhiyi; Chen, Guangxu; Li, Yanbin

Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (1120) and polar (0112) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces andmore » their OER activities can be understood by the increase of Co 4+ sites relative to Co 3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (~0.1 V in overpotential shift at 10 mA cm –2) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. In addition, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.« less

Photocatalytic activity of PANI loaded coordination polymer composite materials: Photoresponse region extension and quantum yields enhancement via the loading of PANI nanofibers on surface of coordination polymer

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

Cui, Zhongping; Qi, Ji; Xu, Xinxin, E-mail: xuxx@mail.neu.edu.cn

2013-09-15

To enhance photocatalytic property of coordination polymer in visible light region, polyaniline (PANI) loaded coordination polymer photocatalyst was synthesized through in-situ chemical oxidation of aniline on the surface of coordination polymer. The photocatalytic activity of PANI loaded coordination polymer composite material for degradation of Rhodamine B (RhB) was investigated. Compared with pure coordination polymer photocatalyst, which can decompose RhB merely under UV light irradiation, PANI loaded coordination polymer photocatalyst displays more excellent photocatalytic activity in visible light region. Furthermore, PANI loaded coordination polymer photocatalyst exhibits outstanding stability during the degradation of RhB. - Graphical abstract: PANI loaded coordination polymer compositemore » material, which displays excellent photocatalytic activity under visible light was firstly synthesized through in-situ chemical oxidation of aniline on surface of coordination polymer. Display Omitted - Highlights: • This PANI loaded coordination polymer composite material represents the first conductive polymer loaded coordination polymer composite material. • PANI/coordination polymer composite material displays more excellent photocatalytic activity for the degradation of MO in visible light region. • The “combination” of coordination polymer and PANI will enable us to design high-activity, high-stability and visible light driven photocatalyst in the future.« less

Cleaning and passivation of copper surfaces to remove surface radioactivity and prevent oxide formation

NASA Astrophysics Data System (ADS)

Hoppe, E. W.; Seifert, A.; Aalseth, C. E.; Bachelor, P. P.; Day, A. R.; Edwards, D. J.; Hossbach, T. W.; Litke, K. E.; McIntyre, J. I.; Miley, H. S.; Schulte, S. M.; Smart, J. E.; Warren, G. A.

2007-08-01

High-purity copper is an attractive material for constructing ultra-low-background radiation measurement devices. Many low-background experiments using high-purity copper have indicated surface contamination emerges as the dominant background. Radon daughters plate out on exposed surfaces, leaving a residual 210Pb background that is difficult to avoid. Dust is also a problem; even under cleanroom conditions, the amount of U and Th deposited on surfaces can represent the largest remaining background. To control these backgrounds, a copper cleaning chemistry has been developed. Designed to replace an effective, but overly aggressive concentrated nitric acid etch, this peroxide-based solution allows for a more controlled cleaning of surfaces. The acidified hydrogen peroxide solution will generally target the Cu +/Cu 2+ species which are the predominant surface participants, leaving the bulk of copper metal intact. This preserves the critical tolerances of parts and eliminates significant waste disposal issues. Accompanying passivation chemistry has also been developed that protects copper surfaces from oxidation. Using a high-activity polonium surface spike, the most difficult-to-remove daughter isotope of radon, the performance of these methods are quantified.

Spatial variation in water loss predicts terrestrial salamander distribution and population dynamics.

PubMed

Peterman, W E; Semlitsch, R D

2014-10-01

Many patterns observed in ecology, such as species richness, life history variation, habitat use, and distribution, have physiological underpinnings. For many ectothermic organisms, temperature relationships shape these patterns, but for terrestrial amphibians, water balance may supersede temperature as the most critical physiologically limiting factor. Many amphibian species have little resistance to water loss, which restricts them to moist microhabitats, and may significantly affect foraging, dispersal, and courtship. Using plaster models as surrogates for terrestrial plethodontid salamanders (Plethodon albagula), we measured water loss under ecologically relevant field conditions to estimate the duration of surface activity time across the landscape. Surface activity time was significantly affected by topography, solar exposure, canopy cover, maximum air temperature, and time since rain. Spatially, surface activity times were highest in ravine habitats and lowest on ridges. Surface activity time was a significant predictor of salamander abundance, as well as a predictor of successful recruitment; the probability of a juvenile salamander occupying an area with high surface activity time was two times greater than an area with limited predicted surface activity. Our results suggest that survival, recruitment, or both are demographic processes that are affected by water loss and the ability of salamanders to be surface-active. Results from our study extend our understanding of plethodontid salamander ecology, emphasize the limitations imposed by their unique physiology, and highlight the importance of water loss to spatial population dynamics. These findings are timely for understanding the effects that fluctuating temperature and moisture conditions predicted for future climates will have on plethodontid salamanders.

A novel theoretical probe of the SrTiO3 surface under water-splitting conditions

NASA Astrophysics Data System (ADS)

Letchworth-Weaver, Kendra; Gunceler, Deniz; Arias, Tomás; Plaza, Manuel; Huang, Xin; Brock, Joel; Rodriguez-López, Joaquin; Abruña, Hector

2014-03-01

Understanding the reaction mechanisms required to generate hydrogen fuel by photoelectrolysis of water is essential to energy conversion research. These reaction pathways are strongly influenced by the geometry and electronic structure of the electrode surface under water-splitting conditions. Electrochemical microscopy has demonstrated that biasing a SrTiO3 (001) surface can lead to an increase in water-splitting activity. In operando X-ray reflectivity measurements at the Cornell High Energy Synchrotron Source (CHESS) correlate this increase in activity to a significant reorganization in the surface structure but are unable to determine the exact nature of this change. Joint Density-Functional Theory (JDFT), a rigorous yet computationally efficient alternative to molecular dynamics, provides a quantum-mechanical description of an electrode surface in contact with an aqueous environment, and a microscopically detailed description of the interfacial liquid structure. Our JDFT calculations determine the structure of the activated SrTiO3 surface and explore why it is correlated with higher activity for water splitting. With no empirical parameters whatsoever, we predict the X-ray crystal truncation rods for SrTiO3, finding excellent agreement with experiment. Funded by the Energy Materials Center at Cornell (EMC2).

Data-based diffraction kernels for surface waves from convolution and correlation processes through active seismic interferometry

NASA Astrophysics Data System (ADS)

Chmiel, Malgorzata; Roux, Philippe; Herrmann, Philippe; Rondeleux, Baptiste; Wathelet, Marc

2018-05-01

We investigated the construction of diffraction kernels for surface waves using two-point convolution and/or correlation from land active seismic data recorded in the context of exploration geophysics. The high density of controlled sources and receivers, combined with the application of the reciprocity principle, allows us to retrieve two-dimensional phase-oscillation diffraction kernels (DKs) of surface waves between any two source or receiver points in the medium at each frequency (up to 15 Hz, at least). These DKs are purely data-based as no model calculations and no synthetic data are needed. They naturally emerge from the interference patterns of the recorded wavefields projected on the dense array of sources and/or receivers. The DKs are used to obtain multi-mode dispersion relations of Rayleigh waves, from which near-surface shear velocity can be extracted. Using convolution versus correlation with a grid of active sources is an important step in understanding the physics of the retrieval of surface wave Green's functions. This provides the foundation for future studies based on noise sources or active sources with a sparse spatial distribution.

Divergent Mitochondrial Antioxidant Activities and Lung Alveolar Architecture in the Lungs of Rats and Mice at High Altitude.

PubMed

Jochmans-Lemoine, Alexandra; Revollo, Susana; Villalpando, Gabriella; Valverde, Ibana; Gonzales, Marcelino; Laouafa, Sofien; Soliz, Jorge; Joseph, Vincent

2018-01-01

Compared with mice, adult rats living at 3,600 m above sea level (SL-La Paz, Bolivia) have high hematocrit, signs of pulmonary hypertension, and low lung volume with reduced alveolar surface area. This phenotype is associated with chronic mountain sickness in humans living at high altitude (HA). We tested the hypothesis that this phenotype is associated with impaired gas exchange and oxidative stress in the lungs. We used rats and mice (3 months old) living at HA (La Paz) and SL (Quebec City, Canada) to measure arterial oxygen saturation under graded levels of hypoxia (by pulse oximetry), the alveolar surface area in lung slices and the activity of pro- (NADPH and xanthine oxidases-NOX and XO) and anti- (superoxide dismutase, and glutathione peroxidase-SOD and GPx) oxidant enzymes in cytosolic and mitochondrial lung protein extracts. HA rats have a lower arterial oxygen saturation and reduced alveolar surface area compared to HA mice and SL rats. Enzymatic activities (NOX, XO, SOD, and GPx) in the cytosol were similar between HA and SL animals, but SOD and GPx activities in the mitochondria were 2-3 times higher in HA vs. SL rats, and only marginally higher in HA mice vs. SL mice. Furthermore, the maximum activity of cytochrome oxidase-c (COX) measured in mitochondrial lung extracts was also 2 times higher in HA rats compared with SL rats, while there was only a small increase in HA mice vs. SL mice. Interestingly, compared with SL controls, alterations in lung morphology are not observed for young rats at HA (15 days after birth), and enzymatic activities are only slightly altered. These results suggest that rats living at HA have a gradual reduction of their alveolar surface area beyond the postnatal period. We can speculate that the elevation of SOD, GPx, and COX activities in the lung mitochondria are not sufficient to compensate for oxidative stress, leading to damage of the lung tissue in rats.

Divergent Mitochondrial Antioxidant Activities and Lung Alveolar Architecture in the Lungs of Rats and Mice at High Altitude

PubMed Central

Jochmans-Lemoine, Alexandra; Revollo, Susana; Villalpando, Gabriella; Valverde, Ibana; Gonzales, Marcelino; Laouafa, Sofien; Soliz, Jorge; Joseph, Vincent

2018-01-01

Compared with mice, adult rats living at 3,600 m above sea level (SL—La Paz, Bolivia) have high hematocrit, signs of pulmonary hypertension, and low lung volume with reduced alveolar surface area. This phenotype is associated with chronic mountain sickness in humans living at high altitude (HA). We tested the hypothesis that this phenotype is associated with impaired gas exchange and oxidative stress in the lungs. We used rats and mice (3 months old) living at HA (La Paz) and SL (Quebec City, Canada) to measure arterial oxygen saturation under graded levels of hypoxia (by pulse oximetry), the alveolar surface area in lung slices and the activity of pro- (NADPH and xanthine oxidases—NOX and XO) and anti- (superoxide dismutase, and glutathione peroxidase—SOD and GPx) oxidant enzymes in cytosolic and mitochondrial lung protein extracts. HA rats have a lower arterial oxygen saturation and reduced alveolar surface area compared to HA mice and SL rats. Enzymatic activities (NOX, XO, SOD, and GPx) in the cytosol were similar between HA and SL animals, but SOD and GPx activities in the mitochondria were 2–3 times higher in HA vs. SL rats, and only marginally higher in HA mice vs. SL mice. Furthermore, the maximum activity of cytochrome oxidase-c (COX) measured in mitochondrial lung extracts was also 2 times higher in HA rats compared with SL rats, while there was only a small increase in HA mice vs. SL mice. Interestingly, compared with SL controls, alterations in lung morphology are not observed for young rats at HA (15 days after birth), and enzymatic activities are only slightly altered. These results suggest that rats living at HA have a gradual reduction of their alveolar surface area beyond the postnatal period. We can speculate that the elevation of SOD, GPx, and COX activities in the lung mitochondria are not sufficient to compensate for oxidative stress, leading to damage of the lung tissue in rats. PMID:29670534

Inhibitory effect of hydrophilic polymer brushes on surface-induced platelet activation and adhesion.

PubMed

Zou, Yuquan; Lai, Benjamin F L; Kizhakkedathu, Jayachandran N; Brooks, Donald E

2010-12-08

Poly(N,N-dimethylacrylamide) (PDMA) brushes are successfully grown from unplasticized poly(vinyl chloride) (uPVC) by well-controlled surface-initiated atom transfer radical polymerization (SI-ATRP). Molecular weights of the grafted PDMA brushes vary from ≈ 35,000 to 2,170000 Da, while the graft density ranges from 0.08 to 1.13 chains · nm(-2). The polydispersity of the grafted PDMA brushes is controlled within 1.20 to 1.80. Platelet activation (expression of CD62) and adhesion studies reveal that the graft densities of the PDMA brushes play an important role in controlling interfacial properties. PDMA brushes with graft densities between 0.35 and 0.50 chains · nm(-2) induce a significantly reduced platelet activation compared to unmodified uPVC. Moreover, the surface adhesion of platelets on uPVC is significantly reduced by the densely grafted PDMA brushes. PDMA brushes that have high molecular weights lead to a relatively lower platelet activation compared to low-molecular-weight brushes. However, the graft density of the brush is more important than molecular weight in controlling platelet interactions with PVC. PDMA brushes do not produce any significant platelet consumption in platelet rich plasma. Up to a seven-fold decrease in the number of platelets adhered on high graft density brushes is observed compared to the bare PVC surface. Unlike the bare PVC, platelets do not form pseudopodes or change morphology on PDMA brush-coated surfaces. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The influence of zeolites fly ash bead/TiO2 composite material surface morphologies on their adsorption and photocatalytic performance

NASA Astrophysics Data System (ADS)

Yang, Lu; Wang, Fazhou; Hakki, Amer; Macphee, Donald E.; Liu, Peng; Hu, Shuguang

2017-01-01

A low cost zeolite fly ash bead/TiO2 (ZFABT) composite materials with various surface structure features were prepared for describing those structures importance on TiO2 coating, adsorbability and photocatalytic performances. The results indicated that fly ash bead (FAB) surface was significantly altered by the precipitation/growth of secondary zeolite phases after alkali activation, which generates abundant open pores and stacked petal-liked spherical beads (∼2 μm, Sodalite zeolites). More importantly, this porosity increases as activation time was increased from 2 h to 12 h, through the precipitation of sodalite and then Na-P1 (lamellar crystals) and Na-X (octahedral crystals) zeolite structures. Compared to those of unsupported TiO2 or inactivated support/TiO2 samples, all of ZFABT samples exhibited a higher adsorption capacity and photocatalytic efficiency for RhB removal. However, adsorption is not only one factor to influence TiO2 surface reaction, the intraparticle diffusion rate of rhodamine B (RhB) molecules, and light penetration are also important parameters. Alkali activated 4 h ZFABT sample exhibited the highest photocatalytic activity, indicating its pore structure provided a better balance for those parameters to achieve a synergistic adsorption/photocatalytic process. The kinetics model suggested its high intraparticle diffusion rate allowed for more RhB molecules to easily reach the reaction surface, which is more important for high efficiency photocatalysis.

Synthesis of molecular imprinted polymer modified TiO{sub 2} nanotube array electrode and their photoelectrocatalytic activity

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

Lu Na; Chen Shuo; Wang Hongtao

2008-10-15

A tetracycline hydrochloride (TC) molecularly imprinted polymer (MIP) modified TiO{sub 2} nanotube array electrode was prepared via surface molecular imprinting. Its surface was structured with surface voids and the nanotubes were open at top end with an average diameter of approximately 50 nm. The MIP-modified TiO{sub 2} nanotube array with anatase phase was identified by XRD and a distinguishable red shift in the absorption spectrum was observed. The MIP-modified electrode also exhibited a high adsorption capacity for TC due to its high surface area providing imprinted sites. Photocurrent was generated on the MIP-modified photoanode using the simulated solar spectrum andmore » increased with the increase of positive bias potential. Under simulated solar light irradiation, the MIP-modified TiO{sub 2} nanotube array electrode exhibited enhanced photoelectrocatalytic (PEC) activity with the apparent first-order rate constant being 1.2-fold of that with TiO{sub 2} nanotube array electrode. The effect of the thickness of the MIP layer on the PEC activity was also evaluated. - Graphical abstract: A tetracycline hydrochloride molecularly imprinted polymer modified TiO{sub 2} nanotube array electrode was prepared via surface molecular imprinting. It showed improved response to simulated solar light and higher adsorption capability for tetracycline hydrochloride, thereby exhibiting increased PEC activity under simulated solar light irradiation. The apparent first-order rate constant was 1.2-fold of that on TiO{sub 2} nanotube array electrode.« less

High Performance Carbon Nanotube Yarn Supercapacitors with a Surface-Oxidized Copper Current Collector.

PubMed

Zhang, Daohong; Wu, Yunlong; Li, Ting; Huang, Yin; Zhang, Aiqing; Miao, Menghe

2015-11-25

Threadlike linear supercapacitors have demonstrated high potential for constructing fabrics to power electronic textiles (eTextiles). To improve the cyclic electrochemical performance and to produce power fabrics large enough for practical applications, a current collector has been introduced into the linear supercapcitors to transport charges produced by active materials along the length of the supercapacitor with high efficiency. Here, we first screened six candidate metal filaments (Pt, Au, Ag, AuAg, PtCu, and Cu) as current collectors for carbon nanotube (CNT) yarn-based linear supercapacitors. Although all of the metal filaments significantly improved the electrochemical performance of the linear supercapacitor, two supercapacitors constructed from Cu and PtCu filaments, respectively, demonstrate far better electrochemical performance than the other four supercapacitors. Further investigation shows that the surfaces of the two Cu-containing filaments are oxidized by the surrounding polymer electrolyte in the electrode. While the unoxidized core of the Cu-containing filaments remains highly conductive and functions as a current collector, the resulting CuO on the surface is an electrochemically active material. The linear supercapacitor architecture incorporating dual active materials CNT + Cu extends the potential window from 1.0 to 1.4 V, leading to significant improvement to the energy density and power density.

High level active n+ doping of strained germanium through co-implantation and nanosecond pulsed laser melting

NASA Astrophysics Data System (ADS)

Pastor, David; Gandhi, Hemi H.; Monmeyran, Corentin P.; Akey, Austin J.; Milazzo, Ruggero; Cai, Yan; Napolitani, Enrico; Gwilliam, Russell M.; Crowe, Iain F.; Michel, Jurgen; Kimerling, L. C.; Agarwal, Anuradha; Mazur, Eric; Aziz, Michael J.

2018-04-01

Obtaining high level active n+ carrier concentrations in germanium (Ge) has been a significant challenge for further development of Ge devices. By ion implanting phosphorus (P) and fluorine (F) into Ge and restoring crystallinity using Nd:YAG nanosecond pulsed laser melting (PLM), we demonstrate 1020 cm-3 n+ carrier concentration in tensile-strained epitaxial germanium-on-silicon. Scanning electron microscopy shows that after laser treatment, samples implanted with P have an ablated surface, whereas P + F co-implanted samples have good crystallinity and a smooth surface topography. We characterize P and F concentration depth profiles using secondary ion mass spectrometry and spreading resistance profiling. The peak carrier concentration, 1020 cm-3 at 80 nm below the surface, coincides with the peak F concentration, illustrating the key role of F in increasing donor activation. Cross-sectional transmission electron microscopy of the co-implanted sample shows that the Ge epilayer region damaged during implantation is a single crystal after PLM. High-resolution X-ray diffraction and Raman spectroscopy measurements both indicate that the as-grown epitaxial layer strain is preserved after PLM. These results demonstrate that co-implantation and PLM can achieve the combination of n+ carrier concentration and strain in Ge epilayers necessary for next-generation, high-performance Ge-on-Si devices.

Anatomy of a Visible Light Activated Photocatalyst for Water Splitting

DOE PAGES

Phivilay, Somphonh Peter; Roberts, Charles; Gamalski, Andrew; ...

2018-06-08

The supported mixed oxide (Rh 2-yCr yO 3)/(Ga 1-xZn x)(N 1-xO x) photocatalyst, highly active for splitting of H 2O, was extensively characterized for its bulk and surface properties with the objective of developing fundamental structure-photoactivity relationships. Raman and UV-vis spectroscopy revealed that the molecular and electronic structures, respectively, of the oxynitride (Ga 1-xZn x)(N 1-xO x) support are not perturbed by the deposition of the (Rh 2-yCr yO 3) NPs. Photoluminescence (PL) spectroscopy, however, showed that the oxynitride (Ga 1-xZn x)(N 1-xO x) support is the source of excited electrons/holes and the (Rh 2-yCr yO 3) NPs greatly reducemore » the undesirable recombination of photoexcited electron/holes by acting as efficient electron traps as well as increase the lifetimes of the excitons. High Resolution-XPS and High Sensitivity-LEIS surface analyses reveal that the surfaces of the (Rh 2-yCr yO 3) NPs consist of Rh +3 and Cr +3 mixed oxide species. In Situ AP-XPS help to reveal that the Rh+3 and surface N atoms are involved in water splitting. Dispersed RhOx species on the (Ga 1-xZn x)(N 1-xO x) support and on CrO x NPs were found to be the photocatalytic active sites for H 2 generation and N and Zn sites from the (Ga 1-xZn x)(N 1-xO x) support are the photocatalytic active site for O 2 generation. The current investigation establishes the fundamental structure-photoactivity relationships of these visible light activated photocatalysts.« less

Anatomy of a Visible Light Activated Photocatalyst for Water Splitting

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

Phivilay, Somphonh Peter; Roberts, Charles; Gamalski, Andrew

The supported mixed oxide (Rh 2-yCr yO 3)/(Ga 1-xZn x)(N 1-xO x) photocatalyst, highly active for splitting of H 2O, was extensively characterized for its bulk and surface properties with the objective of developing fundamental structure-photoactivity relationships. Raman and UV-vis spectroscopy revealed that the molecular and electronic structures, respectively, of the oxynitride (Ga 1-xZn x)(N 1-xO x) support are not perturbed by the deposition of the (Rh 2-yCr yO 3) NPs. Photoluminescence (PL) spectroscopy, however, showed that the oxynitride (Ga 1-xZn x)(N 1-xO x) support is the source of excited electrons/holes and the (Rh 2-yCr yO 3) NPs greatly reducemore » the undesirable recombination of photoexcited electron/holes by acting as efficient electron traps as well as increase the lifetimes of the excitons. High Resolution-XPS and High Sensitivity-LEIS surface analyses reveal that the surfaces of the (Rh 2-yCr yO 3) NPs consist of Rh +3 and Cr +3 mixed oxide species. In Situ AP-XPS help to reveal that the Rh+3 and surface N atoms are involved in water splitting. Dispersed RhOx species on the (Ga 1-xZn x)(N 1-xO x) support and on CrO x NPs were found to be the photocatalytic active sites for H 2 generation and N and Zn sites from the (Ga 1-xZn x)(N 1-xO x) support are the photocatalytic active site for O 2 generation. The current investigation establishes the fundamental structure-photoactivity relationships of these visible light activated photocatalysts.« less

Real-time color measurement using active illuminant

NASA Astrophysics Data System (ADS)

Tominaga, Shoji; Horiuchi, Takahiko; Yoshimura, Akihiko

2010-01-01

This paper proposes a method for real-time color measurement using active illuminant. A synchronous measurement system is constructed by combining a high-speed active spectral light source and a high-speed monochrome camera. The light source is a programmable spectral source which is capable of emitting arbitrary spectrum in high speed. This system is the essential advantage of capturing spectral images without using filters in high frame rates. The new method of real-time colorimetry is different from the traditional method based on the colorimeter or the spectrometers. We project the color-matching functions onto an object surface as spectral illuminants. Then we can obtain the CIE-XYZ tristimulus values directly from the camera outputs at every point on the surface. We describe the principle of our colorimetric technique based on projection of the color-matching functions and the procedure for realizing a real-time measurement system of a moving object. In an experiment, we examine the performance of real-time color measurement for a static object and a moving object.

Relationships among particle number, surface area, and respirable mass concentrations in automotive engine manufacturing.

PubMed

Heitbrink, William A; Evans, Douglas E; Ku, Bon Ki; Maynard, Andrew D; Slavin, Thomas J; Peters, Thomas M

2009-01-01

This study investigated the relationships between particle number, surface area, and respirable mass concentration measured simultaneously in a foundry and an automotive engine machining and assembly center. Aerosol concentrations were measured throughout each plant with a condensation particle counter for number concentration, a diffusion charger for active surface area concentration, and an optical particle counter for respirable mass concentration. At selected locations, particle size distributions were characterized with the optical particle counter and an electrical low pressure impactor. Statistical analyses showed that active surface area concentration was correlated with ultrafine particle number concentration and weakly correlated with respirable mass concentration. Correlation between number and active surface area concentration was stronger during winter (R2 = 0.6 for both plants) than in the summer (R2 = 0.38 and 0.36 for the foundry and engine plant respectively). The stronger correlation in winter was attributed to use of direct-fire gas fired heaters that produced substantial numbers of ultrafine particles with a modal diameter between 0.007 and 0.023 mu m. These correlations support findings obtained through theoretical analysis. Such analysis predicts that active surface area increasingly underestimates geometric surface area with increasing particle size, particularly for particles larger than 100 nm. Thus, a stronger correlation between particle number concentration and active surface area concentration is expected in the presence of high concentrations of ultrafine particles. In general, active surface area concentration may be a concentration metric that is distinct from particle number concentration and respirable mass concentration. For future health effects or toxicological studies involving nano-materials or ultrafine aerosols, this finding needs to be considered, as exposure metrics may influence data interpretation.

Effective adsorption of phenolic compound from aqueous solutions on activated semi coke

NASA Astrophysics Data System (ADS)

Gao, Xiaoming; Dai, Yuan; Zhang, Yu; Fu, Feng

2017-03-01

Activated Semi coke was prepared by KOH activation and employed as adsorbent to study adsorption function of phenolic compound from aqueous solutions. The adsorption result showed that the adsorption capacity of the activated semi coke for phenolic compound increased with contact time and adsorbent dosage, and slightly affected by temperature. The surface structure property of the activated semi coke was characterized by N2 adsorption, indicating that the activated semi coke was essentially macroporous, and the BET surface area was 347.39 m2 g-1. Scanning electron microscopy indicated that the surface of the activated semi coke had a high developed pore. The adsorption kinetics were investigated according to pseudofirst order, pseudosecond order and intraparticle diffusion, and the kinetics data were fitted by pseudosecond order model, and intraparticle diffusion was not the only rate-controlling step. Adsorption isotherm was studied by Langmuir, Freundlich, Temkin, Redlich-Peterson, Sips and Toth models. The result indicated that adsorption isotherm data could fit well with Langmuir, Redlich-Peterson, Sips and Toth models.

Influence of the Surface Functional Group Density on the Carbon-Nanotube-Induced α-Chymotrypsin Structure and Activity Alterations.

PubMed

Zhao, Xingchen; Hao, Fang; Lu, Dawei; Liu, Wei; Zhou, Qunfang; Jiang, Guibin

2015-08-26

Because of the special properties of carbon nanotubes (CNTs), their applications have been introduced to many fields. The biosafety of these emerging materials is of high concern concomitantly. Because CNTs may initially bind with proteins in biofluids before they exert biological effects, it is of great importance to understand how the target proteins interact with these exogenous nanomaterials. Here we investigated the interaction between α-chymotrypsin (α-ChT) and carboxylized multiwalled CNTs in a simulated biophysical environment utilizing the techniques of fluorescence, UV-vis, circular dichroism spectroscopy, ζ potential, atomic force microscopy, and bicinchoninic acid analysis. It was demonstrated that CNTs interacted with α-ChT through electrostatic forces, causing a decrement in the α-helix and an increment in the β-sheet content of the protein. The protein fluorescence was quenched in a static mode. The increase in the surface modification density of CNTs enhanced the protein absorption and decreased the enzymatic activity correspondingly. α-ChT activity inhibition induced by CNTs with low surface modification density exhibited noncompetitive characteristics; however, a competitive feature was observed when CNTs with high surface modification density interacted with the protein. An increase of the ionic strength in the reaction buffer may help to reduce the interaction between CNTs and α-ChT because the high ionic strength may favor the release of the protein from binding on a CNT surface modified with functional groups. Accordingly, the functionalization density on the CNT surface plays an important role in the regulation of their biological effects and is worthy of concern when new modified CNTs are developed.

Biomass-derived nitrogen-doped porous carbons with tailored hierarchical porosity and high specific surface area for high energy and power density supercapacitors

NASA Astrophysics Data System (ADS)

Sun, Junting; Niu, Jin; Liu, Mengyue; Ji, Jing; Dou, Meiling; Wang, Feng

2018-01-01

Porous carbon materials with hierarchical structures attract intense interest for the development of high-performance supercapacitors. Herein, we demonstrate a facile and efficient strategy to synthesize nitrogen-doped hierarchically porous carbons with tailored porous structure combined with high specific surface area (SSA), which involves a pre-carbonization and a subsequent carbonization combined with KOH activation of silkworm cocoon precursors. Through adjusting the mass ratio of the activator (KOH) to pre-carbonized precursor in the activation process, the hierarchically porous carbon prepared at the mass ratio of 2 (referred to as NHPC-2) possesses a high defect density and a high SSA of 3386 m2 g-1 as well as the relatively high volumetric proportion of mesopores and macropores (45.5%). As a result, the energy density and power density of the symmetric supercapacitor based on NHPC-2 electrode are as high as 34.41 Wh kg-1 and 31.25 kW kg-1 in organic-solvent electrolyte, and are further improved to 112.1 Wh kg-1 and 23.91 kW kg-1 in ionic-liquid electrolyte.

Biocompatible gold nanorods: one-step surface functionalization, highly colloidal stability, and low cytotoxicity.

PubMed

Liu, Kang; Zheng, Yuanhui; Lu, Xun; Thai, Thibaut; Lee, Nanju Alice; Bach, Udo; Gooding, J Justin

2015-05-05

The conjugation of gold nanorods (AuNRs) with polyethylene glycol (PEG) is one of the most effective ways to reduce their cytotoxicity arising from the cetyltrimethylammonium bromide (CTAB) and silver ions used in their synthesis. However, typical PEGylation occurs only at the tips of the AuNRs, producing partially modified AuNRs. To address this issue, we have developed a novel, facile, one-step surface functionalization method that involves the use of Tween 20 to stabilize AuNRs, bis(p-sulfonatophenyl)phenylphosphine (BSPP) to activate the AuNR surface for the subsequent PEGylation, and NaCl to etch silver from the AuNRs. This method allows for the complete removal of the surface-bound CTAB and the most active surface silver from the AuNRs. The produced AuNRs showed far lower toxicity than other methods to PEGylate AuNRs, with no apparent toxicity when their concentration is lower than 5 μg/mL. Even at a high concentration of 80 μg/mL, their cell viability is still four times higher than that of the tip-modified AuNRs.

Tripolar Laplacian electrocardiogram and moment of activation isochronal mapping.

PubMed

Besio, W; Chen, T

2007-05-01

The electrocardiogram (ECG) provides useful global temporal assessment of the cardiac activity, but has limited spatial capabilities. The Laplacian electrocardiogram (LECG), an improvement over the ECG, provides high spatiotemporal distributed information about cardiac electrical activation. We designed and developed LECG tripolar concentric ring electrode active sensors based on the finite element algorithm 'nine-point method' (NPM). The active sensors were used in an array of 6 by 12 (72) locations to record bipolar and tripolar LECG from the body surface over the anterolateral chest. Compared to bipolar LECG, tripolar LECG showed significantly higher spatial selectivity which may be helpful in inferring information about cardiac activations detected on the body surface. In this study the moment of activation (MOA), an indicator of a depolarization wave passing below the active sensors, was used to surmise possible timing information of the cardiac electrical activation below the active sensors' recording sites. The MOA on the body surface was used to generate isochronal maps that may some day be used by clinicians in diagnosing arrhythmias and assessing the efficacy of therapies.

Noble Metal Aerogels—Synthesis, Characterization, and Application as Electrocatalysts

PubMed Central

2015-01-01

Conspectus Metallic and catalytically active materials with high surface area and large porosity are a long-desired goal in both industry and academia. In this Account, we summarize the strategies for making a variety of self-supported noble metal aerogels consisting of extended metal backbone nanonetworks. We discuss their outstanding physical and chemical properties, including their three-dimensional network structure, the simple control over their composition, their large specific surface area, and their hierarchical porosity. Additionally, we show some initial results on their excellent performance as electrocatalysts combining both high catalytic activity and high durability for fuel cell reactions such as ethanol oxidation and the oxygen reduction reaction (ORR). Finally, we give some hints on the future challenges in the research area of metal aerogels. We believe that metal aerogels are a new, promising class of electrocatalysts for polymer electrolyte fuel cells (PEFCs) and will also open great opportunities for other electrochemical energy systems, catalysis, and sensors. The commercialization of PEFCs encounters three critical obstacles, viz., high cost, insufficient activity, and inadequate long-term durability. Besides others, the sluggish kinetics of the ORR and alcohol oxidation and insufficient catalyst stability are important reasons for these obstacles. Various approaches have been taken to overcome these obstacles, e.g., by controlling the catalyst particle size in an optimized range, forming multimetallic catalysts, controlling the surface compositions, shaping the catalysts into nanocrystals, and designing supportless catalysts with extended surfaces such as nanostructured thin films, nanotubes, and porous nanostructures. These efforts have produced plenty of excellent electrocatalysts, but the development of multisynergetic functional catalysts exhibiting low cost, high activity, and high durability still faces great challenges. In this Account, we demonstrate that the sol–gel process represents a powerful “bottom-up” strategy for creating nanostructured materials that tackles the problems mentioned above. Aerogels are unique solid materials with ultralow densities, large open pores, and ultimately high inner surface areas. They magnify the specific properties of nanomaterials to the macroscale via self-assembly, which endow them with superior properties. Despite numerous investigations of metal oxide aerogels, the investigation of metal aerogels is in the early stage. Recently, aerogels including Fe, Co, Ni, Sn, and Cu have been obtained by nanosmelting of hybrid polymer–metal oxide aerogels. We report here exclusively on mono-, bi- and multimetallic noble metal aerogels consisting of Ag, Au, Pt, and Pd and their application as electrocatalysts. PMID:25611348

Strong Effects of a Shelfbreak Jet on Microbial Enzyme Activities

NASA Astrophysics Data System (ADS)

Hoarfrost, A.; Balmonte, J. P.; Ziervogel, K.; Ghobrial, S.; Gawarkiewicz, G.; Arnosti, C.

2016-02-01

The activities of extracellular enzymes are critical in initiating microbial cycling of organic carbon, yet the dynamics of heterotrophic enzyme activities in marine environments are still poorly understood. Variations at a given site in rates of activity and the spectrum of organic substrates hydrolyzed may depend upon environmental context. We measured the extracellular enzymatic hydrolysis of 13 high- and low-molecular-weight organic substrates in surface and bottom waters along a closely spaced 4-station transect at 71 W on the North Atlantic continental shelf, in the vicinity of the shelfbreak front. This transect intersects a robust upwelling cell that typically shows high biologic productivity, and is locatable by changes in T/S profiles and chl a concentrations along sharp spatial gradients. At the time of sampling, cold pool waters over the continental shelf were relatively cold, 3.5 Deg. C, compared to 12 Deg. C over the upper continental slope. Satellite thermal imagery indicated that shelf water extended offshore and interacted with a large crest of the Gulf Stream. The surface and bottom waters associated with the upwelling jet were characterized by enzyme activities a factor of 20 more rapid than closer inshore waters, and surface water chl a concentrations that were two to three times higher than the inshore waters. The spectrum of enzyme activities also differed markedly between surface and bottom waters both within the jet and at near-shore stations. Microbial extracellular enzymatic activities were strongly influenced by differences in their environmental context along the continental slope and shelfbreak front. Constraining the factors controlling heterotrophic activity across the diverse marine environment is an important step in understanding microbial controls on carbon cycling.

Minnowbrook VI: 2009 Workshop on Flow Physics and Control for Internal and External Aerodynamics

NASA Technical Reports Server (NTRS)

LaGraff, John E.; Povinelli, Louis A.; Gostelow, J. Paul; Glauser, Mark

2010-01-01

Topics covered include: Flow Physics and control for Internal and External Aerodynamics (not in TOC...starts on pg13); Breaking CFD Bottlenecks in Gas-Turbine Flow-Path Design; Streamwise Vortices on the Convex Surfaces of Circular Cylinders and Turbomachinery Blading; DNS and Embedded DNS as Tools for Investigating Unsteady Heat Transfer Phenomena in Turbines; Cavitation, Flow Structure and Turbulence in the Tip Region of a Rotor Blade; Development and Application of Plasma Actuators for Active Control of High-Speed and High Reynolds Number Flows; Active Flow Control of Lifting Surface With Flap-Current Activities and Future Directions; Closed-Loop Control of Vortex Formation in Separated Flows; Global Instability on Laminar Separation Bubbles-Revisited; Very Large-Scale Motions in Smooth and Rough Wall Boundary Layers; Instability of a Supersonic Boundary-Layer With Localized Roughness; Active Control of Open Cavities; Amplitude Scaling of Active Separation Control; U.S. Air Force Research Laboratory's Need for Flow Physics and Control With Applications Involving Aero-Optics and Weapon Bay Cavities; Some Issues Related to Integrating Active Flow Control With Flight Control; Active Flow Control Strategies Using Surface Pressure Measurements; Reduction of Unsteady Forcing in a Vaned, Contra-Rotating Transonic Turbine Configuration; Active Flow Control Stator With Coanda Surface; Controlling Separation in Turbomachines; Flow Control on Low-Pressure Turbine Airfoils Using Vortex Generator Jets; Reduced Order Modeling Incompressible Flows; Study and Control of Flow Past Disk, and Circular and Rectangular Cylinders Aligned in the Flow; Periodic Forcing of a Turbulent Axisymmetric Wake; Control of Vortex Breakdown in Critical Swirl Regime Using Azimuthal Forcing; External and Turbomachinery Flow Control Working Group; Boundary Layers, Transitions and Separation; Efficiency Considerations in Low Pressure Turbines; Summary of Conference; and Final Plenary Session Transcript.

Fewer Defects in the Surface Slows the Hydrolysis Rate, Decreases the ROS Generation Potential, and Improves the Non-ROS Antimicrobial Activity of MgO.

PubMed

Anicˇić, Nemanja; Vukomanović, Marija; Koklicˇ, Tilen; Suvorov, Danilo

2018-05-21

Magnesium oxide (MgO) is recognised as exhibiting a contact-based antibacterial activity. However, a comprehensive study of the impact of atomic-scale surface features on MgO's antibacterial activity is lacking. In this study, the nature and abundance of the native surface defects on different MgO powders are thoroughly investigated. Their impacts on the hydrolysis kinetics, antibacterial activity against Escherichia coli (ATCC 47076), Staphylococcus epidermidis and Pseudomonas aeruginosa and the reactive oxygen species (ROS) generation potential are determined and explained. It is shown that a reduction in the abundance of low-coordinated oxygen atoms on the surface of the MgO improves its resistance to both hydrolysis and antibacterial activity. The ROS generation potential, determined in-situ using a fluorescence microplate assay and electron paramagnetic resonance spectroscopy, is not an inherent property of the studied MgO, rather it is a side product of hydrolysis (only for the most highly defected MgO particles) and/or a consequence of the MgO/bacteria interaction. The evaluation of the mutual correlations of the hydrolysis, the antibacterial activity and the ROS generation, with their origin in the surface defects' peculiarities, led to the conclusion that the acid/base reaction between the MgO surface and the bacterial wall contributes considerably to the MgO's antibacterial activity. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hollow Au/Ag nanostars displaying broad plasmonic resonance and high surface-enhanced Raman sensitivity

NASA Astrophysics Data System (ADS)

Garcia-Leis, Adianez; Torreggiani, Armida; Garcia-Ramos, Jose Vicente; Sanchez-Cortes, Santiago

2015-08-01

Bimetallic Au/Ag hollow nanostar (HNS) nanoparticles with different morphologies were prepared in this work. These nanoplatforms were obtained by changing the experimental conditions (concentration of silver and chemical reductors, hydroxylamine and citrate) and by using Ag nanostars as template nanoparticles (NPs) through galvanic replacement. The goal of this research was to create bimetallic Au/Ag star-shaped nanoparticles with advanced properties displaying a broader plasmonic resonance, a cleaner exposed surface, and a high concentration of electromagnetic hot spots on the surface provided by the special morphology of nanostars. The size, shape, and composition of Ag as well as their optical properties were studied by extinction spectroscopy, hyperspectral dark field microscopy, transmission and scanning electron microscopy (TEM and SEM), and energy dispersive X-ray spectroscopy (EDX). Finally, the surface-enhanced Raman scattering (SERS) activity of these HNS was investigated by using thioflavin T, a biomarker of the β-amyloid fibril formation, responsible for Alzheimer's disease. Lucigenin, a molecule displaying different SERS activities on Au and Ag, was also used to explore the presence of these metals on the NP surface. Thus, a relationship between the morphology, plasmon resonance and SERS activity of these new NPs was made.Bimetallic Au/Ag hollow nanostar (HNS) nanoparticles with different morphologies were prepared in this work. These nanoplatforms were obtained by changing the experimental conditions (concentration of silver and chemical reductors, hydroxylamine and citrate) and by using Ag nanostars as template nanoparticles (NPs) through galvanic replacement. The goal of this research was to create bimetallic Au/Ag star-shaped nanoparticles with advanced properties displaying a broader plasmonic resonance, a cleaner exposed surface, and a high concentration of electromagnetic hot spots on the surface provided by the special morphology of nanostars. The size, shape, and composition of Ag as well as their optical properties were studied by extinction spectroscopy, hyperspectral dark field microscopy, transmission and scanning electron microscopy (TEM and SEM), and energy dispersive X-ray spectroscopy (EDX). Finally, the surface-enhanced Raman scattering (SERS) activity of these HNS was investigated by using thioflavin T, a biomarker of the β-amyloid fibril formation, responsible for Alzheimer's disease. Lucigenin, a molecule displaying different SERS activities on Au and Ag, was also used to explore the presence of these metals on the NP surface. Thus, a relationship between the morphology, plasmon resonance and SERS activity of these new NPs was made. Electronic supplementary information (ESI) available: The SERS spectra of ThT on A-E samples are provided at two different excitations: 532 and 785 nm (Fig. S1). See DOI: 10.1039/c5nr02819a

Patterns and drivers of bacterial α- and β-diversity across vertical profiles from surface to subsurface sediments.

PubMed

Luna, Gian Marco; Corinaldesi, Cinzia; Rastelli, Eugenio; Danovaro, Roberto

2013-10-01

We investigated the patterns and drivers of bacterial α- and β-diversity, along with viral and prokaryotic abundance and the carbon production rates, in marine surface and subsurface sediments (down to 1 m depth) in two habitats: vegetated sediments (seagrass meadow) and non-vegetated sediments. Prokaryotic abundance and production decreased with depth in the sediment, but cell-specific production rates and the virus-to-prokaryote ratio increased, highlighting unexpectedly high activity in the subsurface. The highest diversity was observed in vegetated sediments. Bacterial β-diversity between sediment horizons was high, and only a minor number of taxa was shared between surface and subsurface layers. Viruses significantly contributed to explain α- and β-diversity patterns. Despite potential limitations due to the only use of fingerprinting techniques, this study indicates that the coastal subsurface host highly active and diversified bacterial assemblages, that subsurface cells are more active than expected and that viruses promote β-diversity and stimulate bacterial metabolism in subsurface layers. The limited number of taxa shared between habitats, and between surface and subsurface sediment horizons, suggests that future investigations of the shallow subsurface will provide insights into the census of bacterial diversity, and the comprehension of the patterns and drivers of prokaryotic diversity in marine ecosystems. © 2013 John Wiley & Sons Ltd and Society for Applied Microbiology.

High basicity adsorbents from solid residue of cellulose and synthetic polymer co-pyrolysis for phenol removal: Kinetics and mechanism

NASA Astrophysics Data System (ADS)

Lorenc-Grabowska, Ewa; Rutkowski, Piotr

2014-10-01

The activated carbons (ACs) produced from solid residue of cellulose and synthetic polymer co-pyrolysis (CACs) and commercial activated carbon from coconut shell (GC) were used for phenol removal. The adsorption kinetics and mechanism were investigated. All studied activated carbons are predominantly microporous and are characterized by basic surface characteristics. Surface area SBET varies between 1235 and 1499 m2/g, whereas the pHPZC changes from 7.70 to 10.63. The bath adsorption of phenol (P) was carried out at ambient temperature. The equilibrium time and equilibrium sorption capacity were determined. It was found that the boundary layer effect is bigger in AC with high basic characteristics of the surface. The rate controlling step is the intraparticle diffusion in CACs only, whereas in ACs with higher amount of acidic functionalities the adsorbate-surface interaction influences the rate of kinetic as well. The equilibrium isotherms are L2 type for commercial AC and L4 for CACs. The CACs are characterized by very high adsorption capacity that vary between 312 and 417 mg/g. The main mechanism of phenol adsorption is micropore filling within pores smaller than 1.4 nm. In the absence of solvent effect further adsorption of phenol on CACs takes place. The enhanced adsorption is due to dispersive/repulsive interaction induced by oxygen functionalities.

High capacity Li-ion battery anodes: Impact of crystallite size, surface chemistry and PEG-coating

DOE PAGES

Minnici, Krysten; Kwon, Yo Han; Huie, Matthew M.; ...

2017-12-06

Battery electrodes are complex mesoscale systems comprised of an active material, conductive agent, current collector, and polymeric binder. Previous work showed that introduction of poly [3-(potassium-4-butanoate) thiophene] (PPBT) as a binder component coupled with a polyethylene glycol (PEG) surface coating on magnetite (Fe 3O 4) nanoparticles enhanced electron and ion transport in the high capacity anode system. Here, the impact of Fe 3O 4 crystallite size (10 nm vs. 20 nm) and surface chemistry were explored to evaluate their effects on interfacial interactions within the composite PEG/PPBT based electrodes and resultant battery performance. The Fe 3O 4 synthesis methods inevitablymore » lead to differences in surface chemistry. For instance, the Fe 3O 4 particles synthesized using ammonium hydroxide appeared more dispersed, and afforded improved rate capability performance. Notably, chemical interactions between the active nanoparticles and PPBT binder were only seen with particles synthesized using triethylamine. Capacity retention and cycling performance were unaffected. Thus, this study provides fundamental insights into the significant impact of active material synthesis on the design and fabrication of composite battery electrodes.« less

High surface area mesoporous activated carbon-alginate beads for efficient removal of methylene blue.

PubMed

Nasrullah, Asma; Bhat, A H; Naeem, Abdul; Isa, Mohamed Hasnain; Danish, Mohammed

2018-02-01

High surface area mesoporous activated carbon-alginate (AC-alginate) beads were successfully synthesized by entrapping activated carbon powder derived from Mangosteen fruit peel into calcium-alginate beads for methylene blue (MB) removal from aqueous solution. The structure and surface characteristics of AC-alginate beads were analyzed using Fourier transform infra-red (FTIR) spectroscopy, scanning electron microscopy (SEM) and surface area analysis (S BET ), while thermal properties were tested using thermogravimetric analysis (TGA). The effect of AC-alginate dose, pH of solution, contact time, initial concentration of MB solution and temperature on MB removal was elucidated. The results showed that the maximum adsorption capacity of 230mg/g was achieved for 100mg/L of MB solution at pH 9.5 and temperature 25°C. Furthermore, the adsorption of MB on AC-alginate beads followed well pseudo-second order equation and equilibrium adsorption data were better fitted by the Freundlich isotherm model. The findings reveal the feasibility of AC-alginate beads composite to be used as a potential and low cost adsorbent for removal of cationic dyes. Copyright © 2017 Elsevier B.V. All rights reserved.

A novel carbon electrode material for highly improved EDLC performance.

PubMed

Fang, Baizeng; Binder, Leo

2006-04-20

Porous materials, developed by grafting functional groups through chemical surface modification with a surfactant, represent an innovative concept in energy storage. This work reports, in detail, the first practical realization of a novel carbon electrode based on grafting of vinyltrimethoxysilane (vtmos) functional group for energy storage in electric double layer capacitor (EDLC). Surface modification with surfactant vtmos enhances the hydrophobisation of activated carbon and the affinity toward propylene carbonate (PC) solvent, which improves the wettability of activated carbon in the electrolyte solution based on PC solvent, resulting in not only a lower resistance to the transport of electrolyte ions within micropores of activated carbon but also more usable surface area for the formation of electric double layer, and accordingly, higher specific capacitance, energy density, and power capability available from the capacitor based on modified carbon. Especially, the effects from surface modification become superior at higher discharge rate, at which much better EDLC performance (i.e., much higher energy density and power capability) has been achieved by the modified carbon, suggesting that the modified carbon is a novel and very promising electrode material of EDLC for large current applications where both high energy density and power capability are required.

High capacity Li-ion battery anodes: Impact of crystallite size, surface chemistry and PEG-coating

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

Minnici, Krysten; Kwon, Yo Han; Huie, Matthew M.

Battery electrodes are complex mesoscale systems comprised of an active material, conductive agent, current collector, and polymeric binder. Previous work showed that introduction of poly [3-(potassium-4-butanoate) thiophene] (PPBT) as a binder component coupled with a polyethylene glycol (PEG) surface coating on magnetite (Fe 3O 4) nanoparticles enhanced electron and ion transport in the high capacity anode system. Here, the impact of Fe 3O 4 crystallite size (10 nm vs. 20 nm) and surface chemistry were explored to evaluate their effects on interfacial interactions within the composite PEG/PPBT based electrodes and resultant battery performance. The Fe 3O 4 synthesis methods inevitablymore » lead to differences in surface chemistry. For instance, the Fe 3O 4 particles synthesized using ammonium hydroxide appeared more dispersed, and afforded improved rate capability performance. Notably, chemical interactions between the active nanoparticles and PPBT binder were only seen with particles synthesized using triethylamine. Capacity retention and cycling performance were unaffected. Thus, this study provides fundamental insights into the significant impact of active material synthesis on the design and fabrication of composite battery electrodes.« less

Cell wall structure suitable for surface display of proteins in Saccharomyces cerevisiae.

PubMed

Matsuoka, Hiroyuki; Hashimoto, Kazuya; Saijo, Aki; Takada, Yuki; Kondo, Akihiko; Ueda, Mitsuyoshi; Ooshima, Hiroshi; Tachibana, Taro; Azuma, Masayuki

2014-02-01

A display system for adding new protein functions to the cell surfaces of microorganisms has been developed, and applications of the system to various fields have been proposed. With the aim of constructing a cell surface environment suitable for protein display in Saccharomyces cerevisiae, the cell surface structures of cell wall mutants were investigated. Four cell wall mutant strains were selected by analyses using a GFP display system via a GPI anchor. β-Glucosidase and endoglucanase II were displayed on the cell surface in the four mutants, and their activities were evaluated. mnn2 deletion strain exhibited the highest activity for both the enzymes. In particular, endoglucanase II activity using carboxymethylcellulose as a substrate in the mutant strain was 1.9-fold higher than that of the wild-type strain. In addition, the activity of endoglucanase II released from the mnn2 deletion strain by Zymolyase 20T treatment was higher than that from the wild-type strain. The results of green fluorescent protein (GFP) and endoglucanase displays suggest that the amounts of enzyme displayed on the cell surface were increased by the mnn2 deletion. The enzyme activity of the mnn2 deletion strain was compared with that of the wild-type strain. The relative value (mnn2 deletion mutant/wild-type strain) of endoglucanase II activity using carboxymethylcellulose as a substrate was higher than that of β-glucosidase activity using p-nitrophenyl-β-glucopyranoside as a substrate, suggesting that the cell surface environment of the mnn2 deletion strain facilitates the binding of high-molecular-weight substrates to the active sites of the displayed enzymes. Copyright © 2014 John Wiley & Sons, Ltd.

The Pluto system: Initial results from its exploration by New Horizons

NASA Astrophysics Data System (ADS)

Stern, S. A.; Bagenal, F.; Ennico, K.; Gladstone, G. R.; Grundy, W. M.; McKinnon, W. B.; Moore, J. M.; Olkin, C. B.; Spencer, J. R.; Weaver, H. A.; Young, L. A.; Andert, T.; Andrews, J.; Banks, M.; Bauer, B.; Bauman, J.; Barnouin, O. S.; Bedini, P.; Beisser, K.; Beyer, R. A.; Bhaskaran, S.; Binzel, R. P.; Birath, E.; Bird, M.; Bogan, D. J.; Bowman, A.; Bray, V. J.; Brozovic, M.; Bryan, C.; Buckley, M. R.; Buie, M. W.; Buratti, B. J.; Bushman, S. S.; Calloway, A.; Carcich, B.; Cheng, A. F.; Conard, S.; Conrad, C. A.; Cook, J. C.; Cruikshank, D. P.; Custodio, O. S.; Dalle Ore, C. M.; Deboy, C.; Dischner, Z. J. B.; Dumont, P.; Earle, A. M.; Elliott, H. A.; Ercol, J.; Ernst, C. M.; Finley, T.; Flanigan, S. H.; Fountain, G.; Freeze, M. J.; Greathouse, T.; Green, J. L.; Guo, Y.; Hahn, M.; Hamilton, D. P.; Hamilton, S. A.; Hanley, J.; Harch, A.; Hart, H. M.; Hersman, C. B.; Hill, A.; Hill, M. E.; Hinson, D. P.; Holdridge, M. E.; Horanyi, M.; Howard, A. D.; Howett, C. J. A.; Jackman, C.; Jacobson, R. A.; Jennings, D. E.; Kammer, J. A.; Kang, H. K.; Kaufmann, D. E.; Kollmann, P.; Krimigis, S. M.; Kusnierkiewicz, D.; Lauer, T. R.; Lee, J. E.; Lindstrom, K. L.; Linscott, I. R.; Lisse, C. M.; Lunsford, A. W.; Mallder, V. A.; Martin, N.; McComas, D. J.; McNutt, R. L.; Mehoke, D.; Mehoke, T.; Melin, E. D.; Mutchler, M.; Nelson, D.; Nimmo, F.; Nunez, J. I.; Ocampo, A.; Owen, W. M.; Paetzold, M.; Page, B.; Parker, A. H.; Parker, J. W.; Pelletier, F.; Peterson, J.; Pinkine, N.; Piquette, M.; Porter, S. B.; Protopapa, S.; Redfern, J.; Reitsema, H. J.; Reuter, D. C.; Roberts, J. H.; Robbins, S. J.; Rogers, G.; Rose, D.; Runyon, K.; Retherford, K. D.; Ryschkewitsch, M. G.; Schenk, P.; Schindhelm, E.; Sepan, B.; Showalter, M. R.; Singer, K. N.; Soluri, M.; Stanbridge, D.; Steffl, A. J.; Strobel, D. F.; Stryk, T.; Summers, M. E.; Szalay, J. R.; Tapley, M.; Taylor, A.; Taylor, H.; Throop, H. B.; Tsang, C. C. C.; Tyler, G. L.; Umurhan, O. M.; Verbiscer, A. J.; Versteeg, M. H.; Vincent, M.; Webbert, R.; Weidner, S.; Weigle, G. E.; White, O. L.; Whittenburg, K.; Williams, B. G.; Williams, K.; Williams, S.; Woods, W. W.; Zangari, A. M.; Zirnstein, E.

2015-10-01

The Pluto system was recently explored by NASA’s New Horizons spacecraft, making closest approach on 14 July 2015. Pluto’s surface displays diverse landforms, terrain ages, albedos, colors, and composition gradients. Evidence is found for a water-ice crust, geologically young surface units, surface ice convection, wind streaks, volatile transport, and glacial flow. Pluto’s atmosphere is highly extended, with trace hydrocarbons, a global haze layer, and a surface pressure near 10 microbars. Pluto’s diverse surface geology and long-term activity raise fundamental questions about how small planets remain active many billions of years after formation. Pluto’s large moon Charon displays tectonics and evidence for a heterogeneous crustal composition; its north pole displays puzzling dark terrain. Small satellites Hydra and Nix have higher albedos than expected.

Method for surface plasmon amplification by stimulated emission of radiation (SPASER)

DOEpatents

Stockman, Mark I [Atlanta, GA; Bergman, David J [Ramat Hasharon, IL

2011-09-13

A nanostructure is used to generate a highly localized nanoscale optical field. The field is excited using surface plasmon amplification by stimulated emission of radiation (SPASER). The SPASER radiation consists of surface plasmons that undergo stimulated emission, but in contrast to photons can be localized within a nanoscale region. A SPASER can incorporate an active medium formed by two-level emitters, excited by an energy source, such as an optical, electrical, or chemical energy source. The active medium may be quantum dots, which transfer excitation energy by radiationless transitions to a resonant nanosystem that can play the same role as a laser cavity in a conventional laser. The transitions are stimulated by the surface plasmons in the nanostructure, causing the buildup of a macroscopic number of surface plasmons in a single mode.

Surface plasmon amplification by stimulated emission of radiation (SPASER)

DOEpatents

Stockman, Mark I [Atlanta, GA; Bergman, David J [Ramat Hasharon, IL

2009-08-04

A nanostructure is used to generate a highly localized nanoscale optical field. The field is excited using surface plasmon amplification by stimulated emission of radiation (SPASER). The SPASER radiation consists of surface plasmons that undergo stimulated emission, but in contrast to photons can be localized within a nanoscale region. A SPASER can incorporate an active medium formed by two-level emitters, excited by an energy source, such as an optical, electrical, or chemical energy source. The active medium may be quantum dots, which transfer excitation energy by radiationless transitions to a resonant nanosystem that can play the same role as a laser cavity in a conventional laser. The transitions are stimulated by the surface plasmons in the nanostructure, causing the buildup of a macroscopic number of surface plasmons in a single mode.

Surface-Water Quality-Assurance Plan for the Tallahassee Office, U.S. Geological Survey

USGS Publications Warehouse

Tomlinson, Stewart A.

2006-01-01

This Tallahassee Office Surface-Water Quality-Assurance Plan documents the standards, policies, and procedures used by the Tallahassee Office for activities related to the collection, processing, storage, analysis, and publication of surface-water data. This plan serves as a guide to all Tallahassee Office personnel involved in surface-water data activities, and changes as the needs and requirements of the Tallahassee Office, Florida Integrated Science Center, and Water Discipline change. Reg-ular updates to this Plan represent an integral part of the quality-assurance process. In the Tallahassee Office, direct oversight and responsibility by the employee(s) assigned to a surface-water station, combined with team approaches in all work efforts, assure high-quality data, analyses, reviews, and reports for cooperating agencies and the public.

Contact activation of blood-plasma coagulation

NASA Astrophysics Data System (ADS)

Golas, Avantika

Surface engineering of biomaterials with improved hemocompatibility is an imperative, given the widespread global need for cardiovascular devices. Research summarized in this dissertation focuses on contact activation of FXII in buffer and blood plasma frequently referred to as autoactivation. The extant theory of contact activation imparts FXII autoactivation ability to negatively charged, hydrophilic surfaces. According to this theory, contact activation of plasma involves assembly of proteins comprising an "activation complex" on activating surfaces mediated by specific chemical interactions between complex proteins and the surface. This work has made key discoveries that significantly improve our core understanding of contact activation and unravel the existing paradigm of plasma coagulation. It is shown herein that contact activation of blood factor XII (FXII, Hageman factor) in neat-buffer solution exhibits a parabolic profile when scaled as a function of silanized-glass-particle activator surface energy (measured as advancing water adhesion tension t°a=g° Iv costheta in dyne/cm, where g°Iv is water interfacial tension in dyne/cm and theta is the advancing contact angle). Nearly equal activation is observed at the extremes of activator water-wetting properties --36 < t°a < 72 dyne/cm (O° ≤ theta < 120°), falling sharply through a broad minimum within the 20 < t°a < 40 dyne/cm (55° < theta < 75°). Furthermore, contact activation of FXII in buffer solution produces an ensemble of protein fragments exhibiting either procoagulant properties in plasma (proteolysis of blood factor XI or prekallikrein), amidolytic properties (cleavage of s-2302 chromogen), or the ability to suppress autoactivation through currently unknown biochemistry. The relative proportions of these fragments depend on activator surface chemistry/energy. We have also discovered that contact activation is moderated by adsorption of plasma proteins unrelated to coagulation through an "adsorption-dilution" effect that blocks FXII contact with hydrophobic activator surfaces. The adsorption-dilution effect explains the apparent specificity for hydrophilic activators pursued by earlier investigators. Finally a comparison of FXII autoactivation in buffer, serum, protein cocktail, and plasma solutions is shown herein. Activation of blood plasma coagulation in vitro by contact with material surfaces is demonstrably dependent on plasma-volume-to-activator-surface-area ratio. However, activation of factor XII dissolved in buffer, protein cocktail, heat-denatured serum, and FXI deficient plasma does not exhibit activator surface-area dependence. Instead, a highly-variable burst of procoagulant-enzyme yield is measured that exhibits no measurable kinetics, sensitivity to mixing, or solution-temperature dependence. Thus, FXII activation in both buffer and protein-containing solutions does not exhibit characteristics of a biochemical reaction but rather appears to be a "mechanochemical" reaction induced by FXII molecule interactions with hydrophilic activator particles that do not formally adsorb blood proteins from solution. Results strongly suggest that activator surface-area dependence observed in contact activation of plasma coagulation does not solely arise at the FXII activation step of the intrinsic pathway.

Graphene oxide: surface activity and two-dimensional assembly.

PubMed

Kim, Franklin; Cote, Laura J; Huang, Jiaxing

2010-05-04

Graphene oxide (GO) is a promising precursor for preparing graphene-based composites and electronics applications. Like graphene, GO is essentially one-atom thick but can be as wide as tens of micrometers, resulting in a unique type of material building block, characterized by two very different length scales. Due to this highly anisotropic structure, the collective material properties are highly dependent on how these sheets are assembled. Therefore, understanding and controlling the assembly behavior of GO has become an important subject of research. In this Research News article the surface activity of GO and how it can be employed to create two-dimensional assemblies over large areas is discussed.

Design of ultrathin Pt-Mo-Ni nanowire catalysts for ethanol electrooxidation.

PubMed

Mao, Junjie; Chen, Wenxing; He, Dongsheng; Wan, Jiawei; Pei, Jiajing; Dong, Juncai; Wang, Yu; An, Pengfei; Jin, Zhao; Xing, Wei; Tang, Haolin; Zhuang, Zhongbin; Liang, Xin; Huang, Yu; Zhou, Gang; Wang, Leyu; Wang, Dingsheng; Li, Yadong

2017-08-01

Developing cost-effective, active, and durable electrocatalysts is one of the most important issues for the commercialization of fuel cells. Ultrathin Pt-Mo-Ni nanowires (NWs) with a diameter of ~2.5 nm and lengths of up to several micrometers were synthesized via a H 2 -assisted solution route (HASR). This catalyst was designed on the basis of the following three points: (i) ultrathin NWs with high numbers of surface atoms can increase the atomic efficiency of Pt and thus decrease the catalyst cost; (ii) the incorporation of Ni can isolate Pt atoms on the surface and produce surface defects, leading to high catalytic activity (the unique structure and superior activity were confirmed by spherical aberration-corrected electron microscopy measurements and ethanol oxidation tests, respectively); and (iii) the incorporation of Mo can stabilize both Ni and Pt atoms, leading to high catalytic stability, which was confirmed by experiments and density functional theory calculations. Furthermore, the developed HASR strategy can be extended to synthesize a series of Pt-Mo-M (M = Fe, Co, Mn, Ru, etc.) NWs. These multimetallic NWs would open up new opportunities for practical fuel cell applications.

Design of ultrathin Pt-Mo-Ni nanowire catalysts for ethanol electrooxidation

PubMed Central

Mao, Junjie; Chen, Wenxing; He, Dongsheng; Wan, Jiawei; Pei, Jiajing; Dong, Juncai; Wang, Yu; An, Pengfei; Jin, Zhao; Xing, Wei; Tang, Haolin; Zhuang, Zhongbin; Liang, Xin; Huang, Yu; Zhou, Gang; Wang, Leyu; Wang, Dingsheng; Li, Yadong

2017-01-01

Developing cost-effective, active, and durable electrocatalysts is one of the most important issues for the commercialization of fuel cells. Ultrathin Pt-Mo-Ni nanowires (NWs) with a diameter of ~2.5 nm and lengths of up to several micrometers were synthesized via a H2-assisted solution route (HASR). This catalyst was designed on the basis of the following three points: (i) ultrathin NWs with high numbers of surface atoms can increase the atomic efficiency of Pt and thus decrease the catalyst cost; (ii) the incorporation of Ni can isolate Pt atoms on the surface and produce surface defects, leading to high catalytic activity (the unique structure and superior activity were confirmed by spherical aberration–corrected electron microscopy measurements and ethanol oxidation tests, respectively); and (iii) the incorporation of Mo can stabilize both Ni and Pt atoms, leading to high catalytic stability, which was confirmed by experiments and density functional theory calculations. Furthermore, the developed HASR strategy can be extended to synthesize a series of Pt-Mo-M (M = Fe, Co, Mn, Ru, etc.) NWs. These multimetallic NWs would open up new opportunities for practical fuel cell applications. PMID:28875160

Mycobacterium tuberculosis surface protein Rv0227c contains high activity binding peptides which inhibit cell invasion.

PubMed

Rodríguez, Diana Marcela; Ocampo, Marisol; Curtidor, Hernando; Vanegas, Magnolia; Patarroyo, Manuel Elkin; Patarroyo, Manuel Alfonso

2012-12-01

Mycobacterium tuberculosis surface proteins involved in target cell invasion may be identified as a strategy for developing subunit-based, chemically-synthesized vaccines. The Rv0227c protein was thus selected to assess its role in the invasion and infection of Mycobacterium tuberculosis target cells. Results revealed Rv0227c localization on mycobacterial surface by immunoelectron microscopy and Western blot. Receptor-ligand assays using 20-mer, non-overlapping peptides covering the complete Rv0227c protein sequence revealed three high activity binding peptides for U937 phagocytic cells and seven for A549 cells. Peptide 16944 significantly inhibited mycobacterial entry to both cell lines while 16943 and 16949 only managed to inhibit entrance to U937 cells and 16951 to A549 cells. The Jnet bioinformatics tool predicted secondary structure elements for the complete protein, agreeing with elements determined for such chemically-synthesized peptides. It was thus concluded that high activity binding peptides which were able to inhibit mycobacterial entry to target cells are of great importance when selecting peptide candidates for inclusion in an anti-tuberculosis vaccine. Copyright © 2012 Elsevier Inc. All rights reserved.

Functionalized ZnO Nanoparticles with Gallic Acid for Antioxidant and Antibacterial Activity against Methicillin-Resistant S. aureus

PubMed Central

Lee, Joo Min; Choi, Kyong-Hoon; Min, Jeeeun; Kim, Ho-Joong; Jee, Jun-Pil; Park, Bong Joo

2017-01-01

In this study, we report a new multifunctional nanoparticle with antioxidative and antibacterial activities in vitro. ZnO@GA nanoparticles were fabricated by coordinated covalent bonding of the antioxidant gallic acid (GA) on the surface of ZnO nanoparticles. This addition imparts both antioxidant activity and high affinity for the bacterial cell membrane. Antioxidative activities at various concentrations were evaluated using a 2,2′-azino-bis(ethylbenzthiazoline-6-sulfonic acid) (ABTS) radical scavenging method. Antibacterial activities were evaluated against Gram-positive bacteria (Staphylococcus aureus: S. aureus), including several strains of methicillin-resistant S. aureus (MRSA), and Gram-negative bacteria (Escherichia coli). The functionalized ZnO@GA nanoparticles showed good antioxidative activity (69.71%), and the bactericidal activity of these nanoparticles was also increased compared to that of non-functionalized ZnO nanoparticles, with particularly effective inhibition and high selectivity for MRSA strains. The results indicate that multifunctional ZnO nanoparticles conjugated to GA molecules via a simple surface modification process displaying both antioxidant and antibacterial activity, suggesting a possibility to use it as an antibacterial agent for removing MRSA. PMID:29099064

Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

NASA Astrophysics Data System (ADS)

Sych, N. V.; Trofymenko, S. I.; Poddubnaya, O. I.; Tsyba, M. M.; Sapsay, V. I.; Klymchuk, D. O.; Puziy, A. M.

2012-11-01

Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 °C using varied ratio of impregnation (RI). Porous structure of carbons was characterized by nitrogen adsorption and scanning electron microscopy. Surface chemistry was studied by IR and potentiometric titration method. It has been shown that porosity development was peaked at RI = 1.0 (SBET = 2081 m2/g, Vtot = 1.1 cm3/g), while maximum amount of acid surface groups was observed at RI = 1.25. Acid surface groups of phosphoric acid activated carbons from corncob includes phosphate and strongly acidic carboxylic (pK = 2.0-2.6), weakly acidic carboxylic (pK = 4.7-5.0), enol/lactone (pK = 6.7-7.4; 8.8-9.4) and phenol (pK = 10.1-10.7). Corncob derived carbons showed high adsorption capacity to copper, especially at low pH. Maximum adsorption of methylene blue and iodine was observed for carbon with most developed porosity (RI = 1.0).

One-process fabrication of metal hierarchical nanostructures with rich nanogaps for highly-sensitive surface-enhanced Raman scattering.

PubMed

Liu, Gui-qiang; Yu, Mei-dong; Liu, Zheng-qi; Liu, Xiao-shan; Huang, Shan; Pan, Ping-ping; Wang, Yan; Liu, Mu-lin; Gu, Gang

2015-05-08

One-process fabrication of highly active and reproducible surface-enhanced Raman scattering (SERS) substrates via ion beam deposition is reported. The fabricated metal-dielectric-metal (MDM) hierarchical nanostructure possesses rich nanogaps and a tunable resonant cavity. Raman scattering signals of analytes are dramatically strengthened due to the strong near-field coupling of localized surface plasmon resonances (LSPRs) and the strong interaction of LSPRs of metal NPs with surface plasmon polaritons (SPPs) on the underlying metal film by crossing over the dielectric spacer. The maximum Raman enhancement for the highest Raman peak at 1650 cm(-1) is 13.5 times greater than that of a single metal nanoparticle (NP) array. Moreover, the SERS activity can be efficiently tailored by varying the size and number of voids between adjacent metal NPs and the thickness of the dielectric spacer. These findings may broaden the scope of SERS applications of MDM hierarchical nanostructures in biomedical and analytical chemistry.

Fabrication of superhydrophobic Pt3Fe/Fe surface for its application

NASA Astrophysics Data System (ADS)

Cui, Shuo; Lu, Shixiang; Xu, Wenguo; Wu, Bei

2017-10-01

Well-defined Pt3Fe/Fe superhydrophobic materials on iron sheet with special properties, such as corrosion resistance, superhydrophobicity and superoleophilicity, was fabricated. The fabrication process involved etching in hydrochloric acid aqueous solution and simple replacement deposition process without using any seed and organic solvent, and then annealing. The electrochemical measurements show that the resultant surface in 3.5% sodium chloride solution displays good corrosion resistance. Also, it is proved that the obtained surface has better mechanical abrasion resistance via scratch test. The superoleophilicity and low water adhesion force of the obtained surface endow it high oil/water separation capacity. The as-prepared nanocomposites display enhanced catalytic activity and kinetics toward degradation of methyl orange. In particular, it possesses the most efficient degradation capacity (95%) towards methyl orange at a high concentration (17.5 mg/L) in 80 min. The improved stability and excellent catalytic activity of the Pt3Fe/Fe nanocomposites promise new opportunities for the development of waste water treatment.

High-resolution Continental Scale Land Surface Model incorporating Land-water Management in United States

NASA Astrophysics Data System (ADS)

Shin, S.; Pokhrel, Y. N.

2016-12-01

Land surface models have been used to assess water resources sustainability under changing Earth environment and increasing human water needs. Overwhelming observational records indicate that human activities have ubiquitous and pertinent effects on the hydrologic cycle; however, they have been crudely represented in large scale land surface models. In this study, we enhance an integrated continental-scale land hydrology model named Leaf-Hydro-Flood to better represent land-water management. The model is implemented at high resolution (5km grids) over the continental US. Surface water and groundwater are withdrawn based on actual practices. Newly added irrigation, water diversion, and dam operation schemes allow better simulations of stream flows, evapotranspiration, and infiltration. Results of various hydrologic fluxes and stores from two sets of simulation (one with and the other without human activities) are compared over a range of river basin and aquifer scales. The improved simulations of land hydrology have potential to build consistent modeling framework for human-water-climate interactions.

Plasma Surface Modification of Polyaramid Fibers for Protective Clothing

NASA Astrophysics Data System (ADS)

Widodo, Mohamad

2011-12-01

The purpose of this research was to develop a novel process that would achieve biocidal properties on Kevlar fabric via atmospheric pressure plasma jet (APPJ) induced-graft polymerization of monomers. In the course of the study, experiments were carried out to understand plasma-monomer-substrate interactions, particularly, how each of the main parameters in the plasma processing affects the formation of surface radicals and eventually the degree of graft polymerization of monomers. The study also served to explore the possibility of developing plasma-initiated and plasma-controlled graft polymerization for continuous operation. In this regards, three methods of processing were studied, which included two-step plasma graft-polymerization with immersion, two-step and one-step plasma graft-polymerization with pad-dry. In general, plasma treatment did not cause visible damage to the surface of Kevlar fibers, except for the appearance of tiny globules distributed almost uniformly indicating a minor effect of plasma treatment to the surface morphology of the polymer. From the examination of SEM images, however, it was found that a very localized surface etching seemed to have taken place, especially at high RF power (800 W) and long time of exposure (60 s), even in plasma downstream mode of operation. It was suggested that a small amount of charged particles might have escaped and reached the substrate surface. High density of surface radicals, which is the prerequisite for high graft density and high antimicrobial activity, was achieved by the combination of high RF power and short exposure time or low RF power and long time of exposure. This was a clear indication that the formation of surface radicals is a function of amount of the dissipated energy, which also explained the two-factor interaction between the two process parameters. XPS results showed that hydrolysis of the anilide bond of PPTA chains took place to some extent on the surface of Kevlar, leading to the formation carboxylic and phenyl amine groups, which may provide additional active sites for grafting by way of hydrogen abstraction from the latter. Further analysis of XPS data, however, showed that macroradicals and active sites of grafting were formed at least at one of the carbon atoms in the aromatic ring. A reduction of microbial activity up to 3-log reduction was achieved by plasma treated Kevlar grafted by either diallyl diammonium chloride (DADMAC) or 3- ((trimethoxysilyl)-propyl) dimethylammonium chloride (TMS), with the latter being the one with better performance. It was found that high antimicrobial activity was obtained by the combination of high RF power, short time of exposure, and low concentration of monomer. Of the three processing methods studied, the one with immersion method produced higher graft yield. However, one-step plasma graft-polymerization with pad-dry method has proven itself more interesting due to its potential for an open continuous process. This research has been successful in producing effective antimicrobial properties on Kevlar fabric by plasma-initiated and plasma-controlled graft polymerization, which is unprecedented. The design of experiments showed that better results with higher order of log reduction can be obtained by process optimization, e.g. by using response surface methods. It would also be very beneficial to continue the research for the development of plasma graft-polymerization process with more rigorous design, which involves the use of crosslinker and antimicrobial monomers with different chemistry. A study that involves the development of a robust design for processes that perform consistently as intended under a wide range of user's conditions and yet produce high-level performance with high reliability would also be advantageous. The major implication of the findings from this research for the finishing of Kevlar is that a wide array of different surface functionalities may become more readily available now than ever. Plasma technology has made surface chemistry functionalization of Kevlar more straightforward and easier to perform, which opens new avenues for achieving functional and multifunctional Kevlar fabrics using a fast, more economic and environmentally friendly continuous process for niche market such as military applications and protective clothing for emergency responders.

Template-directed assembly of metal-chalcogenide nanocrystals into ordered mesoporous networks.

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

Vamvasakis, Ioannis; Subrahmanyam, Kota S.; Kanatzidis, Mercouri G.

Although great progress in the synthesis of porous networks of metal and metal oxide nanoparticles with highly accessible pore surface and ordered mesoscale pores has been achieved, synthesis of assembled 3D mesostructures of metal-chalcogenide nanocrystals is still challenging. In this work we demonstrate that ordered mesoporous networks, which comprise well-defined interconnected metal sulfide nanocrystals, can be prepared through a polymer-templated oxidative polymerization process. The resulting self-assembled mesostructures that were obtained after solvent extraction of the polymer template impart the unique combination of light-emitting metal chalcogenide nanocrystals, three-dimensional open-pore structure, high surface area, and uniform pores. We show that the poremore » surface of these materials is active and accessible to incoming molecules, exhibiting high photocatalytic activity and stability, for instance, in oxidation of 1-phenylethanol into acetophenone. We demonstrate through appropriate selection of the synthetic components that this method is general to prepare ordered mesoporous materials from metal chalcogenide nanocrystals with various sizes and compositions.« less

Synthesis of hollow NiCo2O4 nanospheres with large specific surface area for asymmetric supercapacitors.

PubMed

Xu, Kaibing; Yang, Jianmao; Hu, Junqing

2018-02-01

Hollow micro-/nanostructured electrode materials with high active surface area are highly desirable for achieving outstanding electrochemical properties. Herein, we report the successful synthesis of hierarchical hollow NiCo 2 O 4 nanospheres with high surface area as electrode materials for supercapacitors. Electrochemical measurements prove that such electrode materials exhibit excellent electrochemical behavior with a specific capacitance reaching 1229 F/g at 1 A/g, remarkable rate performance (∼83.6% retention from 1 to 25 A/g) and good cycling performance (86.3% after 3000 cycles). Furthermore, the asymmetric supercapacitor is fabricated with hollow NiCo 2 O 4 nanospheres electrode and activated carbon (AC) electrode as the positive and negative, respectively. This device exhibits a maximum energy density of 21.5 W h/kg, excellent cycling performance and coulombic efficiency. The results show that hollow NiCo 2 O 4 nanosphere electrode is a promising electrode material for the future application in high performance supercapacitors. Copyright © 2017 Elsevier Inc. All rights reserved.

Smart Pd Catalyst with Improved Thermal Stability Supported on High-Surface-Area LaFeO3 Prepared by Atomic Layer Deposition.

PubMed

Onn, Tzia Ming; Monai, Matteo; Dai, Sheng; Fonda, Emiliano; Montini, Tiziano; Pan, Xiaoqing; Graham, George W; Fornasiero, Paolo; Gorte, Raymond J

2018-04-11

The concept of self-regenerating or "smart" catalysts, developed to mitigate the problem of supported metal particle coarsening in high-temperature applications, involves redispersing large metal particles by incorporating them into a perovskite-structured support under oxidizing conditions and then exsolving them as small metal particles under reducing conditions. Unfortunately, the redispersion process does not appear to work in practice because the surface areas of the perovskite supports are too low and the diffusion lengths for the metal ions within the bulk perovskite too short. Here, we demonstrate reversible activation upon redox cycling for CH 4 oxidation and CO oxidation on Pd supported on high-surface-area LaFeO 3 , prepared as a thin conformal coating on a porous MgAl 2 O 4 support using atomic layer deposition. The LaFeO 3 film, less than 1.5 nm thick, was shown to be initially stable to at least 900 °C. The activated catalysts exhibit stable catalytic performance for methane oxidation after high-temperature treatment.

Facile Synthesis of Highly Efficient Amorphous Mn-MIL-100 Catalysts: Formation Mechanism and Structure Changes during Application in CO Oxidation.

PubMed

Zhang, Xiaodong; Li, Hongxin; Lv, Xutian; Xu, Jingcheng; Wang, Yuxin; He, Chi; Liu, Ning; Yang, Yiqiong; Wang, Yin

2018-06-21

A comprehensive study was carried out on amorphous metal-organic frameworks Mn-MIL-100 as efficient catalysts for CO oxidation. This study focused on explaining the crystalline-amorphous-crystalline transformations during thermolysis of Mn-MIL-100 and studying the structure changes during the CO oxidation reaction. A possible formation mechanism of amorphous Mn-MIL-100 was proposed. Amorphous Mn-MIL-100 obtained by calcination at 250 °C (a-Mn-250) showed a smaller specific surface area (4 m 2  g -1 ) but high catalytic activity. Furthermore, the structure of amorphous Mn-MIL-100 was labile during the reaction. When a-Mn-250 was treated with reaction atmosphere at high temperature (giving used-a-Mn-250-S), the amorphous catalysts transformed into Mn 2 O 3 . Meanwhile, the BET surface area (164 m 2  g -1 ) and catalytic performance both sharply increased. In addition, used-a-Mn-250-S catalyst transformed from Mn 2 O 3 into Mn 3 O 4 , and this resulted in a slight decrease of catalytic activity in the presence of 1 vol % water vapor in the feed stream. A schematic mechanism of the structure changes during the reaction process was proposed. The success of the synthesis relies on the increase in BET surface area by using CO as retreatment atmosphere, and the enhanced catalytic activity was attributed to the unique structure, a large quantity of surface active oxygen species, oxygen vacancies, and good low-temperature reduction behavior. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal desorption study of physical forces at the PTFE surface

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Pepper, S. V.

1987-01-01

Thermal desorption spectroscopy (TDS) of the polytetrafluoroethylene (PTFE) surface was successfully employed to study the possible role of physical forces in the enhancement of metal-PTFE adhesion by radiation. The thermal desorption spectra were analyzed without assumptions to yield the activation energy for desorption over a range of xenon coverage from less than 0.1 monolayer to more than 100 monolayers. For multilayer coverage, the desorption is zero-order with an activation energy equal to the sublimation energy of xenon. For submonolayer coverages, the order for desorption from the unirradiated PTFE surface is 0.73 and the activation energy for desorption is between 3.32 and 3.36 kcal/mol; less than the xenon sublimation energy. The effect of irradiation is to increase the activation energy for desorption to as high as 4 kcal/mol at low coverage.

Thermal desorption study of physical forces at the PTFE surface

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Pepper, S. V.

1985-01-01

Thermal desorption spectroscopy (TDS) of the polytetrafluoroethylene (PTFE) surface was successfully employed to study the possibile role of physical forces in the enhancement of metal-PTFE adhesion by radiation. The thermal desorption spectra were analyzed without assumptions to yield the activation energy for desorption over a range of xenon coverage from less than 0.1 monolayer to more than 100 monolayers. For multilayer coverage, the desorption is zero-order with an activation energy equal to the sublimation energy of xenon. For submonolayer coverages, the order for desorption from the unirradiated PTFE surface is 0.73 and the activation energy for desorption is between 3.32 and 3.36 kcal/mol; less than the xenon sublimation energy. The effect of irradiation is to increase the activation energy for desorption to as high as 4 kcal/mol at low coverage.

Preparation and Characterization of Surface Photocatalytic Activity with NiO/TiO₂ Nanocomposite Structure.

PubMed

Chen, Jian-Zhi; Chen, Tai-Hong; Lai, Li-Wen; Li, Pei-Yu; Liu, Hua-Wen; Hong, Yi-You; Liu, Day-Shan

2015-07-13

This study achieved a nanocomposite structure of nickel oxide (NiO)/titanium dioxide (TiO₂) heterojunction on a TiO₂ film surface. The photocatalytic activity of this structure evaluated by decomposing methylene blue (MB) solution was strongly correlated to the conductive behavior of the NiO film. A p -type NiO film of high concentration in contact with the native n -type TiO₂ film, which resulted in a strong inner electrical field to effectively separate the photogenerated electron-hole pairs, exhibited a much better photocatalytic activity than the controlled TiO₂ film. In addition, the photocatalytic activity of the NiO/TiO₂ nanocomposite structure was enhanced as the thickness of the p -NiO film decreased, which was beneficial for the migration of the photogenerated carriers to the structural surface.

Emplacement of Pahoehoe Toe Networks: Observations of May, 2010 Tube-fed Flows at Kilauea Volcano, Hawai'i

NASA Astrophysics Data System (ADS)

Crown, D. A.; Ramsey, M.; Hon, K.

2010-12-01

Pahoehoe lava flows are compound features that consist of multiple overlapping and interfingering lobes and exhibit morphologically diverse surfaces characterized by channelized zones, smooth-surfaced sheets, and numerous, small toe networks. Previous work compiled detailed planform maps of solidified pahoehoe toe networks to document their morphology, morphometry and connective relationships in order to provide constraints on lava transport models. In order to expand this research to active flow emplacement, we observed slow-moving, tube-fed pahoehoe flows on the coastal plain near Kalapana, Hawaii in May, 2010. The evolution of pahoehoe toe and toe network characteristics over their emplacement history was examined and the role of small-scale flow inflation on the advance of pahoehoe lobes evaluated. We collected both visible video footage and high-speed, high-precision thermal infrared (TIR) data using a FLIR S-40 camera. The TIR data provide surface temperature maps that can be easily used to identify formation of new toes and track their growth and surface cooling. From these maps, lobe development, connective relationships, and frontal and lateral spreading rates can be analyzed. Preliminary results suggest that regular cycles of activity characterize the development of these pahoehoe lobes: 1) emplacement of new toes in local topographic lows at the front, margin, and within the interior of an active lobe forming small interconnected networks, 2) decline and sometimes temporary cessation in the production of new pahoehoe toes, 3) inflation of the recently emplaced flow surface, either partially or en masse depending on the rate of influx of new lava, the degree of irregularity of the pre-flow surface, and/or the slope across the recently emplaced lava surface, and 4) fracturing of the recently emplaced surface crust that feeds emplacement of new toes. Inflation fractures typically cut across several previously emplaced toes and can occur at the front, along the margins, or within the active lobe, even at significant distances behind the flow front.

Path planning and parameter optimization of uniform removal in active feed polishing

NASA Astrophysics Data System (ADS)

Liu, Jian; Wang, Shaozhi; Zhang, Chunlei; Zhang, Linghua; Chen, Huanan

2015-06-01

A high-quality ultrasmooth surface is demanded in short-wave optical systems. However, the existing polishing methods have difficulties meeting the requirement on spherical or aspheric surfaces. As a new kind of small tool polishing method, active feed polishing (AFP) could attain a surface roughness of less than 0.3 nm (RMS) on spherical elements, although AFP may magnify the residual figure error or mid-frequency error. The purpose of this work is to propose an effective algorithm to realize uniform removal of the surface in the processing. At first, the principle of the AFP and the mechanism of the polishing machine are introduced. In order to maintain the processed figure error, a variable pitch spiral path planning algorithm and the dwell time-solving model are proposed. For suppressing the possible mid-frequency error, the uniformity of the synthesis tool path, which is generated by an arbitrary point at the polishing tool bottom, is analyzed and evaluated, and the angular velocity ratio of the tool spinning motion to the revolution motion is optimized. Finally, an experiment is conducted on a convex spherical surface and an ultrasmooth surface is finally acquired. In conclusion, a high-quality ultrasmooth surface can be successfully obtained with little degradation of the figure and mid-frequency errors by the algorithm.

Oxygen Reduction Reaction Activity of Platinum Thin Films with Different Densities

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

Ergul, Busra; Begum, Mahbuba; Kariuki, Nancy

Platinum thin films with different densities were grown on glassy carbon electrodes by high pressure sputtering deposition and evaluated as oxygen reduction reaction catalysts for polymer electrolyte fuel cells using cyclic voltammetry and rotating disk electrode techniques in aqueous perchloric acid electrolyte. The electrochemically active surface area, ORR mass activity (MA) and specific activity (SA) of the thin film electrodes were obtained. MA and SA were found to be higher for low-density films than for high-density film.

Skating on thin ice: surface chemistry under interstellar conditions

NASA Astrophysics Data System (ADS)

Fraser, H.; van Dishoeck, E.; Tielens, X.

Solid CO2 has been observed towards both active star forming regions and quiescent clouds (Gerakines et. al. (1999)). The high abundance of CO2 in the solid phase, and its low abundance in the gas phase, support the idea that CO2 is almost exclusively formed in the solid state. Several possible formation mechanisms have been postulated (Ruffle &Herbst (2001): Charnley &Kaufman (2000)), and the detection of CO2 towards quiescent sources such as Elias 16 (Whittet et. al. (1998)) clearly suggests that CO2 can be produced in the absence of UV or electron mediated processes. The most likely route is via the surface reactions between O atoms, or OH radicals, and CO. The tools of modern surface- science offer us the potential to determine many of the physical and chemical attributes of icy interstellar grain mantles under highly controlled conditions, that closely mimic interstellar environments. The Leiden Surface Reaction Simulation Device ( urfreside) combines UHV (UltraS High Vacuum) surface science techniques with an atomic beam to study chemical reactions occurring on the SURFACE and in the BULK of interstellar ice grain mimics. By simultaneously combining two or more surface analysis techniques, the chemical kinetics, reaction mechanisms and activation energies can be determined directly. The experiment is aimed at identifying the key barrierless reactions and desorption pathways on and in H2 O and CO ices under interstellar conditions. The results from traditional HV (high vacuum) and UHV studies of the CO + O and CO + OH reactions will be presented in this paper. Charnley, S.B., & Kaufman, M.J., 2000, ApJ, 529, L111 Gerakines, P.A., 1999, ApJ, 522, 357 Ruffle, D.P., & Herbst, E., 2001, MNRAS, 324, 1054 Whittet, D.C.B., et.al., 1998, ApJ, 498, L159

Force-activatable coating enables high-resolution cellular force imaging directly on regular cell culture surfaces.

PubMed

Sarkar, Anwesha; Zhao, Yuanchang; Wang, Yongliang; Wang, Xuefeng

2018-06-25

Integrin-transmitted cellular forces are crucial mechanical signals regulating a vast range of cell functions. Although various methods have been developed to visualize and quantify cellular forces at the cell-matrix interface, a method with high performance and low technical barrier is still in demand. Here we developed a force-activatable coating (FAC), which can be simply coated on regular cell culture apparatus' surfaces by physical adsorption, and turn these surfaces to force reporting platforms that enable cellular force mapping directly by fluorescence imaging. The FAC molecule consists of an adhesive domain for surface coating and a force-reporting domain which can be activated to fluoresce by integrin molecular tension. The tension threshold required for FAC activation is tunable in 10-60 piconewton (pN), allowing the selective imaging of cellular force contributed by integrin tension at different force levels. We tested the performance of two FACs with tension thresholds of 12 and 54 pN (nominal values), respectively, on both glass and polystyrene surfaces. Cellular forces were successfully mapped by fluorescence imaging on all the surfaces. FAC-coated surfaces also enable co-imaging of cellular forces and cell structures in both live cells and immunostained cells, therefore opening a new avenue for the study of the interplay of force and structure. We demonstrated the co-imaging of integrin tension and talin clustering in live cells, and concluded that talin clustering always occurs before the generation of integrin tension above 54 pN, reinforcing the notion that talin is an important adaptor protein for integrin tension transmission. Overall, FAC provides a highly convenient approach that is accessible to general biological laboratories for the study of cellular forces with high sensitivity and resolution, thus holding the potential to greatly boost the research of cell mechanobiology.

Onion-derived N, S self-doped carbon materials as highly efficient metal-free electrocatalysts for the oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Yang, Shuting; Mao, Xinxin; Cao, Zhaoxia; Yin, Yanhong; Wang, Zhichao; Shi, Mengjiao; Dong, Hongyu

2018-01-01

Onion-derived nitrogen, sulfur self-doped nanoporous carbon spheres (NSC) as efficient metal-free electrocatalyst were synthesized via a facile hydrothermal and subsequent pyrolysis process. The typical NSC with a high BET specific surface area of 1558 m2 g-1, contains 6.23 at.% N and 0.36 at.% S, and possesses high concentration of pyridinic and graphitic nitrogen species. Experimentally, the best performance was the NSC-A2 which showed excellent catalytic activity to oxygen reduction reaction via a 4 electron mechanism with an onset potential of 0.88 V (vs. RHE), and a superior stability comparable to commercial Pt/C catalyst. The high electrocatalytic activity is attributed to not only the synergistic effect of N and S dual doping in carbon and the sufficient active sites, but also its high BET specific surface area and suitable microporous structure. The results demonstrate that it is a simple and scalable approach for preparing efficient and low-cost carbon-based electrocatalysts for oxygen reduction reaction.

Silica decorated on porous activated carbon nanofiber composites for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Kim, So Yeun; Kim, Bo-Hye

2016-10-01

A hybrid of silica decorated on porous activated carbon nanofibers (ACNFs) is fabricated in the form of a web via electrospinning and an activation process as an electrode material for electrochemical capacitors in an organic electrolyte. The introduction of PhSiH3 (PS) into the polyacrylonitrile (PAN) solution induces a porous ACNF structure containing silica nanoparticles (NPs) via the spontaneous sol-gel process of PS by steam in the subsequent physical activation process. These inorganic-organic hybrid composites of porous ACNF containing silica NPs show superior specific capacitance and energy density in electrochemical tests, along with good rate capability and excellent cycle life in an organic electrolyte, which is attributed to the combination of ACNF's high surface area and silica's hydrophilicity. The electrochemical performance decreases with increasing PS concentration, and this trend is consistent with the specific surface area results, which reveal the rapid formation of a double layer.

Comparing the influence of sunspot activity and geomagnetic activity on winter surface climate

NASA Astrophysics Data System (ADS)

Maliniemi, Ville; Mursula, Kalevi; Roy, Indrani; Asikainen, Timo

2017-04-01

We compare here the effect of geomagnetic activity (using the aa index) and sunspot activity on surface climate using sea level pressure dataset from Hadley centre during northern winter. Previous studies using the multiple linear regression method have been limited to using sunspots as a solar activity predictor. Sunspots and total solar irradiance indicate a robust positive influence around the Aleutian Low. This is valid up to a lag of one year. However, geomagnetic activity yields a positive NAM pattern at high to polar latitudes and a positive signal around Azores High pressure region. Interestingly, while there is a positive signal around Azores High for a 2-year lag in sunspots, the strongest signal in this region is found for aa index at 1-year lag. There is also a weak but significant negative signature present around central Pacific for both sunspots and aa index. The combined influence of geomagnetic activity and Quasi Biannual Oscillation (QBO 30 hPa) produces a particularly strong response at mid to polar latitudes, much stronger than the combined influence of sunspots and QBO, which was mostly studied in previous studies so far. This signal is robust and insensitive to the selected time period during the last century. Our results provide a useful way for improving the prediction of winter weather at middle to high latitudes of the northern hemisphere.

Effects of molecular weight of hyaluronic acid on its viscosity and enzymatic activities of lysozyme and peroxidase.

PubMed

Kim, Jihoon; Chang, Ji-Youn; Kim, Yoon-Young; Kim, Moon-Jong; Kho, Hong-Seop

2018-05-01

To investigate the effects of the molecular weight of hyaluronic acid on its viscosity and enzymatic activities of lysozyme and peroxidase in solution and on the hydroxyapatite surface. Hyaluronic acids of four different molecular weights (10 kDa, 100 kDa, 1 MDa, and 2 MDa), hen egg-white lysozyme, bovine lactoperoxidase, and human whole saliva were used. Viscosity values of hyaluronic acids were measured using a cone-and-plate viscometer at six different concentrations (0.1-5.0 mg/mL). Enzymatic activities of lysozyme and peroxidase were examined by hydrolysis of fluorescein-labeled Micrococcus lysodeikticus and oxidation of fluorogenic 2',7'-dichlorofluorescein to fluorescing 2',7'-dichlorofluorescein, respectively. In solution assays, only 2 MDa-hyaluronic acid significantly inhibited lysozyme activities in saliva. In surface assays, hyaluronic acids inhibited lysozyme and peroxidase activities; the inhibitory activities were more apparent with high-molecular-weight ones in saliva than in purified enzymes. The 100 kDa-hyaluronic acid at 5.0 mg/mL, 1 MDa-one at 0.5 mg/mL, and 2 MDa-one at 0.2 mg/mL showed viscosity values similar to those of human whole saliva at a shear rate range required for normal oral functions. The differences among the influences of the three conditions on the enzymatic activities were not statistically significant. High-molecular-weight hyaluronic acids at low concentration and low-molecular-weight ones at high concentration showed viscosity values similar to those of human whole saliva. Inhibitory effects of hyaluronic acids on lysozyme and peroxidase activities were more significant with high-molecular-weight ones on the surface and in saliva compared with in solution and on purified enzymes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Activated alumina preparation and characterization: The review on recent advancement

NASA Astrophysics Data System (ADS)

Rabia, A. R.; Ibrahim, A. H.; Zulkepli, N. N.

2018-03-01

Aluminum and aluminum based material are significant industrial materials synthesis because of their abandonment, low weight and high-quality corrosion resistance. The most advances in aluminum processing are the ability to synthesize it's under suitable chemical composition and conditions, a porous structure can be formed on the surface. Activated alumina particles (AAP) synthesized by the electrochemically process from aluminum have gained serious attention, inexpensive material that can be employed for water filtration due to its active surface. Thus, the paper present a review study based on recent progress and advances in synthesizing activated alumina, various techniques currently being used in preparing activated alumina and its characteristics are studied and summarized

Highly conductive and porous activated reduced graphene oxide films for high-power supercapacitors.

PubMed

Zhang, Li Li; Zhao, Xin; Stoller, Meryl D; Zhu, Yanwu; Ji, Hengxing; Murali, Shanthi; Wu, Yaping; Perales, Stephen; Clevenger, Brandon; Ruoff, Rodney S

2012-04-11

We present a novel method to prepare highly conductive, free-standing, and flexible porous carbon thin films by chemical activation of reduced graphene oxide paper. These flexible carbon thin films possess a very high specific surface area of 2400 m(2) g(-1) with a high in-plane electrical conductivity of 5880 S m(-1). This is the highest specific surface area for a free-standing carbon film reported to date. A two-electrode supercapacitor using these carbon films as electrodes demonstrated an excellent high-frequency response, an extremely low equivalent series resistance on the order of 0.1 ohm, and a high-power delivery of about 500 kW kg(-1). While higher frequency and power values for graphene materials have been reported, these are the highest values achieved while simultaneously maintaining excellent specific capacitances and energy densities of 120 F g(-1) and 26 W h kg(-1), respectively. In addition, these free-standing thin films provide a route to simplify the electrode-manufacturing process by eliminating conducting additives and binders. The synthetic process is also compatible with existing industrial level KOH activation processes and roll-to-roll thin-film fabrication technologies. © 2012 American Chemical Society

Orientation Control in Thin Films of a High-χ Block Copolymer with a Surface Active Embedded Neutral Layer.

PubMed

Zhang, Jieqian; Clark, Michael B; Wu, Chunyi; Li, Mingqi; Trefonas, Peter; Hustad, Phillip D

2016-01-13

Directed self-assembly (DSA) of block copolymers (BCPs) is an attractive advanced patterning technology being considered for future integrated circuit manufacturing. By controlling interfacial interactions, self-assembled microdomains in thin films of polystyrene-block-poly(methyl methacrylate), PS-b-PMMA, can be oriented perpendicular to surfaces to form line/space or hole patterns. However, its relatively weak Flory interaction parameter, χ, limits its capability to pattern sub-10 nm features. Many BCPs with higher interaction parameters are capable of forming smaller features, but these "high-χ" BCPs typically have an imbalance in surface energy between the respective blocks that make it difficult to achieve the required perpendicular orientation. To address this challenge, we devised a polymeric surface active additive mixed into the BCP solution, referred to as an embedded neutral layer (ENL), which segregates to the top of the BCP film during casting and annealing and balances the surface tensions at the top of the thin film. The additive comprises a second BCP with a "neutral block" designed to provide matched surface tensions with the respective polymers of the main BCP and a "surface anchoring block" with very low surface energy that drives the material to the air interface during spin-casting and annealing. The surface anchoring block allows the film to be annealed above the glass transition temperature of the two materials without intermixing of the two components. DSA was also demonstrated with this embedded neutral top layer formulation on a chemical patterned template using a single step coat and simple thermal annealing. This ENL technology holds promise to enable the use of high-χ BCPs in advanced patterning applications.

Recent studies on activated carbons and fly ashes from Turkish resources

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

Ayhan Demirbas; Gulsin Arslan; Erol Pehlivan

2006-05-15

This article deals with adsorptive properties of activated carbons (ACs) and fly ashes from Turkish coal and biomass resources. ACs because of their high surface area, microporous character and the chemical nature of their surface have been considered potential adsorbents for the removal of heavy metals from industrial wastewater. Pyrolysis is an established process method for preparation of activated carbon from biomass. The bio-char is can be used as AC. The adsorption properties of ACs were strictly defined by the physicochemical nature of their surface and their texture, i.e., pore volume, pore size distribution, surface area. It is well knownmore » that the pH of the solution-adsorbant mixture is an important variable in the adsorption process. Fly ash has the highest adsorption capacity (198.2 mg/g for Cd(II)). Almond shell AC has the lowest adsorption capacity (2.7 mg/g).« less

Controlling cation segregation in perovskite-based electrodes for high electro-catalytic activity and durability.

PubMed

Li, Yifeng; Zhang, Wenqiang; Zheng, Yun; Chen, Jing; Yu, Bo; Chen, Yan; Liu, Meilin

2017-10-16

Solid oxide cell (SOC) based energy conversion systems have the potential to become the cleanest and most efficient systems for reversible conversion between electricity and chemical fuels due to their high efficiency, low emission, and excellent fuel flexibility. Broad implementation of this technology is however hindered by the lack of high-performance electrode materials. While many perovskite-based materials have shown remarkable promise as electrodes for SOCs, cation enrichment or segregation near the surface or interfaces is often observed, which greatly impacts not only electrode kinetics but also their durability and operational lifespan. Since the chemical and structural variations associated with surface enrichment or segregation are typically confined to the nanoscale, advanced experimental and computational tools are required to probe the detailed composition, structure, and nanostructure of these near-surface regions in real time with high spatial and temporal resolutions. In this review article, an overview of the recent progress made in this area is presented, highlighting the thermodynamic driving forces, kinetics, and various configurations of surface enrichment and segregation in several widely studied perovskite-based material systems. A profound understanding of the correlation between the surface nanostructure and the electro-catalytic activity and stability of the electrodes is then emphasized, which is vital to achieving the rational design of more efficient SOC electrode materials with excellent durability. Furthermore, the methodology and mechanistic understanding of the surface processes are applicable to other materials systems in a wide range of applications, including thermo-chemical photo-assisted splitting of H 2 O/CO 2 and metal-air batteries.

The effect of involuntary motor activity on myoelectric pattern recognition: a case study with chronic stroke patients

NASA Astrophysics Data System (ADS)

Zhang, Xu; Li, Yun; Chen, Xiang; Li, Guanglin; Zev Rymer, William; Zhou, Ping

2013-08-01

Objective. This study investigates the effect of the involuntary motor activity of paretic-spastic muscles on the classification of surface electromyography (EMG) signals. Approach. Two data collection sessions were designed for 8 stroke subjects to voluntarily perform 11 functional movements using their affected forearm and hand at relatively slow and fast speeds. For each stroke subject, the degree of involuntary motor activity present in the voluntary surface EMG recordings was qualitatively described from such slow and fast experimental protocols. Myoelectric pattern recognition analysis was performed using different combinations of voluntary surface EMG data recorded from the slow and fast sessions. Main results. Across all tested stroke subjects, our results revealed that when involuntary surface EMG is absent or present in both the training and testing datasets, high accuracies (>96%, >98%, respectively, averaged over all the subjects) can be achieved in the classification of different movements using surface EMG signals from paretic muscles. When involuntary surface EMG was solely involved in either the training or testing datasets, the classification accuracies were dramatically reduced (<89%, <85%, respectively). However, if both the training and testing datasets contained EMG signals with the presence and absence of involuntary EMG interference, high accuracies were still achieved (>97%). Significance. The findings of this study can be used to guide the appropriate design and implementation of myoelectric pattern recognition based systems or devices toward promoting robot-aided therapy for stroke rehabilitation.

Rapid control of mold temperature during injection molding process

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

Liparoti, Sara; Titomanlio, Giuseppe; Hunag, Tsang Min

2015-05-22

The control of mold surface temperature is an important factor that determines surface morphology and its dimension in thickness direction. It can also affect the frozen molecular orientation and the mold surface replicability in injection molded products. In this work, thin thermally active films were used to quickly control the mold surface temperature. In particular, an active high electrical conductivity carbon black loaded polyimide composites sandwiched between two insulating thin polymeric layers was used to condition the mold surface. By controlling the heating time, it was possible to control precisely the temporal variation of the mold temperature surface during themore » entire cycle. The surface heating rate was about 40°C/s and upon contact with the polymer the surface temperature decreased back to 40°C within about 5 s; the overall cycle time increased only slightly. The effect on cross section sample morphology of samples of iPP were analyzed and discussed on the basis of the recorded temperature evolution.« less

X-ray photoemission analysis of clean and carbon monoxide-chemisorbed platinum(111) stepped surfaces using a curved crystal

DOE PAGES

Walter, Andrew L.; Schiller, Frederik; Corso, Martina; ...

2015-11-12

Surface chemistry and catalysis studies could significantly gain from the systematic variation of surface active sites, tested under the very same conditions. Curved crystals are excellent platforms to perform such systematics, which may in turn allow to better resolve fundamental properties and reveal new phenomena. This is demonstrated here for the carbon monoxide/platinum system. We curve a platinum crystal around the high-symmetry (111) direction and carry out photoemission scans on top. This renders the spatial core-level imaging of carbon monoxide adsorbed on a 'tunable' vicinal surface, allowing a straightforward visualization of the rich chemisorption phenomenology at steps and terraces. Throughmore » such photoemission images we probe a characteristic elastic strain variation at stepped surfaces, and unveil subtle stress-release effects on clean and covered vicinal surfaces. Lastly, these results offer the prospect of applying the curved surface approach to rationally investigate the chemical activity of surfaces under real pressure conditions.« less

X-ray photoemission analysis of clean and carbon monoxide-chemisorbed platinum(111) stepped surfaces using a curved crystal

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

Walter, Andrew L.; Schiller, Frederik; Corso, Martina

Surface chemistry and catalysis studies could significantly gain from the systematic variation of surface active sites, tested under the very same conditions. Curved crystals are excellent platforms to perform such systematics, which may in turn allow to better resolve fundamental properties and reveal new phenomena. This is demonstrated here for the carbon monoxide/platinum system. We curve a platinum crystal around the high-symmetry (111) direction and carry out photoemission scans on top. This renders the spatial core-level imaging of carbon monoxide adsorbed on a 'tunable' vicinal surface, allowing a straightforward visualization of the rich chemisorption phenomenology at steps and terraces. Throughmore » such photoemission images we probe a characteristic elastic strain variation at stepped surfaces, and unveil subtle stress-release effects on clean and covered vicinal surfaces. Lastly, these results offer the prospect of applying the curved surface approach to rationally investigate the chemical activity of surfaces under real pressure conditions.« less

Superhydrophobic Blood-Repellent Surfaces.

PubMed

Jokinen, Ville; Kankuri, Esko; Hoshian, Sasha; Franssila, Sami; Ras, Robin H A

2018-06-01

Superhydrophobic surfaces repel water and, in some cases, other liquids as well. The repellency is caused by topographical features at the nano-/microscale and low surface energy. Blood is a challenging liquid to repel due to its high propensity for activation of intrinsic hemostatic mechanisms, induction of coagulation, and platelet activation upon contact with foreign surfaces. Imbalanced activation of coagulation drives thrombogenesis or formation of blood clots that can occlude the blood flow either on-site or further downstream as emboli, exposing tissues to ischemia and infarction. Blood-repellent superhydrophobic surfaces aim toward reducing the thrombogenicity of surfaces of blood-contacting devices and implants. Several mechanisms that lead to blood repellency are proposed, focusing mainly on platelet antiadhesion. Structured surfaces can: (i) reduce the effective area exposed to platelets, (ii) reduce the adhesion area available to individual platelets, (iii) cause hydrodynamic effects that reduce platelet adhesion, and (iv) reduce or alter protein adsorption in a way that is not conducive to thrombus formation. These mechanisms benefit from the superhydrophobic Cassie state, in which a thin layer of air is trapped between the solid surface and the liquid. The connections between water- and blood repellency are discussed and several recent examples of blood-repellent superhydrophobic surfaces are highlighted. © 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cobalt-doping-induced synthesis of ceria nanodisks and their significantly enhanced catalytic activity.

PubMed

Guo, Xiao-Hui; Mao, Chao-Chao; Zhang, Ji; Huang, Jun; Wang, Wa-Nv; Deng, Yong-Hui; Wang, Yao-Yu; Cao, Yong; Huang, Wei-Xin; Yu, Shu-Hong

2012-05-21

High-quality cobalt-doped ceria nanostructures with triangular column, triangular slab, and disklike shapes are synthesized by tuning the doping amount of cobalt nitrate in a facile hydrothermal reaction. The cobalt-doped ceria nanodisks display significantly enhanced catalytic activity in CO oxidation due to exposed highly active crystal planes and the presence of numerous surface defects. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Southern high latitude dune fields on Mars: Morphology, aeolian inactivity, and climate change

USGS Publications Warehouse

Fenton, L.K.; Hayward, R.K.

2010-01-01

In a study area spanning the martian surface poleward of 50?? S., 1190 dune fields have been identified, mapped, and categorized based on dune field morphology. Dune fields in the study area span ??? 116400km2, leading to a global dune field coverage estimate of ???904000km2, far less than that found on Earth. Based on distinct morphological features, the dune fields were grouped into six different classes that vary in interpreted aeolian activity level from potentially active to relatively inactive and eroding. The six dune field classes occur in specific latitude zones, with a sequence of reduced activity and degradation progressing poleward. In particular, the first signs of stabilization appear at ???60?? S., which broadly corresponds to the edge of high concentrations of water-equivalent hydrogen content (observed by the Neutron Spectrometer) that have been interpreted as ground ice. This near-surface ground ice likely acts to reduce sand availability in the present climate state on Mars, stabilizing high latitude dunes and allowing erosional processes to change their morphology. As a result, climatic changes in the content of near-surface ground ice are likely to influence the level of dune activity. Spatial variation of dune field classes with longitude is significant, suggesting that local conditions play a major role in determining dune field activity level. Dune fields on the south polar layered terrain, for example, appear either potentially active or inactive, indicating that at least two generations of dune building have occurred on this surface. Many dune fields show signs of degradation mixed with crisp-brinked dunes, also suggesting that more than one generation of dune building has occurred since they originally formed. Dune fields superposed on early and late Amazonian surfaces provide potential upper age limits of ???100My on the south polar layered deposits and ???3Ga elsewhere at high latitudes. No craters are present on any identifiable dune fields, which can provide a lower age limit through crater counting: assuming all relatively stabilized dune fields represent a single noncontiguous surface of uniform age, their estimated crater retention age is

High-pressure liquid-monopropellant strand combustion.

NASA Technical Reports Server (NTRS)

Faeth, G. M.

1972-01-01

Examination of the influence of dissolved gases on the state of the liquid surface during high-pressure liquid-monopropellant combustion through the use of a strand burning experiment. Liquid surface temperatures were measured, using fine-wire thermocouples, during the strand combustion of ethyl nitrate, normal propyl nitrate, and propylene glycol dinitrate at pressures up to 81 atm. These measurements were compared with the predictions of a variable-property gas-phase analysis assuming an infinite activation energy for the decomposition reaction. The state of the liquid surface was estimated using a conventional low-pressure phase equilibrium model, as well as a high-pressure version that considered the presence of dissolved combustion-product gases in the liquid phase. The high-pressure model was found to give a superior prediction of measured liquid surface temperatures. Computed total pressures required for the surface to reach its critical mixing point during strand combustion were found to be in the range from 2.15 to 4.62 times the critical pressure of the pure propellant. Computed dissolved gas concentrations at the liquid surface were in the range from 35 to 50% near the critical combustion condition.

Activated boron nitride as an effective adsorbent for metal ions and organic pollutants

PubMed Central

Li, Jie; Xiao, Xing; Xu, Xuewen; Lin, Jing; Huang, Yang; Xue, Yanming; Jin, Peng; Zou, Jin; Tang, Chengchun

2013-01-01

Novel activated boron nitride (BN) as an effective adsorbent for pollutants in water and air has been reported in the present work. The activated BN was synthesized by a simple structure-directed method that enabled us to control the surface area, pore volume, crystal defects and surface groups. The obtained BN exhibits an super high surface area of 2078 m2/g, a large pore volume of 1.66 cm3/g and a special multimodal microporous/mesoporous structure located at ~ 1.3, ~ 2.7, and ~ 3.9 nm, respectively. More importantly, the novel activated BN exhibits an excellent adsorption performance for various metal ions (Cr3+, Co2+, Ni2+, Ce3+, Pb2+) and organic pollutants (tetracycline, methyl orange and congo red) in water, as well as volatile organic compounds (benzene) in air. The excellent reusability of the activated BN has also been confirmed. All the features render the activated BN a promising material suitable for environmental remediation. PMID:24220570

Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions.

PubMed

Feng, Zhenxing; Hong, Wesley T; Fong, Dillon D; Lee, Yueh-Lin; Yacoby, Yizhak; Morgan, Dane; Shao-Horn, Yang

2016-05-17

Electrocatalysts play an important role in catalyzing the kinetics for oxygen reduction and oxygen evolution reactions for many air-based energy storage and conversion devices, such as metal-air batteries and fuel cells. Although noble metals have been extensively used as electrocatalysts, their limited natural abundance and high costs have motivated the search for more cost-effective catalysts. Oxides are suitable candidates since they are relatively inexpensive and have shown reasonably high activity for various electrochemical reactions. However, a lack of fundamental understanding of the reaction mechanisms has been a major hurdle toward improving electrocatalytic activity. Detailed studies of the oxide surface atomic structure and chemistry (e.g., cation migration) can provide much needed insights for the design of highly efficient and stable oxide electrocatalysts. In this Account, we focus on recent advances in characterizing strontium (Sr) cation segregation and enrichment near the surface of Sr-substituted perovskite oxides under different operating conditions (e.g., high temperature, applied potential), as well as their influence on the surface oxygen exchange kinetics at elevated temperatures. We contrast Sr segregation, which is associated with Sr redistribution in the crystal lattice near the surface, with Sr enrichment, which involves Sr redistribution via the formation of secondary phases. The newly developed coherent Bragg rod analysis (COBRA) and energy-modulated differential COBRA are uniquely powerful ways of providing information about surface and interfacial cation segregation at the atomic scale for these thin film electrocatalysts. In situ ambient pressure X-ray photoelectron spectroscopy (APXPS) studies under electrochemical operating conditions give additional insights into cation migration. Direct COBRA and APXPS evidence for surface Sr segregation was found for La1-xSrxCoO3-δ and (La1-ySry)2CoO4±δ/La1-xSrxCoO3-δ oxide thin films, and the physical origin of segregation is discussed in comparison with (La1-ySry)2CoO4±δ/La1-xSrxCo0.2Fe0.8O3-δ. Sr enrichment in many electrocatalysts, such as La1-xSrxMO3-δ (M = Cr, Co, Mn, or Co and Fe) and Sm1-xSrxCoO3, has been probed using alternative techniques, including low energy ion scattering, secondary ion mass spectrometry, and X-ray fluorescence-based methods for depth-dependent, element-specific analysis. We highlight a strong connection between cation segregation and electrocatalytic properties, because cation segregation enhances oxygen transport and surface oxygen exchange kinetics. On the other hand, the formation of cation-enriched secondary phases can lead to the blocking of active sites, inhibiting oxygen exchange. With help from density functional theory, the links between cation migration, catalyst stability, and catalytic activity are provided, and the oxygen p-band center relative to the Fermi level can be identified as an activity descriptor. Based on these findings, we discuss strategies to increase a catalyst's activity while maintaining stability to design efficient, cost-effective electrocatalysts.

Real space mapping of ionic diffusion and electrochemical activity in energy storage and conversion materials

DOEpatents

Kalinin, Sergei V; Balke, Nina; Kumar, Amit; Dudney, Nancy J; Jesse, Stephen

2014-05-06

A method and system for probing mobile ion diffusivity and electrochemical reactivity on a nanometer length scale of a free electrochemically active surface includes a control module that biases the surface of the material. An electrical excitation signal is applied to the material and induces the movement of mobile ions. An SPM probe in contact with the surface of the material detects the displacement of mobile ions at the surface of the material. A detector measures an electromechanical strain response at the surface of the material based on the movement and reactions of the mobile ions. The use of an SPM tip to detect local deformations allows highly reproducible measurements in an ambient environment without visible changes in surface structure. The measurements illustrate effective spatial resolution comparable with defect spacing and well below characteristic grain sizes of the material.

Long-term stability of nanostructured thin film electrodes at operating potentials

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

Ahluwalia, Rajesh K.; Peng, J. -K.; Wang, X.

Long-term stability of nanostructured thin film (NSTF) catalysts at operating potentials has been investigated. Compared to high surface area Pt/C catalysts, NSTF electrodes show 20–50x smaller F – emission rates (FER) because of their high specific activity for oxygen reduction reaction (ORR), but are susceptible to poisoning by the products of membrane degradation because of their low electrochemically active surface area (ECSA). The observed voltage degradation rates at potentials corresponding to 1–1.5 A/cm 2 current density are much higher than the allowable 13–14 μV/h. Although F – is not itself responsible for performance decay, cumulative fluoride release (CFR) is amore » good marker for catalyst surface contamination. The observed performance decay is not only due to loss of active Pt sites but also adsorbed impurities impeding ORR kinetics. There is a strong correlation between measured CFR and observed decrease in specific ORR activity and limiting current density and increase in mass transfer overpotentials. Furthermore, the correlations indicate that the target of <10% lifetime performance degradation can be achieved by restricting CFR in NSTF electrodes to 0.7 μg/cm 2, as may be possible with more stable membranes, higher surface area NSTF catalysts, and cell operation at lower temperatures and higher relative humidities.« less

Long-term stability of nanostructured thin film electrodes at operating potentials

DOE PAGES

Ahluwalia, Rajesh K.; Peng, J. -K.; Wang, X.; ...

2017-02-09

Long-term stability of nanostructured thin film (NSTF) catalysts at operating potentials has been investigated. Compared to high surface area Pt/C catalysts, NSTF electrodes show 20–50x smaller F – emission rates (FER) because of their high specific activity for oxygen reduction reaction (ORR), but are susceptible to poisoning by the products of membrane degradation because of their low electrochemically active surface area (ECSA). The observed voltage degradation rates at potentials corresponding to 1–1.5 A/cm 2 current density are much higher than the allowable 13–14 μV/h. Although F – is not itself responsible for performance decay, cumulative fluoride release (CFR) is amore » good marker for catalyst surface contamination. The observed performance decay is not only due to loss of active Pt sites but also adsorbed impurities impeding ORR kinetics. There is a strong correlation between measured CFR and observed decrease in specific ORR activity and limiting current density and increase in mass transfer overpotentials. Furthermore, the correlations indicate that the target of <10% lifetime performance degradation can be achieved by restricting CFR in NSTF electrodes to 0.7 μg/cm 2, as may be possible with more stable membranes, higher surface area NSTF catalysts, and cell operation at lower temperatures and higher relative humidities.« less

Surface similarity-based molecular query-retrieval

PubMed Central

Singh, Rahul

2007-01-01

Background Discerning the similarity between molecules is a challenging problem in drug discovery as well as in molecular biology. The importance of this problem is due to the fact that the biochemical characteristics of a molecule are closely related to its structure. Therefore molecular similarity is a key notion in investigations targeting exploration of molecular structural space, query-retrieval in molecular databases, and structure-activity modelling. Determining molecular similarity is related to the choice of molecular representation. Currently, representations with high descriptive power and physical relevance like 3D surface-based descriptors are available. Information from such representations is both surface-based and volumetric. However, most techniques for determining molecular similarity tend to focus on idealized 2D graph-based descriptors due to the complexity that accompanies reasoning with more elaborate representations. Results This paper addresses the problem of determining similarity when molecules are described using complex surface-based representations. It proposes an intrinsic, spherical representation that systematically maps points on a molecular surface to points on a standard coordinate system (a sphere). Molecular surface properties such as shape, field strengths, and effects due to field super-positioningcan then be captured as distributions on the surface of the sphere. Surface-based molecular similarity is subsequently determined by computing the similarity of the surface-property distributions using a novel formulation of histogram-intersection. The similarity formulation is not only sensitive to the 3D distribution of the surface properties, but is also highly efficient to compute. Conclusion The proposed method obviates the computationally expensive step of molecular pose-optimisation, can incorporate conformational variations, and facilitates highly efficient determination of similarity by directly comparing molecular surfaces and surface-based properties. Retrieval performance, applications in structure-activity modeling of complex biological properties, and comparisons with existing research and commercial methods demonstrate the validity and effectiveness of the approach. PMID:17634096

Photopheresis with UV-A light and 8-methoxypsoralen leads to cell death and to release of blebs with anti-inflammatory phenotype in activated and non-activated lymphocytes

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

Stadler, K.; Frey, B.; Munoz, L.E.

2009-08-14

Background: Extracorporeal photopheresis is a therapy for treatment of autoimmune diseases, cutaneous T-cell lymphoma, organ graft rejection as well as graft-versus-host diseases. The exact mechanism how the combination of 8-methoxypsoralen plus UV-A irradiation (PUVA) acts is still unclear. We investigated the cell death of activated and non-activated lymphocytes after PUVA treatment as well as the rate of released blebs and their antigen composition. Results: In presence of 8-MOP, UV-A light highly significantly increased the cell death of activated lymphocytes. The same was observed to a lesser extent in non-activated cells. Blebs derived from activated lymphocytes after PUVA treatment showed themore » highest surface exposition of phosphatidylserine. These blebs also displayed a high exposure of the antigens CD5 and CD8 as well as a low exposure of CD28 and CD86. Conclusion: PUVA treatment exerts anti-inflammatory effects by inducing apoptosis and apoptotic cell-derived blebs with immune suppressive surface composition.« less

Producing lasting amphiphobic building surfaces with self-cleaning properties

NASA Astrophysics Data System (ADS)

Facio, Dario S.; Carrascosa, Luis A. M.; Mosquera, María J.

2017-06-01

Nowadays, producing building surfaces that prevent water and oil uptake and which present self-cleaning activity is still a challenge. In this study, amphiphobic (superhydrophobic and oleophobic) building surfaces were successfully produced. A simple and low-cost process was developed, which is applicable to large-scale building surfaces, according the following procedure: (1) by spraying a SiO2 nanocomposite which produces a closely-packed nanoparticle uniform topography; (2) by functionalizing the previous coating with a fluorinated alkoxysilane, producing high hydrophobicity and oleophobicity. The formation of a Cassie-Baxter regime, in which air pockets could be trapped between the aggregates of particles, was confirmed by topographic study. The building surface demonstrated an excellent self-cleaning performance. Finally, the surface presented lasting superhydrophobicity with high stability against successive attachment/detachment force cycles. This high durability can be explained by the effective grafting of the silica nanocomposite coating skeleton with the substrate, and with the additional fluorinated coating produced by condensation reactions.

Trapping of Momentum due to Low Salinity Water in the north Bay of Bengal

NASA Astrophysics Data System (ADS)

Chaudhuri, D.; Tandon, A.; Farrar, T.; Weller, R. A.; Venkatesan, R.; S, S.; MacKinnon, J. A.; D'Asaro, E. A.; Sengupta, D.

2016-02-01

We study the relation between near-surface ocean stratification and upper ocean currents (momentum) during the diurnal cycle and subseasonal "active-break cycle" of the summer monsoon in the north Bay of Bengal. We use time series of hourly observations from NIOT moorings BD08, BD09 and an INCOIS mooring near 18 N, 89 E in 2013, and data collected during two research cruises of ORV Sagar Nidhi in August-September 2014 and 2015. Our analyses are based on upper ocean profiles of temperature, salinity and density (from moorings and a shipborne underway conductivity-temperature-depth profiler), velocity (Acoustic Doppler Current Profiler), and surface forcing (meterology sensors on moored buoy and ship). Monsoon breaks are characterized by low rainfall, low wind speed (0-5 m/s) and high incident shortwave radiation, whereas active phases are marked by intense rainfall, high wind speed (8-16 m/s) and low incident sunlight. Our main findings are: (i) Net surface heat flux is positive (ocean gains heat) during break spells, and sea surface temperature (SST) rises by upto 1.5 C in 1-2 weeks. (ii) During breaks, day-night SST difference can reach 1.5C; mixed layer depth (MLD) shoals to 5m during day time, and deepens to 15-20 m by late night/early morning. (iii) During active spells, SST cools on subseasonal scales; MLD is deep (exceeding 20 m), and diurnal re-stratification is weak or absent. (iv) Once very low-salinity water (<30 psu) from rivers arrives at the moorings in late August, MLD remains shallow, and is insensitive to subseasonal changes in surface forcing. (v) Moored data and high-resolution observations from the summer 2014 and 2015 cruises reveal trapping of momentum from winds in a relatively thin surface layer when surface salinity is low and the shallow stratification is strong. Results of ingoing analyses will be presented at the meeting.

Characterization of Missouri surface waters near point sources of pollution reveals potential novel atmospheric route of exposure for bisphenol A and wastewater hormonal activity pattern.

PubMed

Kassotis, Christopher D; Alvarez, David A; Taylor, Julia A; vom Saal, Frederick S; Nagel, Susan C; Tillitt, Donald E

2015-08-15

Surface water contamination by chemical pollutants increasingly threatens water quality around the world. Among the many contaminants found in surface water, there is growing concern regarding endocrine disrupting chemicals, based on their ability to interfere with some aspect of hormone action in exposed organisms, including humans. This study assessed water quality at several sites across Missouri (near wastewater treatment plants and airborne release sites of bisphenol A) based on hormone receptor activation potencies and chemical concentrations present in the surface water. We hypothesized that bisphenol A and ethinylestradiol would be greater in water near permitted airborne release sites and wastewater treatment plant inputs, respectively, and that these two compounds would be responsible for the majority of activities in receptor-based assays conducted with water collected near these sites. Concentrations of bisphenol A and ethinylestradiol were compared to observed receptor activities using authentic standards to assess contribution to total activities, and quantitation of a comprehensive set of wastewater compounds was performed to better characterize each site. Bisphenol A concentrations were found to be elevated in surface water near permitted airborne release sites, raising questions that airborne releases of BPA may influence nearby surface water contamination and may represent a previously underestimated source to the environment and potential for human exposure. Estrogen and androgen receptor activities of surface water samples were predictive of wastewater input, although the lower sensitivity of the ethinylestradiol ELISA relative to the very high sensitivity of the bioassay approaches did not allow a direct comparison. Wastewater-influenced sites also had elevated anti-estrogenic and anti-androgenic equivalence, while sites without wastewater discharges exhibited no antagonist activities. Published by Elsevier B.V.

Characterization of Missouri surface waters near point sources of pollution reveals potential novel atmospheric route of exposure for bisphenol A and wastewater hormonal activity pattern

USGS Publications Warehouse

Kassotis, Christopher D.; Alvarez, David A.; Taylor, Julia A.; vom Saal, Frederick S.; Nagel, Susan C.; Tillitt, Donald E.

2015-01-01

Surface water contamination by chemical pollutants increasingly threatens water quality around the world. Among the many contaminants found in surface water, there is growing concern regarding endocrine disrupting chemicals, based on their ability to interfere with some aspect of hormone action in exposed organisms, including humans. This study assessed water quality at several sites across Missouri (near wastewater treatment plants and airborne release sites of bisphenol A) based on hormone receptor activation potencies and chemical concentrationspresent in the surface water. We hypothesized that bisphenol A and ethinylestradiol would be greater in water near permitted airborne release sites and wastewater treatment plant inputs, respectively, and that these two compounds would be responsible for the majority of activities in receptor-based assays conducted with water collected near these sites. Concentrations of bisphenol A and ethinylestradiol were compared to observed receptor activities using authentic standards to assess contribution to total activities, and quantitation of a comprehensive set of wastewater compounds was performed to better characterize each site. Bisphenol A concentrations were found to be elevated in surface water near permitted airborne release sites, raising questions that airborne releases of BPA may influence nearby surface water contamination and may represent a previously underestimated source to the environment and potential for human exposure. Estrogen and androgen receptor activities of surface water samples were predictive of wastewater input, although the lower sensitivity of the ethinylestradiol ELISA relative to the very high sensitivity of the bioassay approaches did not allow a direct comparison. Wastewater-influenced sites also had elevated anti-estrogenic and anti-androgenic equivalence, while sites without wastewater discharges exhibited no antagonist activities.

Surface modification of mixed-phase hydrogenated TiO2 and corresponding photocatalytic response

NASA Astrophysics Data System (ADS)

Samsudin, Emy Marlina; Hamid, Sharifah Bee Abd; Juan, Joon Ching; Basirun, Wan Jefrey; Kandjani, Ahmad Esmaielzadeh

2015-12-01

Preparation of highly photo-activated TiO2 is achievable by hydrogenation at constant temperature and pressure, with controlled hydrogenation duration. The formation of surface disorders and Ti3+ is responsible for the color change from white unhydrogenated TiO2 to bluish-gray hydrogenated TiO2. This color change, together with increased oxygen vacancies and Ti3+ enhanced the solar light absorption from UV to infra-red region. Interestingly, no band gap narrowing is observed. The photocatalytic activity in the UV and visible region is controlled by Ti3+ and oxygen vacancies respectively. Both Ti3+ and oxygen vacancies increases the electron density on the catalyst surface thus facilitates rad OH radicals formation. The lifespan of surface photo-excited electrons and holes are also sustained thus prevents charge carrier recombination. However, excessive amount of oxygen vacancies deteriorates the photocatalytic activity as it serves as charge traps. Hydrogenation of TiO2 also promotes the growth of active {0 0 1} facets and facilitates the photocatalytic activity by higher concentration of surface OH radicals. However, the growth of {0 0 1} facets is small and insignificant toward the overall photo-kinetics. This work also shows that larger role is played by Ti3+ and oxygen vacancies rather than the surface disorders created during the hydrogenation process. It also demonstrates the ability of hydrogenated TiO2 to absorb wider range of photons even though at a similar band gap as unhydrogenated TiO2. In addition, the photocatalytic activity is shown to be decreased for extended hydrogenation duration due to excessive catalyst growth and loss in the total surface area. Thus, a balance in the physico-chemical properties of hydrogenated TiO2 is crucial to enhance the photocatalytic activity by simply controlling the hydrogenation duration.

Synthesis and catalytic activity of polysaccharide templated nanocrystalline sulfated zirconia

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

Sherly, K. B.; Rakesh, K.

Nanoscaled materials are of great interest due to their unique enhanced optical, electrical and magnetic properties. Sulfate-promoted zirconia has been shown to exhibit super acidic behavior and high activity for acid catalyzed reactions. Nanocrystalline zirconia was prepared in the presence of polysaccharide template by interaction between ZrOCl{sub 2}⋅8H{sub 2}O and chitosan template. The interaction was carried out in aqueous phase, followed by the removal of templates by calcination at optimum temperature and sulfation. The structural and textural features were characterized by powder XRD, TG, SEM and TEM. XRD patterns showed the peaks of the diffractogram were in agreement with themore » theoretical data of zirconia with the catalytically active tetragonal phase and average crystalline size of the particles was found to be 9 nm, which was confirmed by TEM. TPD using ammonia as probe, FTIR and BET surface area analysis were used for analyzing surface features like acidity and porosity. The BET surface area analysis showed the sample had moderately high surface area. FTIR was used to find the type species attached to the surface of zirconia. UV-DRS found the band gap of the zirconia was found to be 2.8 eV. The benzylation of o-xylene was carried out batchwise in atmospheric pressure and 433K temperature using sulfated zirconia as catalyst.« less

Combining an Optical Resonance Biosensor with Enzyme Activity Kinetics to Understand Protein Adsorption and Denaturation

PubMed Central

Wilson, Kerry A.; Finch, Craig A.; Anderson, Phillip; Vollmer, Frank; Hickman, James J.

2014-01-01

Understanding protein adsorption and resultant conformation changes on modified and unmodified silicon dioxide surfaces is a subject of keen interest in biosensors, microfluidic systems and for medical diagnostics. However, it has been proven difficult to investigate the kinetics of the adsorption process on these surfaces as well as understand the topic of the denaturation of proteins and its effect on enzyme activity. A highly sensitive optical whispering gallery mode (WGM) resonator was used to study a catalytic enzyme’s adsorption processes on different silane modified glass substrates (plain glass control, DETA, 13F, and SiPEG). The WGM sensor was able to obtain high resolution kinetic data of glucose oxidase (GO) adsorption with sensitivity of adsorption better than that possible with SPR. The kinetic data, in combination with a functional assay of the enzyme activity, was used to test hypotheses on adsorption mechanisms. By fitting numerical models to the WGM sensograms for protein adsorption, and by confirming numerical predictions of enzyme activity in a separate assay, we were able to identify mechanisms for GO adsorption on different alkylsilanes and infer information about the adsorption of protein on nanostructured surfaces. PMID:25453976

Combining an optical resonance biosensor with enzyme activity kinetics to understand protein adsorption and denaturation.

PubMed

Wilson, Kerry A; Finch, Craig A; Anderson, Phillip; Vollmer, Frank; Hickman, James J

2015-01-01

Understanding protein adsorption and resultant conformation changes on modified and unmodified silicon dioxide surfaces is a subject of keen interest in biosensors, microfluidic systems and for medical diagnostics. However, it has been proven difficult to investigate the kinetics of the adsorption process on these surfaces as well as understand the topic of the denaturation of proteins and its effect on enzyme activity. A highly sensitive optical whispering gallery mode (WGM) resonator was used to study a catalytic enzyme's adsorption processes on different silane modified glass substrates (plain glass control, DETA, 13 F, and SiPEG). The WGM sensor was able to obtain high resolution kinetic data of glucose oxidase (GO) adsorption with sensitivity of adsorption better than that possible with SPR. The kinetic data, in combination with a functional assay of the enzyme activity, was used to test hypotheses on adsorption mechanisms. By fitting numerical models to the WGM sensograms for protein adsorption, and by confirming numerical predictions of enzyme activity in a separate assay, we were able to identify mechanisms for GO adsorption on different alkylsilanes and infer information about the adsorption of protein on nanostructured surfaces. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effects of microwave heating on porous structure of regenerated powdered activated carbon used in xylose.

PubMed

Li, Wei; Wang, Xinying; Peng, Jinhui

2014-01-01

The regeneration of spent powdered activated carbons used in xylose decolourization by microwave heating was investigated. Effects of microwave power and microwave heating time on the adsorption capacity of regenerated activated carbons were evaluated. The optimum conditions obtained are as follows: microwave power 800W; microwave heating time 30min. Regenerated activated carbon in this work has high adsorption capacities for the amount of methylene blue of 16 cm3/0.1 g and the iodine number of 1000.06mg/g. The specific surface areas of fresh commercial activated carbon, spent carbon and regenerated activated carbon were calculated according to the Brunauer, Emmett and Teller method, and the pore-size distributions of these carbons were characterized by non-local density functional theory (NLDFT). The results show that the specific surface area and the total pore volume of regenerated activated carbon are 1064 m2/g and 1.181 mL/g, respectively, indicating the feasibility of regeneration of spent powdered activated carbon used in xylose decolourization by microwave heating. The results of surface fractal dimensions also confirm the results of isotherms and NLDFT.

Nucleotide Catabolism on the Surface of Aortic Valve Xenografts; Effects of Different Decellularization Strategies.

PubMed

Kutryb-Zajac, Barbara; Yuen, Ada H Y; Khalpey, Zain; Zukowska, Paulina; Slominska, Ewa M; Taylor, Patricia M; Goldstein, Steven; Heacox, Albert E; Lavitrano, Marialuisa; Chester, Adrian H; Yacoub, Magdi H; Smolenski, Ryszard T

2016-04-01

Extracellular nucleotide metabolism controls thrombosis and inflammation and may affect degeneration and calcification of aortic valve prostheses. We evaluated the effect of different decellularization strategies on enzyme activities involved in extracellular nucleotide metabolism. Porcine valves were tested intact or decellularized either by detergent treatment or hypotonic lysis and nuclease digestion. The rates of ATP hydrolysis, AMP hydrolysis, and adenosine deamination were estimated by incubation of aorta or valve leaflet sections with substrates followed by HPLC analysis. We demonstrated relatively high activities of ecto-enzymes on porcine valve as compared to the aortic wall. Hypotonic lysis/nuclease digestion preserved >80 % of ATP and AMP hydrolytic activity but reduced adenosine deamination to <10 %. Detergent decellularization completely removed (<5 %) all these activities. These results demonstrate high intensity of extracellular nucleotide metabolism on valve surface and indicate that various valve decellularization techniques differently affect ecto-enzyme activities that could be important in the development of improved valve prostheses.

Coverage-dependent adsorption and desorption of oxygen on Pd(100)

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

Dunnen, Angela den; Jacobse, Leon; Wiegman, Sandra

2016-06-28

We have studied the adsorption and desorption of O{sub 2} on Pd(100) by supersonic molecular beam techniques and thermal desorption spectroscopy. Adsorption measurements on the bare surface confirm that O{sub 2} initially dissociates for all kinetic energies between 56 and 380 meV and surface temperatures between 100 and 600 K via a direct mechanism. At and below 150 K, continued adsorption leads to a combined O/O{sub 2} overlayer. Dissociation of molecularly bound O{sub 2} during a subsequent temperature ramp leads to unexpected high atomic oxygen coverages, which are also obtained at high incident energy and high surface temperature. At intermediatemore » temperatures and energies, these high final coverages are not obtained. Our results show that kinetic energy of the gas phase reactant and reaction energy dissipated during O{sub 2} dissociation on the cold surface both enable activated nucleation of high-coverage surface structures. We suggest that excitation of local substrate phonons may play a crucial role in oxygen dissociation at any coverage.« less

Interfacial Activation of Candida antarctica Lipase B: Combined Evidence from Experiment and Simulation.

PubMed

Zisis, Themistoklis; Freddolino, Peter L; Turunen, Petri; van Teeseling, Muriel C F; Rowan, Alan E; Blank, Kerstin G

2015-09-29

Lipase immobilization is frequently used for altering the catalytic properties of these industrially used enzymes. Many lipases bind strongly to hydrophobic surfaces where they undergo interfacial activation. Candida antarctica lipase B (CalB), one of the most commonly used biocatalysts, is frequently discussed as an atypical lipase lacking interfacial activation. Here we show that CalB displays an enhanced catalytic rate for large, bulky substrates when adsorbed to a hydrophobic interface composed of densely packed alkyl chains. We attribute this increased activity of more than 7-fold to a conformational change that yields a more open active site. This hypothesis is supported by molecular dynamics simulations that show a high mobility for a small "lid" (helix α5) close to the active site. Molecular docking calculations confirm that a highly open conformation of this helix is required for binding large, bulky substrates and that this conformation is favored in a hydrophobic environment. Taken together, our combined approach provides clear evidence for the interfacial activation of CalB on highly hydrophobic surfaces. In contrast to other lipases, however, the conformational change only affects large, bulky substrates, leading to the conclusion that CalB acts like an esterase for small substrates and as a lipase for substrates with large alcohol substituents.

Bio-sensing applications of cerium oxide nanoparticles: Advantages and disadvantages.

PubMed

Charbgoo, Fahimeh; Ramezani, Mohammad; Darroudi, Majid

2017-10-15

Cerium oxide nanoparticles (CNPs) contain several properties such as catalytic activity, fluorescent quencher and electrochemical, high surface area, and oxygen transfer ability, which have attracted considerable attention in developing high-sensitive biosensors. CNPs can be used as a whole sensor or a part of recognition or transducer element. However, reports have shown that applying these nanoparticles in sensor design could remarkably enhance detection sensitivity. CNP's outstanding properties in biosensors which go from high catalytic activity and surface area to oxygen transfer and fluorescent quenching capabilities are also highlighted. Herein, we discuss the advantages and disadvantages of CNPs-based biosensors that function through various detection modes including colorimetric, electrochemistry, and chemoluminescent regarding the detection of small organic chemicals, metal ions and biomarkers. Copyright © 2017 Elsevier B.V. All rights reserved.

Active Optics: stress polishing of toric mirrors for the VLT SPHERE adaptive optics system.

PubMed

Hugot, Emmanuel; Ferrari, Marc; El Hadi, Kacem; Vola, Pascal; Gimenez, Jean Luc; Lemaitre, Gérard R; Rabou, Patrick; Dohlen, Kjetil; Puget, Pascal; Beuzit, Jean Luc; Hubin, Norbert

2009-05-20

The manufacturing of toric mirrors for the Very Large Telescope-Spectro-Polarimetric High-Contrast Exoplanet Research instrument (SPHERE) is based on Active Optics and stress polishing. This figuring technique allows minimizing mid and high spatial frequency errors on an aspherical surface by using spherical polishing with full size tools. In order to reach the tight precision required, the manufacturing error budget is described to optimize each parameter. Analytical calculations based on elasticity theory and finite element analysis lead to the mechanical design of the Zerodur blank to be warped during the stress polishing phase. Results on the larger (366 mm diameter) toric mirror are evaluated by interferometry. We obtain, as expected, a toric surface within specification at low, middle, and high spatial frequencies ranges.

Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting

NASA Astrophysics Data System (ADS)

Fabbri, Emiliana; Nachtegaal, Maarten; Binninger, Tobias; Cheng, Xi; Kim, Bae-Jung; Durst, Julien; Bozza, Francesco; Graule, Thomas; Schäublin, Robin; Wiles, Luke; Pertoso, Morgan; Danilovic, Nemanja; Ayers, Katherine E.; Schmidt, Thomas J.

2017-09-01

The growing need to store increasing amounts of renewable energy has recently triggered substantial R&D efforts towards efficient and stable water electrolysis technologies. The oxygen evolution reaction (OER) occurring at the electrolyser anode is central to the development of a clean, reliable and emission-free hydrogen economy. The development of robust and highly active anode materials for OER is therefore a great challenge and has been the main focus of research. Among potential candidates, perovskites have emerged as promising OER electrocatalysts. In this study, by combining a scalable cutting-edge synthesis method with time-resolved X-ray absorption spectroscopy measurements, we were able to capture the dynamic local electronic and geometric structure during realistic operando conditions for highly active OER perovskite nanocatalysts. Ba0.5Sr0.5Co0.8Fe0.2O3-δ as nano-powder displays unique features that allow a dynamic self-reconstruction of the material’s surface during OER, that is, the growth of a self-assembled metal oxy(hydroxide) active layer. Therefore, besides showing outstanding performance at both the laboratory and industrial scale, we provide a fundamental understanding of the operando OER mechanism for highly active perovskite catalysts. This understanding significantly differs from design principles based on ex situ characterization techniques.

One-Pot Anchoring of Pd Nanoparticles on Nitrogen-Doped Carbon through Dopamine Self-Polymerization and Activity in the Electrocatalytic Methanol Oxidation Reaction.

PubMed

Li, Xin; Niu, Xiangheng; Zhang, Wenchi; He, Yanfang; Pan, Jianming; Yan, Yongsheng; Qiu, Fengxian

2017-03-09

Exploration of advanced electrocatalysts to promote the sluggish methanol oxidation reaction (MOR) is of vital importance for developing high efficiency and low-cost direct methanol fuel cells. Highly dispersed palladium nanoparticles (Pd NPs) anchored on a nitrogen-doped carbon support were fabricated using a facile one-pot dopamine self-polymerization mediated redox strategy, in which dopamine not only acted as a moderate reductant to induce the formation of Pd NPs during self-polymerization but was also the precursor of the nitrogen-doped carbon support for Pd. The synthesized hybrid features the following characteristics: 1) High dispersity of Pd NPs, which exposed a high abundance of active surfaces and sites for heterogeneous electrocatalysis; 2) metal-support interactions, which may affect the surface chemistry and electron distribution of active Pd NPs; 3) the Pd NPs were partially imbedded or encapsulated into the support, thus reducing the possible agglomeration of Pd NPs during cyclic measurements. The electrocatalyst with such favorable features provided higher mass activity (2.2 times that of commercial Pd/C) and better durability (reduced loss of activity during simulated frequent startup-shutdown operations) for the MOR in alkaline media. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tailoring Enzyme-Like Activities of Gold Nanoclusters by Polymeric Tertiary Amines for Protecting Neurons Against Oxidative Stress.

PubMed

Liu, Ching-Ping; Wu, Te-Haw; Lin, Yu-Lung; Liu, Chia-Yeh; Wang, Sabrina; Lin, Shu-Yi

2016-08-01

The cytotoxicity of nanozymes has drawn much attention recently because their peroxidase-like activity can decompose hydrogen peroxide (H2 O2 ) to produce highly toxic hydroxyl radicals (•OH) under acidic conditions. Although catalytic activities of nanozymes are highly associated with their surface properties, little is known about the mechanism underlying the surface coating-mediated enzyme-like activities. Herein, it is reported for the first time that amine-terminated PAMAM dendrimer-entrapped gold nanoclusters (AuNCs-NH2 ) unexpectedly lose their peroxidase-like activity while still retaining their catalase-like activity in physiological conditions. Surprisingly, the methylated form of AuNCs-NH2 (i.e., MAuNCs-N(+) R3 , where R = H or CH3 ) results in a dramatic recovery of the intrinsic peroxidase-like activity while blocking most primary and tertiary amines (1°- and 3°-amines) of dendrimers to form quaternary ammonium ions (4°-amines). However, the hidden peroxidase-like activity is also found in hydroxyl-terminated dendrimer-encapsulated AuNCs (AuNCs-OH, inside backbone with 3°-amines), indicating that 3°-amines are dominant in mediating the peroxidase-like activity. The possible mechanism is further confirmed that the enrichment of polymeric 3°-amines on the surface of dendrimer-encapsulated AuNCs provides sufficient suppression of the critical mediator •OH for the peroxidase-like activity. Finally, it is demonstrated that AuNCs-NH2 with diminished cytotoxicity have great potential for use in primary neuronal protection against oxidative damage. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Porous carbon derived via KOH activation of a hypercrosslinked porous organic polymer for efficient CO{sub 2}, CH{sub 4}, H{sub 2} adsorptions and high CO{sub 2}/N{sub 2} selectivity

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

Modak, Arindam; Bhaumik, Asim, E-mail: msab@iacs.res.in

2015-12-15

Microporous carbon having Brunauer-Emmett-Teller (BET) surface area of 2186 m{sup 2} g{sup −1} and micropore volume of 0.85 cm{sup 3} g{sup −1} has been synthesized via KOH induced high temperature carbonization of a non-conjugated hypercrosslinked organic polymer. Owing to the templating and activation by KOH, we have succeeded in making a microporous carbon from this porous polymer and the resultant carbon material showed high uptake for CO{sub 2} (7.6 mmol g{sup −1}) and CH{sub 4} (2.4 mmol g{sup −1}) at 1 atm, 273 K together with very good selectivity for the CO{sub 2}/N{sub 2} (30.2) separation. Furthermore, low pressure (1more » atm) H{sub 2} (2.6 wt%, 77 K) and water uptake (57.4 wt%, 298 K) ability of this polymer derived porous activated carbon is noteworthy. - Graphical abstract: Microporous carbon with BET surface area of 2186 m{sup 2} g{sup −1} has been synthesized via KOH activation of a porous organic polymer and it showed high uptake for CO{sub 2} (7.6 mmol g{sup −1}), CH{sub 4} (2.4 mmol g{sup −1}) and H{sub 2} (2.6 wt%) at 1 atm together with very good selectivity for CO{sub 2}. - Highlights: • Porous carbon from hypercrosslinked organic polymer. • KOH activated carbon with BET surface area 2186 m{sup 2} g{sup −1}. • High CO2 uptake (7.6 mmol g{sup −1}) and CO{sub 2}/N{sub 2} selectivity (30.2). • Porous carbon also showed high H{sub 2} (2.6 wt%) and H{sub 2}O (57.4 wt%) uptakes.« less

The Pluto system: Initial results from its exploration by New Horizons.

PubMed

Stern, S A; Bagenal, F; Ennico, K; Gladstone, G R; Grundy, W M; McKinnon, W B; Moore, J M; Olkin, C B; Spencer, J R; Weaver, H A; Young, L A; Andert, T; Andrews, J; Banks, M; Bauer, B; Bauman, J; Barnouin, O S; Bedini, P; Beisser, K; Beyer, R A; Bhaskaran, S; Binzel, R P; Birath, E; Bird, M; Bogan, D J; Bowman, A; Bray, V J; Brozovic, M; Bryan, C; Buckley, M R; Buie, M W; Buratti, B J; Bushman, S S; Calloway, A; Carcich, B; Cheng, A F; Conard, S; Conrad, C A; Cook, J C; Cruikshank, D P; Custodio, O S; Dalle Ore, C M; Deboy, C; Dischner, Z J B; Dumont, P; Earle, A M; Elliott, H A; Ercol, J; Ernst, C M; Finley, T; Flanigan, S H; Fountain, G; Freeze, M J; Greathouse, T; Green, J L; Guo, Y; Hahn, M; Hamilton, D P; Hamilton, S A; Hanley, J; Harch, A; Hart, H M; Hersman, C B; Hill, A; Hill, M E; Hinson, D P; Holdridge, M E; Horanyi, M; Howard, A D; Howett, C J A; Jackman, C; Jacobson, R A; Jennings, D E; Kammer, J A; Kang, H K; Kaufmann, D E; Kollmann, P; Krimigis, S M; Kusnierkiewicz, D; Lauer, T R; Lee, J E; Lindstrom, K L; Linscott, I R; Lisse, C M; Lunsford, A W; Mallder, V A; Martin, N; McComas, D J; McNutt, R L; Mehoke, D; Mehoke, T; Melin, E D; Mutchler, M; Nelson, D; Nimmo, F; Nunez, J I; Ocampo, A; Owen, W M; Paetzold, M; Page, B; Parker, A H; Parker, J W; Pelletier, F; Peterson, J; Pinkine, N; Piquette, M; Porter, S B; Protopapa, S; Redfern, J; Reitsema, H J; Reuter, D C; Roberts, J H; Robbins, S J; Rogers, G; Rose, D; Runyon, K; Retherford, K D; Ryschkewitsch, M G; Schenk, P; Schindhelm, E; Sepan, B; Showalter, M R; Singer, K N; Soluri, M; Stanbridge, D; Steffl, A J; Strobel, D F; Stryk, T; Summers, M E; Szalay, J R; Tapley, M; Taylor, A; Taylor, H; Throop, H B; Tsang, C C C; Tyler, G L; Umurhan, O M; Verbiscer, A J; Versteeg, M H; Vincent, M; Webbert, R; Weidner, S; Weigle, G E; White, O L; Whittenburg, K; Williams, B G; Williams, K; Williams, S; Woods, W W; Zangari, A M; Zirnstein, E

2015-10-16

The Pluto system was recently explored by NASA's New Horizons spacecraft, making closest approach on 14 July 2015. Pluto's surface displays diverse landforms, terrain ages, albedos, colors, and composition gradients. Evidence is found for a water-ice crust, geologically young surface units, surface ice convection, wind streaks, volatile transport, and glacial flow. Pluto's atmosphere is highly extended, with trace hydrocarbons, a global haze layer, and a surface pressure near 10 microbars. Pluto's diverse surface geology and long-term activity raise fundamental questions about how small planets remain active many billions of years after formation. Pluto's large moon Charon displays tectonics and evidence for a heterogeneous crustal composition; its north pole displays puzzling dark terrain. Small satellites Hydra and Nix have higher albedos than expected. Copyright © 2015, American Association for the Advancement of Science.

ROLE OF HCL IN ADSORPTION OF ELEMENTAL MERCURY VAPOR BY CALCIUM-BASED SORBENTS

EPA Science Inventory

The paper gives results of a study to identify active sites and surface functional groups that may contribute to the adsorption of elemental mercury (Hg?) by relatively inexpensive calcium (Ca)-based sorbents. (NOTE: Hg? capture has been mostly investigated using high-surface-ar...

Nano-organocatalyst: Magnetically retrievable ferrite-anchored glutathione for microwave-assisted Paal-Knorr reaction, Aza-Michael addition and pyrazole synthesis

EPA Science Inventory

Postsynthetic surface modification of magnetic nanoparticles by glutathione imparts desirable chemical functionality and enables the generation of catalytic sites on the surfaces of ensuing organocatalysts. In this article, we discuss the developments, unique activity and high s...

Low proliferation and high apoptosis of osteoblastic cells on hydrophobic surface are associated with defective Ras signaling

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

Chang, Eun-Ju; Kim, Hong-Hee; Huh, Jung-Eun

2005-02-01

The hydrophobic (HPB) nature of most polymeric biomaterials has been a major obstacle in using those materials in vivo due to low compatibility with cells. However, there is little knowledge of the molecular detail to explain how surface hydrophobicity affects cell responses. In this study, we compared the proliferation and apoptosis of human osteoblastic MG63 cells adhered to hydrophilic (HPL) and hydrophobic surfaces. On the hydrophobic surface, less formation of focal contacts and actin stress fibers, a delay in cell cycle progression, and an increase in apoptosis were observed. By using fibroblast growth factor 1 (FGF1) as a model growthmore » factor, we also investigated intracellular signaling pathways on hydrophilic and hydrophobic surfaces. The activation of Ras, Akt, and ERK by FGF1 was impaired in MG63 cells on the hydrophobic surface. The overexpression of constitutively active form of Ras and Akt rescued those cells from apoptosis and recovered cell cycle progression. Furthermore, their overexpression also restored the actin cytoskeletal organization on the hydrophobic surface. Finally, the proliferative, antiapoptotic, and cytoskeletal effects of constitutively active Ras in MG63 cells on the hydrophobic surface were blocked by wortmannin and PD98059 that inhibit Akt and ERK activation, respectively. Therefore, our results suggest that the activation of Ras and its downstream molecules Akt and ERK to an appropriate level is one of crucial elements in the determination of osteoblast cell responses. The Ras pathway may represent a cell biological target that should be considered for successful surface modification of biomaterials to induce adequate cell responses in the bone tissue.« less

High-resolution lidar topography of the Puget Lowland, Washington - A bonanza for earth science

USGS Publications Warehouse

Haugerud, R.A.; Harding, D.J.; Johnson, S.Y.; Harless, J.L.; Weaver, C.S.; Sherrod, B.L.

2003-01-01

More than 10,000 km2 of high-resolution, public-domain topography acquired by the Puget Sound Lidar Consortium is revolutionizing investigations of active faulting, continental glaciation, landslides, and surficial processes in the seismically active Puget Lowland. The Lowland-the population and economic center of the Pacific Northwest-presents special problems for hazards investigations, with its young glacial topography, dense forest cover, and urbanization. Lidar mapping during leaf-off conditions has led to a detailed digital model of the landscape beneath the forest canopy. The surface thus revealed contains a rich and diverse record of previously unknown surface-rupturing faults, deep-seated landslides, uplifted Holocene and Pleistocene beaches, and subglacial and periglacial features. More than half a dozen suspected postglacial fault scarps have been identified to date. Five scarps that have been trenched show evidence of large, Holocene, surface-rupturing earthquakes.

Electrocatalysis paradigm for protection of cathode materials in high-voltage lithium-ion batteries

DOE PAGES

Shkrob, Ilya A.; Abraham, Daniel P.

2016-07-06

A new mechanistic framework is suggested to account for the protective action of certain electrolyte additives on high-voltage positive electrode (cathode) materials. The mechanism involves inactivation of catalytically active centers on the electrode active materials through fragmentation reactions involving molecules at its surface. The cathode protection additives oxidize before the solvent and serve as sacrificial inhibitors of the catalytic centers. Without the additive, the surface oxidation of the solvent (like solvent oxidation in the bulk) yields H loss radicals and releases the proton that can combine with anions forming corrosive acids. This proton-release reaction is demonstrated experimentally for boronate additives.more » Specific radical reactions for the latter additives on the electrode surface are suggested. Furthermore, the same approach can be used to rationalize the protective action of other additives and account for various observations regarding their performance.« less

Pleurochrysis pseudoroscoffensis (Prymnesiophyceae) blooms on the surface of the Salton Sea, California

USGS Publications Warehouse

Reifel, K.M.; McCoy, M.P.; Tiffany, M.A.; Rocke, T.E.; Trees, C.C.; Barlow, S.B.; Faulkner, D.J.; Hurlbert, S.H.

2001-01-01

Dense populations of the coccolithophore Pleurochrysis pseudoroscoffensis were found in surface films at several locations around the Salton Sea in February-August, 1999. An unidentified coccolithophorid was also found in low densities in earlier studies of the lake (1955-1956). To our knowledge, this is the first record of this widespread marine species in any lake. Samples taken from surface films typically contained high densities of one or two other phytoplankton species as well as high densities of the coccolithophore. Presence or absence of specific algal pigments was used to validate direct cell counts. In a preliminary screen using a brine shrimp lethality assay, samples showed moderate activity. Extracts were then submitted to a mouse bioassay, and no toxic activity was observed. These results indicate that blooms of P. pseudoroscoffensis are probably not toxic to vertebrates and do not contribute to the various mortality events of birds and fish that occur in the Salton Sea.

Adsorbed Natural Gas Storage in Optimized High Surface Area Microporous Carbon

NASA Astrophysics Data System (ADS)

Romanos, Jimmy; Rash, Tyler; Nordwald, Erik; Shocklee, Joshua Shawn; Wexler, Carlos; Pfeifer, Peter

2011-03-01

Adsorbed natural gas (ANG) is an attractive alternative technology to compressed natural gas (CNG) or liquefied natural gas (LNG) for the efficient storage of natural gas, in particular for vehicular applications. In adsorbants engineered to have pores of a few molecular diameters, a strong van der Walls force allows reversible physisorption of methane at low pressures and room temperature. Activated carbons were optimized for storage by varying KOH:C ratio and activation temperature. We also consider the effect of mechanical compression of powders to further enhance the volumetric storage capacity. We will present standard porous material characterization (BET surface area and pore-size distribution from subcritical N2 adsorption) and methane isotherms up to 250 bar at 293K. At sufficiently high pressure, specific surface area, methane binding energy and film density can be extracted from supercritical methane adsorption isotherms. Research supported by the California Energy Commission (500-08-022).

Electrocatalysis paradigm for protection of cathode materials in high-voltage lithium-ion batteries

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

Shkrob, Ilya A.; Abraham, Daniel P.

A new mechanistic framework is suggested to account for the protective action of certain electrolyte additives on high-voltage positive electrode (cathode) materials. The mechanism involves inactivation of catalytically active centers on the electrode active materials through fragmentation reactions involving molecules at its surface. The cathode protection additives oxidize before the solvent and serve as sacrificial inhibitors of the catalytic centers. Without the additive, the surface oxidation of the solvent (like solvent oxidation in the bulk) yields H loss radicals and releases the proton that can combine with anions forming corrosive acids. This proton-release reaction is demonstrated experimentally for boronate additives.more » Specific radical reactions for the latter additives on the electrode surface are suggested. Furthermore, the same approach can be used to rationalize the protective action of other additives and account for various observations regarding their performance.« less

Carbon nanotubes decorated with Pt nanoparticles via electrostatic self-assembly: a highly active oxygen reduction electrocatalyst

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

Zhang, Sheng; Shao, Yuyan; Yin, Geping

2010-03-20

Carbon nanotubes (CNTs) are noncovalently functionalized with poly(allylamine hydrochloride) (PAH) and then employed as the support of Pt nanoparticles. X-Ray photoelectron spectroscopy confirms the successful functionalization of CNTs with PAH. The negatively charged Pt precursors are adsorbed on positively charged PAH-wrapping CNTs surface via electrostatic self-assembly and then in situ reduced in ethylene glycol. X-Ray diffraction and transmission electron microscope images reveal that Pt nanoparticles with an average size of 2.6 nm are uniformly dispersed on CNT surface. Pt/PAH-CNTs exhibit unexpectedly high activity towards oxygen reduction reaction, which can be attributed to the large electrochemical surface area of Pt nanoparticles.more » It also shows enhanced electrochemical stability due to the structural integrity of PAH-CNTs. This provides a facile approach to synthesize CNTs-based nanoelectrocatalysts.« less

Cleaning and passivation of copper surfaces to remove surface radioactivity and prevent oxide formation

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

Hoppe, Eric W.; Seifert, Allen; Aalseth, Craig E.

High-purity copper is an attractive material for constructing ultra-low-background radiation measurement devices. Many low-background experiments using high-purity copper have indicated surface contamination emerges as the dominant background. Radon daughters plate out on exposed surfaces, leaving a residual 210Pb background that is difficult to avoid. Dust is also a problem; even under cleanroom conditions, the amount of U and Th deposited on surfaces can represent the largest remaining background. To control these backgrounds, a copper cleaning chemistry has been developed. Designed to replace an effective, but overly aggressive concentrated nitric acid etch, this peroxide-based solution allows for a more controlled cleaningmore » of surfaces. The acidified hydrogen peroxide solution will generally target the Cu+/Cu2+ species which are the predominant surface participants, leaving the bulk of copper metal intact. This preserves the critical tolerances of parts and eliminates significant waste disposal issues. Accompanying passivation chemistry has also been developed that protects copper surfaces from oxidation. Using a high-activity polonium surface spike, the most difficult-to-remove daughter isotope of radon, the performance of these methods are quantified. © 2001 Elsevier Science. All rights reserved« less

Comparison of vision through surface modulated and spatial light modulated multifocal optics.

PubMed

Vinas, Maria; Dorronsoro, Carlos; Radhakrishnan, Aiswaryah; Benedi-Garcia, Clara; LaVilla, Edward Anthony; Schwiegerling, Jim; Marcos, Susana

2017-04-01

Spatial-light-modulators (SLM) are increasingly used as active elements in adaptive optics (AO) systems to simulate optical corrections, in particular multifocal presbyopic corrections. In this study, we compared vision with lathe-manufactured multi-zone (2-4) multifocal, angularly and radially, segmented surfaces and through the same corrections simulated with a SLM in a custom-developed two-active-element AO visual simulator. We found that perceived visual quality measured through real manufactured surfaces and SLM-simulated phase maps corresponded highly. Optical simulations predicted differences in perceived visual quality across different designs at Far distance, but showed some discrepancies at intermediate and near.

Comparison of vision through surface modulated and spatial light modulated multifocal optics

PubMed Central

Vinas, Maria; Dorronsoro, Carlos; Radhakrishnan, Aiswaryah; Benedi-Garcia, Clara; LaVilla, Edward Anthony; Schwiegerling, Jim; Marcos, Susana

2017-01-01

Spatial-light-modulators (SLM) are increasingly used as active elements in adaptive optics (AO) systems to simulate optical corrections, in particular multifocal presbyopic corrections. In this study, we compared vision with lathe-manufactured multi-zone (2-4) multifocal, angularly and radially, segmented surfaces and through the same corrections simulated with a SLM in a custom-developed two-active-element AO visual simulator. We found that perceived visual quality measured through real manufactured surfaces and SLM-simulated phase maps corresponded highly. Optical simulations predicted differences in perceived visual quality across different designs at Far distance, but showed some discrepancies at intermediate and near. PMID:28736655

Synthesis and study of electrolytic materials with a high-energy defect structure and a developed surface

NASA Astrophysics Data System (ADS)

Gryzunova, N. N.; Vikarchuk, A. A.; Tyur'kov, M. N.

2016-10-01

The defect structure of the electrolytic copper coatings formed upon mechanical activation of a cathode is described. These coatings are shown to have a fragmented structure containing disclination-type defects, namely, terminating dislocation, disclination and twin boundaries; partial disclinations, misorientation bands; and twin layers. They have both growth and deformation origins. The mechanisms of formation of the structural defects are discussed. It is experimentally proved that part of the elastic energy stored in the crystal volume during electrocrystallization can be converted into surface energy. As a result, catalytically active materials with a large developed surface can be synthesized.

An alkaline active xylanase: insights into mechanisms of high pH catalytic adaptation.

PubMed

Mamo, Gashaw; Thunnissen, Marjolein; Hatti-Kaul, Rajni; Mattiasson, Bo

2009-09-01

The alkaliphilic bacterium, Bacillus halodurans S7, produces an alkaline active xylanase (EC 3.2.1.8), which differs from many other xylanases in being operationally stable under alkaline conditions as well as at elevated temperature. Compared to non-alkaline active xylanases, this enzyme has a high percent composition of acidic amino acids which results in high ratio of negatively to positively charged residues. A positive correlation was observed between the charge ratio and the pH optima of xylanases. The recombinant xylanase was crystallized using a hanging drop diffusion method. The crystals belong to the space group P2(1)2(1)2(1) and the structure was determined at a resolution of 2.1 A. The enzyme has the common eight-fold TIM-barrel structure of family 10 xylanases; however, unlike non-alkaline active xylanases, it has a highly negatively charged surface and a deeper active site cleft. Mutational analysis of non-conserved amino acids which are close to the acid/base residue has shown that Val169, Ile170 and Asp171 are important to hydrolyze xylan at high pH. Unlike the wild type xylanase which has optimum pH at 9-9.5, the triple mutant xylanase (V169A, I170F and D171N), which was constructed using sequence information of alkaline sensitive xylanses was optimally active around pH 7. Compared to non-alkaline active xylanases, the alkaline active xylanases have highly acidic surfaces and fewer solvent exposed alkali labile residues. Based on these results obtained from sequence, structural and mutational analysis, the possible mechanisms of high pH stability and catalysis are discussed. This will provide useful information to understand the mechanism of high pH adaptation and engineering of enzymes that can be operationally stable at high pH.

A novel electroless method to prepare a platinum electrocatalyst on diamond for fuel cell applications

NASA Astrophysics Data System (ADS)

Lyu, Xiao; Hu, Jingping; Foord, John S.; Wang, Qiang

2013-11-01

A novel electroless deposition method was demonstrated to prepare a platinum electrocatalyst on boron doped diamond (BDD) substrates without the need for pre-activation. This green method addresses the uniformity and particle size issues associated with electrodeposition and circumvents the pre-activation procedure which is necessary for conventional electroless deposition. The inert BDD substrate formed a galvanic couple with an iron wire, to overcome the activation barrier associated with conventional electroless deposition on diamond, leading to the formation of Pt nanoparticles on the electrode surface in a galvanic process coupled to a chemical process. When sodium hypophosphite was employed as the reducing agent to drive the electroless reaction Pt deposits which were contaminated with iron and phosphorus resulted. In contrast, the reducing agent ascorbic acid gave rise to high purity Pt nanoparticles. Optimal deposition conditions with respect to bath temperature, pH value and stabilizing additives are identified. Using this approach, high purity and uniformly distributed platinum nanoparticles are obtained on the diamond electrode surface, which demonstrate a high electrochemical activity towards methanol oxidation.

Mesoporous MnCeO x solid solutions for low temperature and selective oxidation of hydrocarbons

DOE PAGES

Zhang, Pengfei; Lu, Hanfeng; Zhou, Ying; ...

2015-10-15

The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C–H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn 0.5Ce 0.5O x solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100–120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140–160 °C, conversion: 3-5%). Finally, the high activity can be attributed to the formation of a Mn 0.5Ce 0.5O xmore » solid solution with an ultrahigh manganese doping concentration in the CeO 2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn 4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface.« less

Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons

PubMed Central

Zhang, Pengfei; Lu, Hanfeng; Zhou, Ying; Zhang, Li; Wu, Zili; Yang, Shize; Shi, Hongliang; Zhu, Qiulian; Chen, Yinfei; Dai, Sheng

2015-01-01

The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C–H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn0.5Ce0.5Ox solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100–120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140–160 °C, conversion: 3-5%). The high activity can be attributed to the formation of a Mn0.5Ce0.5Ox solid solution with an ultrahigh manganese doping concentration in the CeO2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface. PMID:26469151

Fabrication of high flux and antifouling mixed matrix fumarate-alumoxane/PAN membranes via electrospinning for application in membrane bioreactors

NASA Astrophysics Data System (ADS)

Moradi, Golshan; Zinadini, Sirus; Rajabi, Laleh; Dadari, Soheil

2018-01-01

The nanofibrous Polyacrylonitrile (PAN) membranes embedded with fumarate-alumoxane (Fum-A) nanoparticles were prepared via electrospinning technique as high flux and antifouling membranes for membrane bioreactor (MBR) applications. The effect of Fum-A nanoparticles on membrane morphology, surface hydrophilicity, pure water flux, effluent turbidity and the antifouling property was investigated. Fum-A is a carboxylate-alumoxane nanoparticle covered by extra hydroxyl and carboxylate groups on its surface. By embedding Fum-A nanoparticles into the spinning solution, the surface hydrophilicity and pure water flux of the resulted membranes were improved. The smooth surface of fibers at the low amount of nanoparticles and the agglomeration of nanoparticles at their high concentration were shown in SEM images of the membranes surface. The energy dispersive spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR) analysis of the prepared Fum-A/PAN membrane confirmed the presence of carboxylate and hydroxyl functional groups of Fum-A nanoparticles on the surface of the Fum-A nanoparticles containing membrane. The results obtained from the filtration of activated sludge suspension revealed that by addition of a low amount of Fum-A nanoparticles, the irreversible fouling was significantly decreased due to the higher hydrophilicity. The Fum-A/PAN membranes showed superior permeate flux and antifouling properties compared to bare electrospun PAN membrane. Finally, 2 wt.% Fum-A/PAN membrane exhibited the highest FRR of 96% and the lowest irreversible fouling of 4% with excellent durability of antifouling property during twenty repeated activated sludge filtrations.

The Role of Ru Redox in pH-Dependent Oxygen Evolution on Rutile Ruthenium Dioxide Surfaces

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

Stoerzinger, Kelsey A.; Rao, Reshma R.; Wang, Xiao Renshaw

Rutile RuO 2 is known to exhibit high catalytic activity for the oxygen evolution reaction (OER) and large pseudocapacitance associated with redox of surface Ru, however the mechanistic link between these properties and the role of pH is yet to be understood. Here we report that the OER activities of the (101), (001) and (111) RuO 2 surfaces were found to increase while the potential of a pseudocapacitive feature just prior to OER shifted to lower potentials (“super-Nernstian” shift) with increasing pH on the reversible hydrogen electrode (RHE) scale. This behavior is in contrast to the (100) and (110) surfacesmore » that have pH-independent Ru redox and OER activity. The link in catalytic and pseudocapacitive behavior illustrates the importance of this redox feature in generating active sites, building new mechanistic understanding of the OER.« less

Total pollen counts do not influence active surface measurements

NASA Astrophysics Data System (ADS)

Moshammer, Hanns; Schinko, Herwig; Neuberger, Manfred

We investigated the temporal association of various aerosol parameters with pollen counts in the pollen season (April 2001) in Linz, Austria. We were especially interested in the relationship between active surface (or Fuchs' surface) because we had shown previously (Atmos. Environ. 37 (2003) 1737-1744) that this parameter during the same observation period was a better predictor for acute respiratory symptoms in school children (like wheezing, shortness of breath, and cough) and reduced lung function on the same day than particle mass (PM 10). While active surface is most sensitive for fine particles with a diameter of less than 100 nm it has no strict upper cut-off regarding particle size and so could eventually be influenced also by larger particles if their numbers were high. All particle mass parameters tested (TSP, PM 10, PM 1) were weakly ( r approximately 0.2) though significantly correlated with pollen counts but neither was active surface nor total particle counts (CPC). The weak association of particle mass and pollen counts was due mainly to similar diurnal variations and a linear trend over time. Only the mass of the coarse fraction (TSP minus PM 10) remained associated with pollen counts significantly after controlling for these general temporal patterns.

Landscape linkages between geothermal activity and solute composition and ecological response in surface waters draining the Atlantic slope of Costa Rica

USGS Publications Warehouse

Pringle, Catherine M.; Rowe, Gary L.; Triska, Frank J.; Fernandez, Jose F.; West, John

1993-01-01

Surface waters draining three different volcanoes in Costa Rica, ranging from dormant to moderately active to explosive, have a wide range of solute compositions that partly reflects the contribution of different types of solute-rich, geothermal waters. Three major physical transport vectors affect flows of geothermally derived solutes: thermally driven convection of volcanic gases and geothermal fluids; lateral and gravity-driven downward transport of geothermal fluids; and wind dispersion of ash, gases, and acid rain. Specific vector combinations interact to determine landscape patterns in solute chemistry and biota: indicator taxa of algae and bacteria reflect factors such as high temperature, wind-driven or hydrologically transported acidity, high concentrations of various solutes, and chemical precipitation reactions. Many streams receiving geothermally derived solutes have high levels of soluble reactive phosphorus (SRP) (up to 400 µg liter−1), a nutrient that is typically not measured in geochemical studies of geothermal waters. Regional differences in levels of SRP and other solutes among volcanoes were typically not significant due to high local variation in solute levels among geothermally modified streams and between geothermally modified and unmodified streams on each volcano. Geothermal activity along the volcanic spine of Costa Rica provides a natural source of phosphorus, silica, and other solutes and plays an important role in determining emergent landscape patterns in the solute chemistry of surface waters and aquatic biota.

Optimization of preparation of antioxidative peptides from pumpkin seeds using response surface method.

PubMed

Fan, Sanhong; Hu, Yanan; Li, Chen; Liu, Yanrong

2014-01-01

Protein isolates of pumpkin (Cucurbita pepo L) seeds were hydrolyzed by acid protease to prepare antioxidative peptides. The hydrolysis conditions were optimized through Box-Behnken experimental design combined with response surface method (RSM). The second-order model, developed for the DPPH radical scavenging activity of pumpkin seed hydrolysates, showed good fit with the experiment data with a high value of coefficient of determination (0.9918). The optimal hydrolysis conditions were determined as follows: hydrolyzing temperature 50°C, pH 2.5, enzyme amount 6000 U/g, substrate concentration 0.05 g/ml and hydrolyzing time 5 h. Under the above conditions, the scavenging activity of DPPH radical was as high as 92.82%.

A RecA Protein Surface Required for Activation of DNA Polymerase V

PubMed Central

Gruber, Angela J.; Erdem, Aysen L.; Sabat, Grzegorz; Karata, Kiyonobu; Jaszczur, Malgorzata M.; Vo, Dan D.; Olsen, Tayla M.; Woodgate, Roger; Goodman, Myron F.; Cox, Michael M.

2015-01-01

DNA polymerase V (pol V) of Escherichia coli is a translesion DNA polymerase responsible for most of the mutagenesis observed during the SOS response. Pol V is activated by transfer of a RecA subunit from the 3'-proximal end of a RecA nucleoprotein filament to form a functional complex called DNA polymerase V Mutasome (pol V Mut). We identify a RecA surface, defined by residues 112-117, that either directly interacts with or is in very close proximity to amino acid residues on two distinct surfaces of the UmuC subunit of pol V. One of these surfaces is uniquely prominent in the active pol V Mut. Several conformational states are populated in the inactive and active complexes of RecA with pol V. The RecA D112R and RecA D112R N113R double mutant proteins exhibit successively reduced capacity for pol V activation. The double mutant RecA is specifically defective in the ATP binding step of the activation pathway. Unlike the classic non-mutable RecA S117F (recA1730), the RecA D112R N113R variant exhibits no defect in filament formation on DNA and promotes all other RecA activities efficiently. An important pol V activation surface of RecA protein is thus centered in a region encompassing amino acid residues 112, 113, and 117, a surface exposed at the 3'-proximal end of a RecA filament. The same RecA surface is not utilized in the RecA activation of the homologous and highly mutagenic RumA'2B polymerase encoded by the integrating-conjugative element (ICE) R391, indicating a lack of structural conservation between the two systems. The RecA D112R N113R protein represents a new separation of function mutant, proficient in all RecA functions except SOS mutagenesis. PMID:25811184

ENHANCED BIODEGRADATION OF IOPROMIDE AND TRIMETHOPRIM IN NITRIFYING ACTIVATED SLUDGE

EPA Science Inventory

Iopromide and trimethoprim are frequently detected pharmaceuticals in effluents of wastewater treatment plants and in surface waters due to their persistence and high usage. Laboratory scale experiments showed that a significantly higher removal rate in nutrifying activated sludg...

Peeling the astronomical onion.

PubMed

Rosu-Finsen, Alexander; Marchione, Demian; Salter, Tara L; Stubbing, James W; Brown, Wendy A; McCoustra, Martin R S

2016-11-23

Water ice is the most abundant solid in the Universe. Understanding the formation, structure and multiplicity of physicochemical roles for water ice in the cold, dense interstellar environments in which it is predominantly observed is a crucial quest for astrochemistry as these are regions active in star and planet formation. Intuitively, we would expect the mobility of water molecules deposited or synthesised on dust grain surfaces at temperatures below 50 K to be very limited. This work delves into the thermally-activated mobility of H 2 O molecules on model interstellar grain surfaces. The energy required to initiate this process is studied by reflection-absorption infrared spectroscopy of small quantities of water on amorphous silica and highly oriented pyrolytic graphite surfaces as the surface is annealed. Strongly non-Arrhenius behaviour is observed with an activation energy of 2 kJ mol -1 on the silica surface below 25 K and 0 kJ mol -1 on both surfaces between 25 and 100 K. The astrophysical implication of these results is that on timescales shorter than that estimated for the formation of a complete monolayer of water ice on a grain, aggregation of water ice will result in a non-uniform coating of water, hence leaving bare grain surface exposed. Other molecules can thus be formed or adsorbed on this bare surface.

Effects of Surface Oxygen on the Performance of Carbon as an Anode in Lithium-Ion Batteries

NASA Technical Reports Server (NTRS)

Hung, Ching-Cheh; Clark, Gregory W.

2001-01-01

Carbon materials with similar bulk structure but different surface oxygen were compared for their performance as anodes in lithium-ion battery. The bulk structure was such that the graphene planes were perpendicular to the surface. Three types of surfaces were examined: surface containing C=O type oxygen. surface containing -O-C type oxygen, and surface containing high concentration of active sites. The test involved cycles of lithium insertion into and release from the carbon materials, which was in the half cells of carbon/saturated LiI-50/50 (vol %) EC and DMC/lithium. During the first cycle of lithium insertion, the presence of adsorbed oxygen, -O-C type oxygen, active carbon sites, and C=O type oxygen resulted in the formation of solid-electrolyte interface (SEI) when the carbon's voltage relative to lithium metal was >1.35, 1 to 1.35, 0.5 to 1, and 0.67 to 0.7 V, respectively. An optimum -O-C type oxygen and a minimum C=O type oxygen was found to increase the reversible and decrease the irreversible capacity of carbon. Active sites on the carbon surface result in a large irreversible capacity and a second lithium insertion-release mechanism. However, this new mechanism has a short cycle life.

Microbial population and functional dynamics associated with surface potential and carbon metabolism

PubMed Central

Ishii, Shun'ichi; Suzuki, Shino; Norden-Krichmar, Trina M; Phan, Tony; Wanger, Greg; Nealson, Kenneth H; Sekiguchi, Yuji; Gorby, Yuri A; Bretschger, Orianna

2014-01-01

Microbial extracellular electron transfer (EET) to solid surfaces is an important reaction for metal reduction occurring in various anoxic environments. However, it is challenging to accurately characterize EET-active microbial communities and each member's contribution to EET reactions because of changes in composition and concentrations of electron donors and solid-phase acceptors. Here, we used bioelectrochemical systems to systematically evaluate the synergistic effects of carbon source and surface redox potential on EET-active microbial community development, metabolic networks and overall electron transfer rates. The results indicate that faster biocatalytic rates were observed under electropositive electrode surface potential conditions, and under fatty acid-fed conditions. Temporal 16S rRNA-based microbial community analyses showed that Geobacter phylotypes were highly diverse and apparently dependent on surface potentials. The well-known electrogenic microbes affiliated with the Geobacter metallireducens clade were associated with lower surface potentials and less current generation, whereas Geobacter subsurface clades 1 and 2 were associated with higher surface potentials and greater current generation. An association was also observed between specific fermentative phylotypes and Geobacter phylotypes at specific surface potentials. When sugars were present, Tolumonas and Aeromonas phylotypes were preferentially associated with lower surface potentials, whereas Lactococcus phylotypes were found to be closely associated with Geobacter subsurface clades 1 and 2 phylotypes under higher surface potential conditions. Collectively, these results suggest that surface potentials provide a strong selective pressure, at the species and strain level, for both solid surface respirators and fermentative microbes throughout the EET-active community development. PMID:24351938

Incorporating Rich Mesoporosity into a Ceria-Based Catalyst via Mechanochemistry

DOE PAGES

Zhan, Wangcheng; Yang, Shize; Zhang, Pengfei; ...

2017-08-15

Ceria-based materials possessing mesoporous structures afford higher activity than the corresponding bulk materials in CO oxidation and other catalytic applications, because of the wide pore channel and high surface area. The development of a direct, template-free, and scalable technology for directing porosity inside ceriabased materials is highly welcome. Here in this paper, a family of mesoporous transition-metaldoped ceria catalysts with specific surface areas up to 122 m 2 g -1 is constructed by mechanochemical grinding. No templates, additives, or solvents are needed in this process, while the mechanochemistry-mediated restructuring and the decomposing of the organic group led to plentiful mesopores.more » Interestingly, the copper species are evenly dispersed in the ceria matrix at the atomic scale, as observed in high resolution scanning transmission electron microscopy in high angle annular dark field. The copper-doped ceria materials show good activity in the CO oxidation.« less

High-Performance Ru1 /CeO2 Single-Atom Catalyst for CO Oxidation: A Computational Exploration.

PubMed

Li, Fengyu; Li, Lei; Liu, Xinying; Zeng, Xiao Cheng; Chen, Zhongfang

2016-10-18

By means of density functional theory computations, we examine the stability and CO oxidation activity of single Ru on CeO 2 (111), TiO 2 (110) and Al 2 O 3 (001) surfaces. The heterogeneous system Ru 1 /CeO 2 has very high stability, as indicated by the strong binding energies and high diffusion barriers of a single Ru atom on the ceria support, while the Ru atom is rather mobile on TiO 2 (110) and Al 2 O 3 (001) surfaces and tends to form clusters, excluding these systems from having a high efficiency per Ru atom. The Ru 1 /CeO 2 exhibits good catalytic activity for CO oxidation via the Langmuir-Hinshelwood mechanism, thus is a promising single-atom catalyst. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A key parameter on the adsorption of diluted aniline solutions with activated carbons: The surface oxygen content.

PubMed

Pardo, Beatrice; Ferrer, Nabí; Sempere, Julià; Gonzalez-Olmos, Rafael

2016-11-01

A total of 11 different commercial activated carbons (AC) with well characterized textural properties and oxygen surface content were tested as adsorbents for the removal of aniline as a target water pollutant. The maximum adsorption capacity of aniline for the studied AC was from 138.9 to 257.9 mg g(-1) at 296.15 K and it was observed to be strongly related to the textural properties of the AC, mainly with the BET surface area and the micropore volume. It was not observed any influence of the oxygen surface content of the AC on the maximum adsorption capacity. However, it was found that at low aniline aqueous concentration, the presence of oxygen surface groups plays a dominant role during the adsorption. A high concentration of oxygen surface groups, mainly carboxylic and phenolic groups, decreases the aniline adsorption regardless of the surface area of the AC. Copyright © 2016 Elsevier Ltd. All rights reserved.

Adsorption and reaction of CO and H2O on WC(0001) surface: A first-principles investigation

NASA Astrophysics Data System (ADS)

Tong, Yu-Jhe; Wu, Shiuan-Yau; Chen, Hsin-Tsung

2018-01-01

We have performed a spin-polarized density functional theory (DFT) study for understanding the detailed reaction mechanism of CO and H2O on WC (0001) surface. The adsorption properties and vibrational frequencies of H2O, OH, O, H, CO and CO2 on the WC (0001) surface were illustrated. These results are well in consistent with the experimental observations studied by temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). Based on the adsorption results, potential energy profiles of H2O and OH dehydrogenation and HCO, COH, COOH, and CO2 formation on the WC (0001) surface were predicted. The calculation results demonstrated that the WC (0001) surface as Fe (110) surface exhibits significantly reaction activity toward the dehydrogenation of H2O and OH but less activity toward the formation of HCO, COH, COOH and CO2 compared to the Cu (111) and Pt (111) surfaces.

Fundamental Pathways for the Adsorption and Transport of Hydrogen on TiO2 Surfaces: Origin for Effective Sensing at about Room Temperature.

PubMed

Wang, Zhuo; Xia, Xiaohong; Guo, Meilan; Shao, Guosheng

2016-12-28

Effective detection of hydrogen at lowered temperature is highly desirable in promoting safety in using this abundant gas as a clean energy source. Through first-principle calculations in the framework of density functional theory, we find that the high-energy (002) surface for rutile TiO 2 is significantly more effective in adsorbing hydrogen atoms through dissociating hydrogen molecules. The pathways for the dissociation of hydrogen molecules and sequential migration of hydrogen atoms are identified through searching along various transitional states. Pathways of low potential barriers indicate promise for hydrogen sensing, even close to room temperature. This has been proven through sensors made of thin films of well-aligned rutile nanorods, wherein the high-energy (002) surface dictates the top surface of the active layer of the sensors.

2D and 3D imaging of the gas phase close to an operating model catalyst by planar laser induced fluorescence

NASA Astrophysics Data System (ADS)

Blomberg, Sara; Zhou, Jianfeng; Gustafson, Johan; Zetterberg, Johan; Lundgren, Edvin

2016-11-01

In recent years, efforts have been made in catalysis related surface science studies to explore the possibilities to perform experiments at conditions closer to those of a technical catalyst, in particular at increased pressures. Techniques such as high pressure scanning tunneling/atomic force microscopy (HPSTM/AFM), near ambient pressure x-ray photoemission spectroscopy (NAPXPS), surface x-ray diffraction (SXRD) and polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS) at semi-realistic conditions have been used to study the surface structure of model catalysts under reaction conditions, combined with simultaneous mass spectrometry (MS). These studies have provided an increased understanding of the surface dynamics and the structure of the active phase of surfaces and nano particles as a reaction occurs, providing novel information on the structure/activity relationship. However, the surface structure detected during the reaction is sensitive to the composition of the gas phase close to the catalyst surface. Therefore, the catalytic activity of the sample itself will act as a gas-source or gas-sink, and will affect the surface structure, which in turn may complicate the assignment of the active phase. For this reason, we have applied planar laser induced fluorescence (PLIF) to the gas phase in the vicinity of an active model catalysts. Our measurements demonstrate that the gas composition differs significantly close to the catalyst and at the position of the MS, which indeed should have a profound effect on the surface structure. However, PLIF applied to catalytic reactions presents several beneficial properties in addition to investigate the effect of the catalyst on the effective gas composition close to the model catalyst. The high spatial and temporal resolution of PLIF provides a unique tool to visualize the on-set of catalytic reactions and to compare different model catalysts in the same reactive environment. The technique can be applied to a large number of molecules thanks to the technical development of lasers and detectors over the last decades, and is a complementary and visual alternative to traditional MS to be used in environments difficult to asses with MS. In this article we will review general considerations when performing PLIF experiments, our experimental set-up for PLIF and discuss relevant examples of PLIF applied to catalysis.

Combining surface enhanced Raman scattering (SERS) and high-performance thin-layer chromatography (HPTLC)

NASA Astrophysics Data System (ADS)

Koglin, E.

A new method for preparing SERS active surfaces using silver colloidal spheres deposited on HPTLC plates, used for thin-layer chromatography, is discussed in detail. The sensitivity of these activated HPTLC plates is so high that in-situ vibrational investigations of chromatogram spots are possible at the nanogram level. The HPTLC/SERS spectra of purine, benzoic acid and 1-nitro-pyrene adsorbed on silver colloidal activated silica gel plates are measured in the nanogram region. In addition we also report in this paper on the results of a feasibility study performed to evaluate the analytical potential of micro-Raman spectroscopy (triple monochromator, multichannel detection system) in SERS/HPTLC spot characterization. It permits the acquisition of Raman spectra from HPTLC spots down to 1 μm in size or other forms of microsamples approaching the picogram level in mass.

Surface Electrochemical Modification of a Nickel Substrate to Prepare a NiFe-based Electrode for Water Oxidation.

PubMed

Guo, Dingyi; Qi, Jing; Zhang, Wei; Cao, Rui

2017-01-20

The slow kinetics of water oxidation greatly jeopardizes the efficiency of water electrolysis for H 2 production. Developing highly active water oxidation electrodes with affordable fabrication costs is thus of great importance. Herein, a Ni II Fe III surface species on Ni metal substrate was generated by electrochemical modification of Ni in a ferrous solution by a fast, simple, and cost-effective procedure. In the prepared Ni II Fe III catalyst film, Fe III was incorporated uniformly through controlled oxidation of Fe II cations on the electrode surface. The catalytically active Ni II originated from the Ni foam substrate, which ensured the close contact between the catalyst and the support toward improved charge-transfer efficiency. The as-prepared electrode exhibited high activity and long-term stability for electrocatalytic water oxidation. The overpotentials required to reach water oxidation current densities of 50, 100, and 500 mA cm -2 are 276, 290, and 329 mV, respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biomass-derived functional porous carbons as novel electrode material for the practical detection of biomolecules in human serum and snail hemolymph.

PubMed

Veeramani, Vediyappan; Madhu, Rajesh; Chen, Shen-Ming; Lou, Bih-Show; Palanisamy, Jayabal; Vasantha, Vairathevar Sivasamy

2015-05-22

The biomass-derived activated carbons (ACs) have been prepared with high surface areas up to 793 m(2) g(-1) is by ZnCl2 activation at three different temperatures, viz. AC700, AC800, and AC900. The AC samples were characterized by a variety of analytical and spectroscopy techniques. The as-synthesized ACs were adopted for the simultaneous electrochemical detection of ascorbic acid (AA), dopamine (DA), and uric acid (UA). For comparison, reduced graphene oxide (RGO) was employed for the proposed sensor. The high surface area, modulated pore size and the presence of oxygen surface functional groups like heteroatoms (83.427% C, 1.085% N, 0.383% S, and 0.861% H) in the biomass-derived AC is found to be responsible for the excellent catalytic activities of biomolecules. Fascinatingly, the facile sensor further used to detect biomolecules levels in the snail hemolymph and human blood serum. Notably, the obtained analytical parameters for the biomolecules detection over the AC modified GCE, outperforming several carbon-based modified electrodes in literatures.

Biomass-derived functional porous carbons as novel electrode material for the practical detection of biomolecules in human serum and snail hemolymph

PubMed Central

Veeramani, Vediyappan; Madhu, Rajesh; Chen, Shen-Ming; Lou, Bih-Show; Palanisamy, Jayabal; Vasantha, Vairathevar Sivasamy

2015-01-01

The biomass-derived activated carbons (ACs) have been prepared with high surface areas up to 793 m2 g−1 is by ZnCl2 activation at three different temperatures, viz. AC700, AC800, and AC900. The AC samples were characterized by a variety of analytical and spectroscopy techniques. The as-synthesized ACs were adopted for the simultaneous electrochemical detection of ascorbic acid (AA), dopamine (DA), and uric acid (UA). For comparison, reduced graphene oxide (RGO) was employed for the proposed sensor. The high surface area, modulated pore size and the presence of oxygen surface functional groups like heteroatoms (83.427% C, 1.085% N, 0.383% S, and 0.861% H) in the biomass-derived AC is found to be responsible for the excellent catalytic activities of biomolecules. Fascinatingly, the facile sensor further used to detect biomolecules levels in the snail hemolymph and human blood serum. Notably, the obtained analytical parameters for the biomolecules detection over the AC modified GCE, outperforming several carbon-based modified electrodes in literatures. PMID:25998156

Biomass-derived functional porous carbons as novel electrode material for the practical detection of biomolecules in human serum and snail hemolymph

NASA Astrophysics Data System (ADS)

Veeramani, Vediyappan; Madhu, Rajesh; Chen, Shen-Ming; Lou, Bih-Show; Palanisamy, Jayabal; Vasantha, Vairathevar Sivasamy

2015-05-01

The biomass-derived activated carbons (ACs) have been prepared with high surface areas up to 793 m2 g-1 is by ZnCl2 activation at three different temperatures, viz. AC700, AC800, and AC900. The AC samples were characterized by a variety of analytical and spectroscopy techniques. The as-synthesized ACs were adopted for the simultaneous electrochemical detection of ascorbic acid (AA), dopamine (DA), and uric acid (UA). For comparison, reduced graphene oxide (RGO) was employed for the proposed sensor. The high surface area, modulated pore size and the presence of oxygen surface functional groups like heteroatoms (83.427% C, 1.085% N, 0.383% S, and 0.861% H) in the biomass-derived AC is found to be responsible for the excellent catalytic activities of biomolecules. Fascinatingly, the facile sensor further used to detect biomolecules levels in the snail hemolymph and human blood serum. Notably, the obtained analytical parameters for the biomolecules detection over the AC modified GCE, outperforming several carbon-based modified electrodes in literatures.

Synthesis of Platinum-nickel Nanowires and Optimization for Oxygen Reduction Performance.

PubMed

Alia, Shaun M; Pivovar, Bryan S

2018-04-27

Platinum-nickel (Pt-Ni) nanowires were developed as fuel cell electrocatalysts, and were optimized for the performance and durability in the oxygen reduction reaction. Spontaneous galvanic displacement was used to deposit Pt layers onto Ni nanowire substrates. The synthesis approach produced catalysts with high specific activities and high Pt surface areas. Hydrogen annealing improved Pt and Ni mixing and specific activity. Acid leaching was used to preferentially remove Ni near the nanowire surface, and oxygen annealing was used to stabilize near-surface Ni, improving durability and minimizing Ni dissolution. These protocols detail the optimization of each post-synthesis processing step, including hydrogen annealing to 250 °C, exposure to 0.1 M nitric acid, and oxygen annealing to 175 °C. Through these steps, Pt-Ni nanowires produced increased activities more than an order of magnitude than Pt nanoparticles, while offering significant durability improvements. The presented protocols are based on Pt-Ni systems in the development of fuel cell catalysts. These techniques have also been used for a variety of metal combinations, and can be applied to develop catalysts for a number of electrochemical processes.

Antiproliferative activity of Curcuma phaeocaulis Valeton extract using ultrasonic assistance and response surface methodology.

PubMed

Wang, Xiaoqin; Jiang, Ying; Hu, Daode

2017-01-02

The objective of the study was to optimize the ultrasonic-assisted extraction of curdione, furanodienone, curcumol, and germacrone from Curcuma phaeocaulis Valeton (Val.) and investigate the antiproliferative activity of the extract. Under the suitable high-performance liquid chromatography condition, the calibration curves for these four tested compounds showed high levels of linearity and the recoveries of these four compounds were between 97.9 and 104.3%. Response surface methodology (RSM) combining central composite design and desirability function (DF) was used to define optimal extraction parameters. The results of RSM and DF revealed that the optimum conditions were obtained as 8 mL g -1 for liquid-solid ratio, 70% ethanol concentration, and 20 min of ultrasonic time. It was found that the surface structures of the sonicated herbal materials were fluffy and irregular. The C. phaeocaulis Val. extract significantly inhibited the proliferation of RKO and HT-29 cells in vitro. The results reveal that the RSM can be effectively used for optimizing the ultrasonic-assisted extraction of bioactive components from C. phaeocaulis Val. for antiproliferative activity.

Electricity generation from real industrial wastewater using a single-chamber air cathode microbial fuel cell with an activated carbon anode.

PubMed

Mohamed, Hend Omar; Obaid, M; Sayed, Enas Taha; Liu, Yang; Lee, Jinpyo; Park, Mira; Barakat, Nasser A M; Kim, Hak Yong

2017-08-01

This study introduces activated carbon (AC) as an effective anode for microbial fuel cells (MFCs) using real industrial wastewater without treatment or addition of external microorganism mediators. Inexpensive activated carbon is introduced as a proper electrode alternative to carbon cloth and carbon paper materials, which are considered too expensive for the large-scale application of MFCs. AC has a porous interconnected structure with a high bio-available surface area. The large surface area, in addition to the high macro porosity, facilitates the high performance by reducing electron transfer resistance. Extensive characterization, including surface morphology, material chemistry, surface area, mechanical strength and biofilm adhesion, was conducted to confirm the effectiveness of the AC material as an anode in MFCs. The electrochemical performance of AC was also compared to other anodes, i.e., Teflon-treated carbon cloth (CCT), Teflon-treated carbon paper (CPT), untreated carbon cloth (CC) and untreated carbon paper (CP). Initial tests of a single air-cathode MFC display a current density of 1792 mAm -2 , which is approximately four times greater than the maximum value of the other anode materials. COD analyses and Coulombic efficiency (CE) measurements for AC-MFC show the greatest removal of organic compounds and the highest CE efficiency (60 and 71%, respectively). Overall, this study shows a new economical technique for power generation from real industrial wastewater with no treatment and using inexpensive electrode materials.

Self-organized TiO2 nanotube arrays in the photocatalytic degradation of methylene blue under UV light irradiation

NASA Astrophysics Data System (ADS)

Chung, Eun Hyuk; Baek, Seong Rim; Yu, Seong Mi; Kim, Jong Pil; Hong, Tae Eun; Kim, Hyun Gyu; Bae, Jong-Seong; Jeong, Euh Duck; Khan, F. Nawaz; Jung, Ok-sang

2015-04-01

Nanostructured titanium dioxide (NTiO2) is known to possess efficient photocatalytic activity and to have diverse applications in many fields due to its chemical stability, high surface area/volume ratio, high transmittance, and high refractive index in the visible and the near-ultraviolet regions. These facts prompted us to develop TiO2 nanotube (TiO2 NT) arrays through electrochemical anodic oxidation involving different electrolytes comprised of phosphoric acid — hydrofluoric acid aqueous systems by varying the voltage and the time. The annealing temperature of the nanotubes, TiO2 NTs, were varied to modify the surface morphology and were characterized by using X-ray diffraction and scanning electron microscopy. Scanning electron microscopy and X-ray diffraction results showed that the samples had uniform morphologies and good crystalline structures of the anatase phase at lower annealing temperatures and of the rutile phase at higher annealing temperatures. A secondary-ion mass-spectrometry analysis was used to investigate the surface atoms and to conduct a depth profile analysis of the TiO2 NTs. The efficiency of the photocatalytic activity of the TiO2 NT arrays in degrading methylene blue (MB) was investigated under UV-Vis light irradiation. The maximum photocatalytic activity was achieved for the samples with lower annealing temperatures due to their being in the anatase phase and having a higher surface area and a smaller crystal size, which play important roles in the degradation of organic pollutants.

Nickel hydroxide/cobalt-ferrite magnetic nanocatalyst for alcohol oxidation.

PubMed

Bhat, Pooja B; Inam, Fawad; Bhat, Badekai Ramachandra

2014-08-11

A magnetically separable, active nickel hydroxide (Brønsted base) coated nanocobalt ferrite catalyst has been developed for oxidation of alcohols. High surface area was achieved by tuning the particle size with surfactant. The surface area of 120.94 m2 g(-1) has been achieved for the coated nanocobalt ferrite. Improved catalytic activity and selectivity were obtained by synergistic effect of transition metal hydroxide (basic hydroxide) on nanocobalt ferrite. The nanocatalyst oxidizes primary and secondary alcohols efficiently (87%) to corresponding carbonyls in good yields.

Construction of titanium dioxide nanorod/graphite microfiber hybrid electrodes for a high performance electrochemical glucose biosensor

NASA Astrophysics Data System (ADS)

Zhang, Jian; Yu, Xin; Guo, Weibo; Qiu, Jichuan; Mou, Xiaoning; Li, Aixue; Liu, Hong

2016-04-01

The demand for a highly sensitive and selective glucose biosensor which can be used for implantable or on-time monitoring is constantly increasing. In this work, TiO2 nanorods were synthesized in situ on the surface of graphite microfibers to yield TiO2 nanorod/graphite microfiber hybrid electrodes. The TiO2 nanorods not only retain the high activity of the immobilized glucose molecule, but also promote the direct electron transfer process on the electrode surface. As a working electrode in an electrochemical glucose biosensor in a flowing system, the microfiber hybrid electrodes exhibit high sensitivity, selectivity and stability. Due to its simplicity, low cost, high stability, and unique morphology, the TiO2 nanorod/graphite microfiber hybrid electrode is expected to be an excellent candidate for an implantable biosensor or for in situ flow monitoring.The demand for a highly sensitive and selective glucose biosensor which can be used for implantable or on-time monitoring is constantly increasing. In this work, TiO2 nanorods were synthesized in situ on the surface of graphite microfibers to yield TiO2 nanorod/graphite microfiber hybrid electrodes. The TiO2 nanorods not only retain the high activity of the immobilized glucose molecule, but also promote the direct electron transfer process on the electrode surface. As a working electrode in an electrochemical glucose biosensor in a flowing system, the microfiber hybrid electrodes exhibit high sensitivity, selectivity and stability. Due to its simplicity, low cost, high stability, and unique morphology, the TiO2 nanorod/graphite microfiber hybrid electrode is expected to be an excellent candidate for an implantable biosensor or for in situ flow monitoring. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01360k

Solar Surface Velocity in the Large Scale estimated by Magnetic Element Tracking Method

NASA Astrophysics Data System (ADS)

Fujiyama, M.; Imada, S.; Iijima, H.; Machida, S.

2017-12-01

The 11years variation in the solar activity is one of the important sources of decadal variation in the solar-terrestrial environment. Therefore, predicting the solar cycle activity is crucial for the space weather. To build the prediction schemes for the next solar cycle is a key for the long-term space weather study. Recently, the relationship between polar magnetic field at the solar minimum and next solar cycle activity is intensively discussed. Nowadays, many people believe that the polar magnetic field at the solar minimum is one of the best predictor for the next solar cycle. To estimate polar magnetic field, Surface Flux Transport (SFT) model have been often used. On the other hand, SFT model needs several parameters, for example Meridional circulation, differential rotation, turbulent diffusion etc.. So far, those parameters have not been fully understood, and their uncertainties may affect the accuracy of the prediction. In this study, we try to discuss the parameters which are used in SFT model. We focus on two kinds of the solar surface motions, Differential rotation and Meridional circulation. First, we have developed Magnetic Element Tracking (MET) module, which is able to obtain the surface velocity by using the magnetic field data. We have used SOHO/MDI and SDO/HMI for the magnetic field data. By using MET, we study the solar surface motion over 2 cycle (nearly 24 years), and we found that the velocity variation is related to the active region belt. This result is consistent with [Hathaway et al., 2011]. Further, we apply our module to the Hinode/SOT data which spatial resolution is high. Because of its high resolution, we can discuss the surface motion close to the pole which has not been discussed enough. Further, we discuss the relationship between the surface motion and the magnetic field strength and the location of longitude.

Production of activated carbon from rice husk Vietnam

NASA Astrophysics Data System (ADS)

Korobochkin, V. V.; Tu, N. V.; Hieu, N. M.

2016-09-01

This work is dedicated to the production of activated carbon from rice husk from Delta of the Red River in Viet Nam. At the first stage, carbonization of a rice husk was carried out to obtain material containing 43.1% carbon and 25 % silica with a specific surface area of 51.5 m2/g. After separating of silica (the second stage), the specific surface area of the product increased to 204 m2/g and the silica content decreased to 1.23% by weight as well. The most important stage in the formation of the porous structure of the material is the activation. The products with the high specific surface area in the range of 800-1345 m2/g were obtained by activation of carbonized product with water vapour or carbon dioxide at temperatures of 700 °C and 850 °C, with varying the flow rate of the activating agent and activation time. The best results were achieved by activation of carbon material with water vapour at the flow rate of 0.08 dm3/min per 500 g of material and the temperature of 850 °C.

Block copolymer modified surfaces for conjugation of biomacromolecules with control of quantity and activity.

PubMed

Li, Xin; Wang, Mengmeng; Wang, Lei; Shi, Xiujuan; Xu, Yajun; Song, Bo; Chen, Hong

2013-01-29

Polymer brush layers based on block copolymers of poly(oligo(ethylene glycol) methacrylate) (POEGMA) and poly(glycidyl methacrylate) (PGMA) were formed on silicon wafers by activators generated by electron transfer atom transfer radical polymerization (AGET ATRP). Different types of biomolecule can be conjugated to these brush layers by reaction of PGMA epoxide groups with amino groups in the biomolecule, while POEGMA, which resists nonspecific protein adsorption, provides an antifouling environment. Surfaces were characterized by water contact angle, ellipsometry, and Fourier transform infrared spectroscopy (FTIR) to confirm the modification reactions. Phase segregation of the copolymer blocks in the layers was observed by AFM. The effect of surface properties on protein conjugation was investigated using radiolabeling methods. It was shown that surfaces with POEGMA layers were protein resistant, while the quantity of protein conjugated to the diblock copolymer modified surfaces increased with increasing PGMA layer thickness. The activity of lysozyme conjugated on the surface could also be controlled by varying the thickness of the copolymer layer. When biotin was conjugated to the block copolymer grafts, the surface remained resistant to nonspecific protein adsorption but showed specific binding of avidin. These properties, that is, well-controlled quantity and activity of conjugated biomolecules and specificity of interaction with target biomolecules may be exploited for the improvement of signal-to-noise ratio in sensor applications. More generally, such surfaces may be useful as biological recognition elements of high specificity for functional biomaterials.

Carborane-Based Metal-Organic Framework with High Methane and Hydrogen Storage Capacities

DTIC Science & Technology

2013-01-01

guest solvent molecules were removed via supercritical CO2 (see the Supporting Information for activation details),30,31 the samples were further...unique geometry of the carborane unit, NU-135 has a very high volumetric BET surface area of ca. 1900 m2/cm3. CH4, CO2 , and H2 adsorption isotherms...NU-135 has a very high volumetric BET surface area of ca. 1900 m2/cm3. CH4, CO2 , and H2 adsorption isotherms were measured over a broad range of

IV-VI compound midinfrared high-reflectivity mirrors and vertical-cavity surface-emitting lasers grown by molecular-beam epitaxy

NASA Astrophysics Data System (ADS)

Shi, Z.; Xu, G.; McCann, P. J.; Fang, X. M.; Dai, N.; Felix, C. L.; Bewley, W. W.; Vurgaftman, I.; Meyer, J. R.

2000-06-01

Midinfrared broadband high-reflectivity Pb1-xSrxSe/BaF2 distributed Bragg reflectors and vertical-cavity surface-emitting lasers (VCSELs) with PbSe as the active material were grown by molecular-beam epitaxy. Because of an extremely high index contrast, mirrors with only three quarter-wave layer pairs had reflectivities exceeding 99%. For pulsed optical pumping, a lead salt VCSEL emitting at the cavity wavelength of 4.5-4.6 μm operated nearly to room temperature (289 K).

Nonleachable Imidazolium-Incorporated Composite for Disruption of Bacterial Clustering, Exopolysaccharide-Matrix Assembly, and Enhanced Biofilm Removal.

PubMed

Hwang, Geelsu; Koltisko, Bernard; Jin, Xiaoming; Koo, Hyun

2017-11-08

Surface-grown bacteria and production of an extracellular polymeric matrix modulate the assembly of highly cohesive and firmly attached biofilms, making them difficult to remove from solid surfaces. Inhibition of cell growth and inactivation of matrix-producing bacteria can impair biofilm formation and facilitate removal. Here, we developed a novel nonleachable antibacterial composite with potent antibiofilm activity by directly incorporating polymerizable imidazolium-containing resin (antibacterial resin with carbonate linkage; ABR-C) into a methacrylate-based scaffold (ABR-modified composite; ABR-MC) using an efficient yet simplified chemistry. Low-dose inclusion of imidazolium moiety (∼2 wt %) resulted in bioactivity with minimal cytotoxicity without compromising mechanical integrity of the restorative material. The antibiofilm properties of ABR-MC were assessed using an exopolysaccharide-matrix-producing (EPS-matrix-producing) oral pathogen (Streptococcus mutans) in an experimental biofilm model. Using high-resolution confocal fluorescence imaging and biophysical methods, we observed remarkable disruption of bacterial accumulation and defective 3D matrix structure on the surface of ABR-MC. Specifically, the antibacterial composite impaired the ability of S. mutans to form organized bacterial clusters on the surface, resulting in altered biofilm architecture with sparse cell accumulation and reduced amounts of EPS matrix (versus control composite). Biofilm topology analyses on the control composite revealed a highly organized and weblike EPS structure that tethers the bacterial clusters to each other and to the surface, forming a highly cohesive unit. In contrast, such a structured matrix was absent on the surface of ABR-MC with mostly sparse and amorphous EPS, indicating disruption in the biofilm physical stability. Consistent with lack of structural organization, the defective biofilm on the surface of ABR-MC was readily detached when subjected to low shear stress, while most of the biofilm biomass remained on the control surface. Altogether, we demonstrate a new nonleachable antibacterial composite with excellent antibiofilm activity without affecting its mechanical properties, which may serve as a platform for development of alternative antifouling biomaterials.

The Extraordinary Albedo Variations on Pluto Detected by New Horizons and Implications for Dwarf Planet Eris

NASA Astrophysics Data System (ADS)

Buratti, Bonnie J.; Hofgartner, Jason D.; Stern, S. Alan; Weaver, Harold A.; Verbiscer, Anne J.; Ennico, Kimberly; Olkin, Catherine B.; Young, Leslie; New Horizons Geology and Geophysics Team

2016-10-01

The New Horizons mission returned stunning observations of active geology on the surface of Pluto (Stern et al., 2015, Science 350, 292). One of the markers for activity on planets or moons is normal albedos approaching 1.0, as is the case for Enceladus (Buratti et al., 1984, Icarus 58, 254; Verbiscer et al., 2005, Icarus 173, 66). When all corrections for viewing geometry are made for Pluto, it has normal albedos that approach unity in the regions that show evidence for activity by a lack of craters, notably the region informally named Sputnik Planum. On the other hand, Pluto also has a very dark (normal albedo ~0.10) equatorial belt.The geometric albedo of Eris, another large dwarf planet in the Kuiper Belt, is 0.96 (Sicardy et al., 2011, Nature 478, 493), close to that of Enceladus. Coupled with a high density of 2.5 gm/cc (Sicardy et al., ibid.), implying an even larger amount of radiogenic heating than that for Pluto (with a density near 1.9 gm/cc), we find it highly likely that Eris is also active with some type of solid state convection or cryovolcanism on its surface. Alternate explanations such as complete condensation of methane frost onto its surface in the colder environment at nearly 100 AUs would not lead to the high albedo observed.Another implication of the extreme albedo variations on Pluto is that the temperature varies by at least 20K on its surface, spawning possible aeolian processes and associated features such as wind streaks and dunes, which are currently being sought on New Horizons images. Finally, low albedo regions on Pluto, with normal reflectances less than 0.10, provide possible evidence for dust in the Kuiper Belt that is accreting onto the surface of Pluto. Another - or additional - explanation for this low-albedo dust is native material created in Pluto's hazy atmosphere.New Horizons funding by NASA is gratefully acknowledged.

Miniature Convection Cooled Plug-type Heat Flux Gauges

NASA Technical Reports Server (NTRS)

Liebert, Curt H.

1994-01-01

Tests and analysis of a new miniature plug-type heat flux gauge configuration are described. This gauge can simultaneously measure heat flux on two opposed active surfaces when heat flux levels are equal to or greater than about 0.2 MW/m(sup 2). The performance of this dual active surface gauge was investigated over a wide transient and steady heat flux and temperature range. The tests were performed by radiatively heating the front surface with an argon arc lamp while the back surface was convection cooled with air. Accuracy is about +20 percent. The gauge is responsive to fast heat flux transients and is designed to withstand the high temperature (1300 K), high pressure (15 MPa), erosive and corrosive environments in modern engines. This gauge can be used to measure heat flux on the surfaces of internally cooled apparatus such as turbine blades and combustors used in jet propulsion systems and on the surfaces of hypersonic vehicles. Heat flux measurement accuracy is not compromised when design considerations call for various size gauges to be fabricated into alloys of various shapes and properties. Significant gauge temperature reductions (120 K), which can lead to potential gauge durability improvement, were obtained when the gauges were air-cooled by forced convection.

Enhanced visible light photocatalytic property of red phosphorus via surface roughening

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

Li, Weibing, E-mail: lwbing@qust.edu.cn; Yue, Jiguang; Hua, Fangxia

Highlights: • Photocatalytic RhB degradation of red phosphorus was studied for the first time. • Surface rough can increase the photocatalysis reaction active sites. • Surface rough red phosphorus possesses high photocatalytic performance. • Surface rough red phosphorus has high industrial application value. - Abstract: Red phosphorus with rough surface (SRP) was prepared by catalyst-assisted hydrothermal synthesis using Co{sup 2+} catalyst. The photocatalytic Rhodamine B (RhB) degradation of red phosphorus (RP) and SRP was studied for the first time in this work. Rough surface can enhance the dye adsorption ability of RP. About 75% RhB was absorbed by SRP aftermore » 30-min adsorption in 100 ml RhB solution with concentration of 10 mg l{sup −1} in dark. After only 10 min of illumination by visible light, more than 95% RhB was degraded, indicating that SRP has a great application potential in the area of photocatalysis. The photocatalytic RhB degradation properties of RP are much weaker than those of SRP. The increase of the number of the active sites for the photocatalytic reactions, the electron mobility and the lifetime of the photogenerated electrons cause the significant improvement of the photocatalytic performance of SRP based on the experimental results obtained.« less

Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production [Chemical and phase evolution of amorphous molybdenum sulfide catalysts for electrochemical hydrogen production directly observed using environmental transmission electron microscopy

DOE PAGES

Lee, Sang Chul; Benck, Jesse D.; Tsai, Charlie; ...

2015-12-01

Amorphous MoS x is a highly active, earth-abundant catalyst for the electrochemical hydrogen evolution reaction. Previous studies have revealed that this material initially has a composition of MoS 3, but after electrochemical activation, the surface is reduced to form an active phase resembling MoS 2 in composition and chemical state. However, structural changes in the Mo Sx catalyst and the mechanism of the activation process remain poorly understood. In this study, we employ transmission electron microscopy (TEM) to image amorphous MoS x catalysts activated under two hydrogen-rich conditions: ex situ in an electrochemical cell and in situ in an environmentalmore » TEM. For the first time, we directly observe the formation of crystalline domains in the MoS x catalyst after both activation procedures as well as spatially localized changes in the chemical state detected via electron energy loss spectroscopy. Using density functional theory calculations, we investigate the mechanisms for this phase transformation and find that the presence of hydrogen is critical for enabling the restructuring process. Our results suggest that the surface of the amorphous MoS x catalyst is dynamic: while the initial catalyst activation forms the primary active surface of amorphous MoS 2, continued transformation to the crystalline phase during electrochemical operation could contribute to catalyst deactivation. Finally, these results have important implications for the application of this highly active electrocatalyst for sustainable H 2 generation.« less

The Europa Imaging System (EIS): High-Resolution, 3-D Insight into Europa's Geology, Ice Shell, and Potential for Current Activity

NASA Astrophysics Data System (ADS)

Turtle, E. P.; McEwen, A. S.; Collins, G. C.; Fletcher, L. N.; Hansen, C. J.; Hayes, A.; Hurford, T., Jr.; Kirk, R. L.; Barr, A.; Nimmo, F.; Patterson, G.; Quick, L. C.; Soderblom, J. M.; Thomas, N.

2015-12-01

The Europa Imaging System will transform our understanding of Europa through global decameter-scale coverage, three-dimensional maps, and unprecedented meter-scale imaging. EIS combines narrow-angle and wide-angle cameras (NAC and WAC) designed to address high-priority Europa science and reconnaissance goals. It will: (A) Characterize the ice shell by constraining its thickness and correlating surface features with subsurface structures detected by ice penetrating radar; (B) Constrain formation processes of surface features and the potential for current activity by characterizing endogenic structures, surface units, global cross-cutting relationships, and relationships to Europa's subsurface structure, and by searching for evidence of recent activity, including potential plumes; and (C) Characterize scientifically compelling landing sites and hazards by determining the nature of the surface at scales relevant to a potential lander. The NAC provides very high-resolution, stereo reconnaissance, generating 2-km-wide swaths at 0.5-m pixel scale from 50-km altitude, and uses a gimbal to enable independent targeting. NAC observations also include: near-global (>95%) mapping of Europa at ≤50-m pixel scale (to date, only ~14% of Europa has been imaged at ≤500 m/pixel, with best pixel scale 6 m); regional and high-resolution stereo imaging at <1-m/pixel; and high-phase-angle observations for plume searches. The WAC is designed to acquire pushbroom stereo swaths along flyby ground-tracks, generating digital topographic models with 32-m spatial scale and 4-m vertical precision from 50-km altitude. These data support characterization of cross-track clutter for radar sounding. The WAC also performs pushbroom color imaging with 6 broadband filters (350-1050 nm) to map surface units and correlations with geologic features and topography. EIS will provide comprehensive data sets essential to fulfilling the goal of exploring Europa to investigate its habitability and perform collaborative science with other investigations, including cartographic and geologic maps, regional and high-resolution digital topography, GIS products, color and photometric data products, a geodetic control network tied to radar altimetry, and a database of plume-search observations.

Development of advanced micromirror arrays by flip-chip assembly

NASA Astrophysics Data System (ADS)

Michalicek, M. Adrian; Bright, Victor M.

2001-10-01

This paper presents the design, commercial prefabrication, modeling and testing of advanced micromirror arrays fabricated using a novel, simple and inexpensive flip-chip assembly technique. Several polar piston arrays and rectangular cantilever arrays were fabricated using flip-chip assembly by which the upper layers of the array are fabricated on a separate chip and then transferred to a receiving module containing the lower layers. Typical polar piston arrays boast 98.3% active surface area, highly planarized surfaces, low address potentials compatible with CMOS electronics, highly standardized actuation between devices, and complex segmentation of mirror surfaces which allows for custom aberration configurations. Typical cantilever arrays boast large angles of rotation as well as an average surface planarity of only 1.779 nm of RMS roughness across 100 +m mirrors. Continuous torsion devices offer stable operation through as much as six degrees of rotation while binary operation devices offer stable activated positions with as much as 20 degrees of rotation. All arrays have desirable features of costly fabrication services like five structural layers and planarized mirror surfaces, but are prefabricated in the less costly MUMPs process. Models are developed for all devices and used to compare empirical data.

Analysis and Modeling of Boundary Layer Separation Method (BLSM).

PubMed

Pethő, Dóra; Horváth, Géza; Liszi, János; Tóth, Imre; Paor, Dávid

2010-09-01

Nowadays rules of environmental protection strictly regulate pollution material emission into environment. To keep the environmental protection laws recycling is one of the useful methods of waste material treatment. We have developed a new method for the treatment of industrial waste water and named it boundary layer separation method (BLSM). We apply the phenomena that ions can be enriched in the boundary layer of the electrically charged electrode surface compared to the bulk liquid phase. The main point of the method is that the boundary layer at correctly chosen movement velocity can be taken out of the waste water without being damaged, and the ion-enriched boundary layer can be recycled. Electrosorption is a surface phenomenon. It can be used with high efficiency in case of large electrochemically active surface of electrodes. During our research work two high surface area nickel electrodes have been prepared. The value of electrochemically active surface area of electrodes has been estimated. The existence of diffusion part of the double layer has been experimentally approved. The electrical double layer capacity has been determined. Ion transport by boundary layer separation has been introduced. Finally we have tried to estimate the relative significance of physical adsorption and electrosorption.

A Combined Omics Approach to Generate the Surface Atlas of Human Naive CD4+ T Cells during Early T-Cell Receptor Activation*

PubMed Central

Graessel, Anke; Hauck, Stefanie M.; von Toerne, Christine; Kloppmann, Edda; Goldberg, Tatyana; Koppensteiner, Herwig; Schindler, Michael; Knapp, Bettina; Krause, Linda; Dietz, Katharina; Schmidt-Weber, Carsten B.; Suttner, Kathrin

2015-01-01

Naive CD4+ T cells are the common precursors of multiple effector and memory T-cell subsets and possess a high plasticity in terms of differentiation potential. This stem-cell-like character is important for cell therapies aiming at regeneration of specific immunity. Cell surface proteins are crucial for recognition and response to signals mediated by other cells or environmental changes. Knowledge of cell surface proteins of human naive CD4+ T cells and their changes during the early phase of T-cell activation is urgently needed for a guided differentiation of naive T cells and may support the selection of pluripotent cells for cell therapy. Periodate oxidation and aniline-catalyzed oxime ligation technology was applied with subsequent quantitative liquid chromatography-tandem MS to generate a data set describing the surface proteome of primary human naive CD4+ T cells and to monitor dynamic changes during the early phase of activation. This led to the identification of 173 N-glycosylated surface proteins. To independently confirm the proteomic data set and to analyze the cell surface by an alternative technique a systematic phenotypic expression analysis of surface antigens via flow cytometry was performed. This screening expanded the previous data set, resulting in 229 surface proteins, which were expressed on naive unstimulated and activated CD4+ T cells. Furthermore, we generated a surface expression atlas based on transcriptome data, experimental annotation, and predicted subcellular localization, and correlated the proteomics result with this transcriptional data set. This extensive surface atlas provides an overall naive CD4+ T cell surface resource and will enable future studies aiming at a deeper understanding of mechanisms of T-cell biology allowing the identification of novel immune targets usable for the development of therapeutic treatments. PMID:25991687

Twin defects engineered Pd cocatalyst on C3N4 nanosheets for enhanced photocatalytic performance in CO2 reduction reaction

NASA Astrophysics Data System (ADS)

Lang, Qingqing; Hu, Wenli; Zhou, Penghui; Huang, Tianlong; Zhong, Shuxian; Yang, Lining; Chen, Jianrong; Bai, Song

2017-12-01

Photocatalytic conversion of CO2 to value-added chemicals, a potential route to addressing the depletion of fossil fuels and anthropogenic climate change, is greatly limited by the low-efficient semiconductor photocatalyst. The integration of cocatalyst with light-harvesting semiconductor is a promising approach to enhancing the photocatalytic performance in CO2 reduction reaction. The enhancement is greatly determined by the catalytic active sites on the surface of cocatalyst. Herein, we demonstrate that the photocatalytic performance in the CO2 reduction reaction is greatly promoted by twin defects engineered Pd cocatalyst. In this work, Pd nanoicosahedrons with twin defects were in situ grown on C3N4 nanosheets, which effectively improve the photocatalytic performance in reduction of CO2 to CO and CH4 in comparison with Pd nanotetrahedrons without twin defects. It is proposed that the twin boundary (TB) terminations on the surface of Pd cocatalysts are highly catalytic active sites for CO2 reduction reaction. Based on the proposed mechanism, the photocatalytic activity and selectivity in CO2 reduction were further advanced through reducing the size of Pd icosahedral cocatalyst resulted from the increased surface density of TB terminations. The defect engineering on the surface of cocatalyst represents a novel route in realizing high-performance photocatalytic applications.

Featured Image: Active Cryovolcanism on Europa?

NASA Astrophysics Data System (ADS)

Kohler, Susanna

2017-05-01

Nighttime thermal image from the Galileo Photopolarimeter-Radiometer, revealing a thermal anomaly around the region where the plumes were observed. [Sparks et al. 2017]This image shows a 1320 900 km, high-resolution Galileo/Voyager USGS map of the surface of Europa, one of Jupiters moons. In March 2014, observations of Europa revealed a plume on its icy surface coming from somewhere within the green ellipse. In February 2016, another plume was observed, this time originating from somewhere within the cyan ellipse. In addition, a nighttime thermal image from the Galileo Photopolarimeter-Radiometer has revealed a thermal anomaly a region of unusually high temperature near the same location. In a recent study led by William Sparks (Space Telescope Science Institute), a team of scientists presents these observations and argues that they provide mounting evidence of active water-vapor venting from ongoing cryovolcanism beneath Europas icy surface. If this is true, then Europas surface is active and provides access to the liquid water at depth boosting the case for Europas potential habitability and certainly making for an interesting target point for future spacecraft exploration of this moon. For more information, check out the paper below!CitationW. B. Sparks et al 2017 ApJL 839 L18. doi:10.3847/2041-8213/aa67f8

Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites

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

Hensley, Alyssa J. R.; Wang, Yong; Mei, Donghai

A mechanistic understanding of the roles of water is essential for developing highly active and selective catalysts for hydrodeoxygenation (HDO) reactions since water is ubiquitous in such reaction systems. Here, we present a study for phenol HDO on Fe catalysts using density functional theory which examines the effect of water on three elementary pathways for phenol HDO using an explicit solvation model. The presence of water is found to significantly decrease activation barriers required by hydrogenation reactions via two pathways. First, the proton transfer in the hydrogen bonding network of the liquid water phase is nearly barrierless, which significantly promotesmore » the direct through space tautomerization of phenol. Second, due to the high degree of oxophilicity on Fe, liquid water molecules are found to be easily dissociated into surface hydroxyl groups that can act as Brønsted acid sites. These sites dramatically promote hydrogenation reactions on the Fe surface. As a result, the hydrogen assisted dehydroxylation becomes the dominant phenol HDO pathway. This work provides new fundamental insights into aqueous phase HDO of biomass-derived oxygenates over Fe-based catalysts; e.g., the activity of Fe-based catalysts can be optimized by tuning the surface coverage of Brønsted acid sites via surface doping.« less

Experimental and QSAR study on the surface activities of alkyl imidazoline surfactants

NASA Astrophysics Data System (ADS)

Kong, Xiangjun; Qian, Chengduo; Fan, Weiyu; Liang, Zupei

2018-03-01

15 alkyl imidazoline surfactants with different structures were synthesized and their critical micelle concentration (CMC) and surface tension under the CMC (σcmc) in aqueous solution were measured at 298 K. 54 kinds of molecular structure descriptors were selected as independent variables and the quantitative structure-activity relationship (QSAR) between surface activities of alkyl imidazoline and molecular structure were built through the genetic function approximation (GFA) method. Experimental results showed that the maximum surface excess of alkyl imidazoline molecules at the gas-liquid interface increased and the area occupied by each surfactant molecule and the free energies of micellization ΔGm decreased with increasing carbon number (NC) of the hydrophobic chain or decreasing hydrophilicity of counterions, which resulted in a CMC and σcmc decrease, while the log CMC and NC had a linear relationship and a negative correlation. The GFA-QSAR model, which was generated by a training set composed of 13 kinds of alkyl imidazoline though GFA method regression analysis, was highly correlated with predicted values and experimental values of the CMC. The correlation coefficient R was 0.9991, which means high prediction accuracy. The prediction error of 2 kinds of alkyl imidazoline CMCs in the Validation Set that quantitatively analyzed the influence of the alkyl imidazoline molecular structure on the CMC was less than 4%.

Twin defects engineered Pd cocatalyst on C3N4 nanosheets for enhanced photocatalytic performance in CO2 reduction reaction.

PubMed

Lang, Qingqing; Hu, Wenli; Zhou, Penghui; Huang, Tianlong; Zhong, Shuxian; Yang, Lining; Chen, Jianrong; Bai, Song

2017-12-01

Photocatalytic conversion of CO 2 to value-added chemicals, a potential route to addressing the depletion of fossil fuels and anthropogenic climate change, is greatly limited by the low-efficient semiconductor photocatalyst. The integration of cocatalyst with light-harvesting semiconductor is a promising approach to enhancing the photocatalytic performance in CO 2 reduction reaction. The enhancement is greatly determined by the catalytic active sites on the surface of cocatalyst. Herein, we demonstrate that the photocatalytic performance in the CO 2 reduction reaction is greatly promoted by twin defects engineered Pd cocatalyst. In this work, Pd nanoicosahedrons with twin defects were in situ grown on C 3 N 4 nanosheets, which effectively improve the photocatalytic performance in reduction of CO 2 to CO and CH 4 in comparison with Pd nanotetrahedrons without twin defects. It is proposed that the twin boundary (TB) terminations on the surface of Pd cocatalysts are highly catalytic active sites for CO 2 reduction reaction. Based on the proposed mechanism, the photocatalytic activity and selectivity in CO 2 reduction were further advanced through reducing the size of Pd icosahedral cocatalyst resulted from the increased surface density of TB terminations. The defect engineering on the surface of cocatalyst represents a novel route in realizing high-performance photocatalytic applications.

A Comparative Study of Molecular Structure, pKa, Lipophilicity, Solubility, Absorption and Polar Surface Area of Some Antiplatelet Drugs.

PubMed

Remko, Milan; Remková, Anna; Broer, Ria

2016-03-19

Theoretical chemistry methods have been used to study the molecular properties of antiplatelet agents (ticlopidine, clopidogrel, prasugrel, elinogrel, ticagrelor and cangrelor) and several thiol-containing active metabolites. The geometries and energies of most stable conformers of these drugs have been computed at the Becke3LYP/6-311++G(d,p) level of density functional theory. Computed dissociation constants show that the active metabolites of prodrugs (ticlopidine, clopidogrel and prasugrel) and drugs elinogrel and cangrelor are completely ionized at pH 7.4. Both ticagrelor and its active metabolite are present at pH = 7.4 in neutral undissociated form. The thienopyridine prodrugs ticlopidine, clopidogrel and prasugrel are lipophilic and insoluble in water. Their lipophilicity is very high (about 2.5-3.5 logP values). The polar surface area, with regard to the structurally-heterogeneous character of these antiplatelet drugs, is from very large interval of values of 3-255 Ų. Thienopyridine prodrugs, like ticlopidine, clopidogrel and prasugrel, with the lowest polar surface area (PSA) values, exhibit the largest absorption. A high value of polar surface area (PSA) of cangrelor (255 Ų) results in substantial worsening of the absorption in comparison with thienopyridine drugs.

A Comparative Study of Molecular Structure, pKa, Lipophilicity, Solubility, Absorption and Polar Surface Area of Some Antiplatelet Drugs

PubMed Central

Remko, Milan; Remková, Anna; Broer, Ria

2016-01-01

Theoretical chemistry methods have been used to study the molecular properties of antiplatelet agents (ticlopidine, clopidogrel, prasugrel, elinogrel, ticagrelor and cangrelor) and several thiol-containing active metabolites. The geometries and energies of most stable conformers of these drugs have been computed at the Becke3LYP/6-311++G(d,p) level of density functional theory. Computed dissociation constants show that the active metabolites of prodrugs (ticlopidine, clopidogrel and prasugrel) and drugs elinogrel and cangrelor are completely ionized at pH 7.4. Both ticagrelor and its active metabolite are present at pH = 7.4 in neutral undissociated form. The thienopyridine prodrugs ticlopidine, clopidogrel and prasugrel are lipophilic and insoluble in water. Their lipophilicity is very high (about 2.5–3.5 logP values). The polar surface area, with regard to the structurally-heterogeneous character of these antiplatelet drugs, is from very large interval of values of 3–255 Å2. Thienopyridine prodrugs, like ticlopidine, clopidogrel and prasugrel, with the lowest polar surface area (PSA) values, exhibit the largest absorption. A high value of polar surface area (PSA) of cangrelor (255 Å2) results in substantial worsening of the absorption in comparison with thienopyridine drugs. PMID:27007371